RU2648769C1 - Bronze color product with hybrid energy-saving coating on glass substrate - Google Patents

Abstract

FIELD: manufacturing technology.

SUBSTANCE: invention relates to products of bronze color with a hybrid energy-saving coating. Multilayer coating comprises layers in the following order from the surface of the glass substrate: the first layer of titanium dioxide TiO2; the first contact layer of Zn-Al-O; the first layer of silver Ag, reflecting infrared radiation; the first cover layer of Zn-Al-O; an intermediate layer of Zn-Sn-O; a second contact layer of Zn-Al-O; the second layer of silver Ag, reflecting infrared radiation; Zn-Al-O layer, which is the second cover layer; outer layer of Zn-Sn-O to protect the entire previously listed layer structure. Thickness of the intermediate layer Zn-Sn-O is from 50 to 75 nm, the thickness of the TiO2 layer is from 25 to 37 nm. Ratio of the thickness of the TiO2 layer to the thickness of the outer protective layer Zn-Sn-O is in the range from 0.6 to 1.3. Cumulative thickness of the two infrared-reflecting layers containing silver Ag is such that the resulting surface ohmic resistance of the product with the hybrid energy-saving coating does not exceed 4 Ω/□(square). Ratio of the thickness of the first layer of silver Ag to the thickness of the second layer of silver Ag is from 1.1 to 1.4. Ratio of the thickness of the first Zn-Al-O covering layer to the thickness of the first Zn-Al-O contact layer and the ratio of the thickness of the second Zn-Al-O coating layer to the thickness of the second Zn-Al-O contact layer are equal to and not more than 0.585.

EFFECT: reduction in the coefficient of direct transmission of solar radiation, a decrease in radiative heat losses during cold weather, increased light transparency, reduced transmission of ultraviolet radiation of near UV part of the spectrum.

1 cl, 2 dwg

Description

The present invention relates to energy-saving coatings, in particular to energy-saving coatings located on glass substrates, and having hybrid qualities of energy efficiency in combination with a bronze color as a means of architectural expression.

Thin-film optical coatings are applied to optically transparent substrates to change the intensity of the electromagnetic radiation coming from them of a particular wavelength range due to, for example, its total or partial absorption or reflection. Thus, conductive optical coatings, that is, coatings containing at least one metal layer with a low emissivity, are intended to attenuate the transmission of infrared radiation. Currently, they are widely used as coatings applied to the surface of sheet architectural glass and glasses used in the construction of various vehicles and serve to reduce heat loss and control the influx of electromagnetic radiation from external sources, including solar radiation, as a full spectrum , and its individual selected ranges. Optical coatings typically include two or more different layers, each of which has a thickness in the range from less than 1 to more than 500 nm.

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

Thin-film deposition products on a glass substrate are also known, the coating composition of which includes several metal layers separated by ceramic layers, described, for example, in RF patent No. 2415968. Such products, often called highly selective, in addition to a reduced emissivity, compared to ordinary silicate glass, also have a low SHGC coefficient of solar heat gain, due to a decrease in the transmission of electromagnetic radiation throughout the 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 fall to the radiation coating. And although translucent structures using these products, in addition to reducing heat loss from the room to the street during the cold season, associated with the mechanism of transfer of thermal energy by radiation, also provide a reduction in the intensity of excess direct thermal solar radiation into the room, such products, however, have a reduced ratio to low-emission products of thin-film deposition on a glass substrate with a transmission coefficient of electromagnetic radiation of visible wavelengths, which camping on their reduced energy efficiency from the point of view of the optimal use of daylight, especially in countries with cold climates, allowing to provide additional power savings consumed for domestic interior lighting. In addition, these products, along with the low-emission products of thin-film deposition on a glass substrate, do not generally have a reduced direct transmission in the near long-wavelength region of the ultraviolet part of the electromagnetic spectrum, which is responsible for the part of the ultraviolet radiation that is not absorbed by the glass mass of the glass substrate, which leads to to fading of coatings and fabrics of interior items, and thus do not provide the desired for energy-efficient oduktov thin film deposition, used in the context of large-translucent building constructions described properties prevent leakage effect when using them.

The described coatings may have, in combination with the specified energy efficiency properties and / or transmission parameters, additional aesthetic qualities necessary from the point of view 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 spraying on a glass substrate can serve as coatings described in RF patents No. 2563527 and US No. 7166359. Often, however, the variety of shades of known products in combination with their level of direct transmission of sunlight in the visible wavelength range does not meet the needs of the current state of the architectural industry, especially in the case of highly selective products, the choice of products with a saturated highlighted color of the outdoor (from the room to the street) reflection among which is currently extremely limited. In particular, there is a need to implement a product with the so-called “bronze” tint of external reflection of the glass substrate surface from the side opposite to the deposited energy-efficient thin-film optical coating, and characterized by the following reflection tint parameters in color quasicoordinates a * / b * of the international CEILAB standard ( D65 / 10 °): a * from +6.8 to +10.8, and b * from +17.6 to +21.6.

Currently, in this area there is a need for a product coated on a glass substrate with hybrid qualities, expressed in the total implementation in it of a combination of predetermined sun-protection properties with respect to excessive solar thermal effects, energy efficiency qualities from the point of view of reducing radiative heat losses in cold weather, increased translucency with respect to the wavelengths of the visible part of the solar electromagnetic spectrum, a reduced level of direct transmission of ultraviolet radiation ovogo emission wavelength near UV portion of the solar spectrum and the desired bronze colored reflection from the glass surface of the substrate opposite the side on which the thin film coated optical energy efficient coating.

The closest to the claimed solution for the totality of features is RF patent No. 2563527, which describes a product with an energy-saving bronze-colored coating, including one reflective IR radiation layer, 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 bronze reflective color of the glass surface in combination with the specified sun-protection 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 *.

However, this product does not allow, along with a reduction in radiative heat loss from the room during the cold season and a bronze hue of external reflection, to achieve hybrid energy-efficiency qualities, namely, additional combined provision of sun protection with respect to excessive thermal solar exposure, increased translucency with respect to wavelengths the visible part of the solar electromagnetic spectrum, as well as a reduced level of direct transmission of ultraviolet radiation days of the long-wave UV part of the spectrum of solar radiation.

, повышенной светопрозрачности по отношению к длинам волн видимой части солнечного электромагнитного спектра, характеризуемой коэффициентом пропускания видимого излучения T_vis, составляющим не менее 60%, и сниженного уровня прямого пропускания ультрафиолетового излучения ближней длинноволновой УФ-части спектра солнечного излучения по сравнению с прозрачной стеклянной подложкой без дополнительного тонкопленочного энергосберегающего оптического покрытия, характеризуемого коэффициентом пропускания ультрафиолетового излучения T_uv, составляющим не более 70%.The technical result of the present invention is directed to providing a bronze color reflecting the surface of the glass substrate of the energy-saving coating from the side opposite to the side on which the thin-film energy-efficient optical coating is applied, characterized by the following reflection hue parameters in color quasicoordinates a * / b * of the international standard CEILAB (D65 / 10 ° ): a * from +6.8 to +10.8, and b * from +17.6 to +21.6, along with hybrid qualities of energy efficiency, expressed in the combined combination of the following properties: solar properties with respect to excessive thermal solar exposure, characterized by a direct solar transmission coefficient T _{sol of} not more than 44%, energy efficiency qualities from the point of view of reducing radiative heat loss in the cold, corresponding to the emissivity of the product, specified by the surface ohmic resistance of the thin-film coating, not exceeding 4

, increased translucency with respect to the wavelengths of the visible part of the solar electromagnetic spectrum, characterized by a transmittance of visible radiation T _{vis of} at least 60%, and a reduced level of direct transmission of ultraviolet radiation from the near long-wave UV portion of the solar spectrum compared to a transparent glass substrate without additional energy saving thin film optical coating, characterized by the ultraviolet radiation transmittance T _uv, leaving no more than 70%.

The technical result is achieved by the fact that a bronze-colored product with a hybrid energy-saving coating on a glass substrate is proposed, including a multilayer coating that contains directly contacting layers in the following order from the surface of the glass substrate:

the first layer adjacent to the surface of the glass substrate contains titanium dioxide TiO ₂ ,

a subsequent layer, which is the first contact layer, which contains aluminum oxide doped zinc Zn-Al-O,

followed by a layer containing Ag silver, which is the first layer reflecting infrared radiation,

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

followed by an intermediate layer containing zinc doped tin oxide Zn-Sn-O,

the subsequent layer is the second contact layer and contains aluminum oxide doped zinc Zn-Al-O,

it is followed by a layer containing silver Ag, which is the second layer reflecting infrared radiation,

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

then an outer layer follows to protect the entire previously listed layer structure containing zinc doped tin oxide Zn-Sn-O,

, причем отношение толщины первого слоя, отражающего инфракрасное излучение, содержащего серебро Ag, к толщине второго слоя, отражающего инфракрасное излучение, содержащего серебро Ag, составляет от 1,1 до 1,4, при этом отношение толщины первого укрывного слоя, который содержит оксид легированного алюминием цинка Zn-Al-O, к толщине первого контактного слоя, содержащего оксид легированного алюминием цинка Zn-Al-O, и отношение толщины второго укрывного слоя, который содержит оксид легированного алюминием цинка Zn-Al-O, к толщине второго контактного слоя, содержащего оксид легированного алюминием цинка Zn-Al-O, равны и составляют не более 0,585.the thickness of the intermediate layer containing zinc doped tin oxide Zn-Sn-O is from 50 to 75 nm, and the thickness of the layer containing titanium dioxide TiO ₂ is from 25 to 37 nm, while the ratio of the thickness of the layer containing titanium dioxide TiO ₂ , to the thickness of the outer protective layer containing zinc oxide doped with tin Zn-Sn-O, is in the range from 0.6 to 1.3, in addition, the total thickness of the two infrared reflective layers containing silver Ag is such that the resulting surface ohmic resistance of the product with bending energy-saving coating does not exceed 4

moreover, the ratio of the thickness of the first layer reflecting infrared radiation containing silver Ag to the thickness of the second layer reflecting infrared radiation containing silver Ag is from 1.1 to 1.4, while the ratio of the thickness of the first covering layer that contains doped oxide Zn-Al-O zinc aluminum to the thickness of the first contact layer containing Zn-Al-O zinc oxide and the ratio of the thickness of the second covering layer, which contains Zn-Al-O zinc oxide, to the thickness of the second contact layer containing aluminum oxide doped with zinc Zn-Al-O, are equal and are not more than 0.585.

In addition, in a particular case, it is proposed to connect the glass substrate with a multilayer coating deposited on its surface with at least one additional transparent substrate that faces the outer coating layer containing zinc doped tin oxide Zn-Sn-O.

. Осаждение тонкопленочного слоя в виде стехиометрического диоксида титана TiO₂ со стехиометрическим индексом 2 необходимо для поддержания коэффициента преломления осаждаемого слоя, равного n=2,3, что, в свою очередь, приводит к проявлению слоем т.н. "эффекта просветления", когда отражающую поверхность покрывают неотражающей пленкой для расщепления луча приходящего излучения за счет того, что поглощение света в пленке очень мало по сравнению с полупрозрачными слоями последующего осаждаемого тонкопленочного металла (в данном случае слоями отражающего ИК-излучения серебра Ag), в результате чего становится возможным в дальнейшем свести к минимуму искажение расщепленного луча при прохождении барьерного слоя металла и добиться желаемой повышенной светопрозрачности изделия по отношению к длинам волн видимой части солнечного спектра электромагнитного излучения. Наконец, экспериментально было показано, что использование именно титана в качестве одиночной металлической компоненты первого, прилегающего к поверхности стеклянной подложки слоя, проявляющего ПРТ качества, из всей группы подходящих металлов, состоящей из Ti, Si, Zn, Sn, In, Zr, Al, Cr, Nb, Mo, Hf, Та и W, способствует дополнительному формированию наиболее устойчивых связей с последующеим осаждаемым первым контактным слоем, содержащим оксид легированного алюминием цинка Zn-Al-O, причины выбора которого в качестве первого контактного слоя и необходимость в использовании его как слоя в целом приведены ниже. Последнее обеспечивает поддержание высокого уровня адгезии на границе индивидуальных слоев тонкопленочного покрытия изделия, что необходимо для обеспечения его структурной целостности и механической устойчивости к внешним воздействиям в ходе использования.The use of stoichiometric titanium dioxide TiO ₂ as the first layer of a hybrid energy-saving coating is due to the combination of the qualities listed below, manifested by this material, and the requirements for the qualities, shown 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 “cross-linking” effect with short-range crystalline precipitates of the quasi-amorphous structure of the glass melt through free chemical bonds of oxygen atoms with the formation of predominantly covalent polar bonds, which is necessary to ensure reliable retention of subsequent deposited layers on the surface of the substrate. In addition, titanium dioxide TiO ₂ belongs to the group of materials that contribute to preventing crack propagation (PRT), consisting of metal oxides 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 the propagation of cracks in the brittle, glassy outer layer of various optical coatings during industrial post-processing for the manufacture of glass units. 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 infrared reflecting layers containing silver Ag, which allows to achieve the desired qualities of sun protection with respect to excessive thermal solar exposure, as well as energy efficiency qualities with point of view of reducing radiative heat loss in cold weather, corresponding to the value of emissivity and products specified by the surface ohmic resistance of a thin-film coating not exceeding 4

. The deposition of a thin film layer in the form of stoichiometric titanium dioxide TiO ₂ with a stoichiometric index of 2 is necessary to maintain the refractive index of the deposited layer equal to n = 2.3, which, in turn, leads to the manifestation of the so-called layer. the “bleaching effect”, when the reflective surface is coated with a non-reflective film to split the incoming radiation beam due to the fact that the absorption of light in the film is very small compared to the translucent layers of the subsequent deposited thin-film metal (in this case, the layers of reflecting infrared silver Ag), as a result of which it becomes possible in the future to minimize the distortion of the split beam during the passage of the metal barrier layer and to achieve the desired increased translucency of the product by the ratio th to the wavelengths of the visible part of the solar spectrum of electromagnetic radiation. Finally, it was experimentally shown that the use of precisely titanium as a single metal component of the first layer adjacent to the surface of the glass substrate exhibiting PST quality from the entire group of suitable metals consisting of Ti, Si, 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 aluminum oxide doped zinc Zn-Al-O, the reasons for choosing which as the first contact layer and the need in using it as a layer as a whole 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 product, which is necessary to ensure its structural integrity and mechanical resistance to external influences during use.

, за счет структурной однородности отражающего ИК-излучение электропроводящего слоя серебра Ag в силу сопутствующей минимизации паразитного сопротивления на границах кристаллических конгломератов тонкопленочного серебряного слоя с катализируемым контактным слоем Zn-Al-O, снижением количества последних. В данную группу материалов входят биметалические оксиды цинка Zn, легированного элементом группы легких металлов, таких как алюминий Al и олово Sn. Также, альтернативно, возможно использовать в качестве контактного слоя биметаллические оксиды сплавов индия In, легированного элементом группы легких металлов, таких как алюминий Al или олово Sn. Однако эмпирически было выявлено, что только использование в качестве контактного отражающему ИК-излучение слою серебра Ag тонкопленочного слоя оксида легированного алюминием цинка Zn-Al-O из всей группы перечисленных материалов позволяет, помимо достижения указанных качеств, добиться препятствованию экстинкции электропроводящих металлических слоев покрытия, при одновременном уменьшении их толщины, в результате чего становится достижимым обеспечение повышенной светопрозрачности изделия по отношению к длинам волн видимой части солнечного электромагнитного спектра за счет снижения поглощения в данном диапазоне длин волн на электропроводящих металлических слоях, при одновременном, необходимом согласно постановке решаемой настоящим изобретением технической задачи сохранении качеств изделия, выраженных в совокупном сочетании следующих свойств: солнцезащитных свойствах по отношению к избыточному тепловому солнечному воздействию и, вместе с тем, качеств энергоэффективности с точки зрения снижения излучательных теплопотерь в холодное время.In this case, the deposition of a subsequent layer containing aluminum oxide doped with zinc Zn-Al-O is necessary to ensure stable contact between the first layer of titanium dioxide TiO ₂ adjacent to the surface of the glass substrate and the electrically conductive silver metal layer Ag, which is the first infrared reflective layer. It is generally accepted to call layers that perform these functions contact. The choice of a Zn-Al-O oxide doped with zinc aluminum as a specific material is related to the fact that the oxide of this alloy belongs to the group of materials that contribute to the formation of uniformly homogeneous layers of noble metals on top of them, including, which is relevant in this particular case of silver. This, in turn, contributes, along with ensuring stable contact between the first layer of titanium dioxide TiO ₂ adjacent to the surface of the glass substrate and the electrically conductive metallic layer of silver Ag, which is the first layer reflecting infrared radiation, the possibility of achieving energy-efficient qualities of the product in terms of reducing radiative heat loss in cold weather, corresponding to the value of the emissivity of the product, specified by the surface ohmic resistance of the thin-film coating, does not exceed sewing 4

due to the structural uniformity of the infrared reflecting Ag radiation of the silver Ag layer due to the concomitant minimization of parasitic resistance at the boundaries of crystalline conglomerates of a thin film silver layer with a catalyzed Zn-Al-O contact layer, a decrease in the number of the latter. This group of materials includes bimetallic zinc oxides Zn doped with an element of the group of light metals such as aluminum Al and tin Sn. It is also alternatively possible to use bimetallic oxides of indium In alloys doped with an element of a group of light metals such as aluminum Al or tin Sn as a contact layer. However, it was empirically revealed that only the use of an Ag silver reflective layer as a contact layer of a silver thin film of aluminum oxide doped with zinc Zn-Al-O from the entire group of materials listed above allows, in addition to achieving the indicated qualities, to prevent extinction of the electrically conductive metal coating layers, at the same time reducing their thickness, as a result of which it becomes achievable to provide increased translucency of the product with respect to the wavelengths of the visible part of the sun electromagnetic spectrum by reducing absorption in this wavelength range on the electrically conductive metal layers, while maintaining, according to the formulation of the technical problem solved by the present invention, preservation of the product qualities expressed in the combined combination of the following properties: sun protection with respect to excessive thermal sun exposure and, at the same time, the qualities of energy efficiency in terms of reducing radiative heat loss in cold weather.

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

In order to realize the quality of the sun-protection properties of the product with respect to excessive thermal sun exposure, the subsequent layer structure of the thin-film coating of the product is carried out according to a highly selective platform with two coating layers reflecting infrared radiation and containing silver, separated by ceramic layers. Due to a decrease in the transmission of electromagnetic radiation over the entire infrared wavelength range, along with the preservation of a relatively high level of visible light transmission, which is realized due to interference processes occurring during the consecutive overcoming of two nanoscale layers of silver Ag by radiation incident on the coating, the described product, in addition to reduced Compared with ordinary silicate glass, the emissivity coefficient, also has a low coefficient of solar heat gain SHGC , which, in turn, provides a manifestation of sun protection with respect to excess thermal solar exposure, characterized by a low direct transmittance of solar radiation T _sol . Since the chosen scheme for constructing a thin-film optical energy-saving coating of a product involves repeating the general structure of successively sequential materials in the case of reflecting infrared radiation layers containing silver Ag and surrounding layers of dielectrics, for convenience, silver reflective layers are called the first and second, respectively their order from the surface of the optically transparent glass substrate to the outside, and a similar naming rule is also used for Oev, contact with respect to the silver layers.

The need to use the so-called covering layer applied after the silver-reflecting infrared reflective layer is caused by the requirement to protect the silver layer from partial or complete destruction upon contact with oxygen-containing radicals during subsequent deposition of oxidized dielectric layers of a thin-film optical energy-saving coating during the reaction with oxygen and the formation of a porous structure, which, in turn, leads to a sharp decrease in transmittance visible light and reduced reflectance in the infrared. The covering layer should be barrier to oxygen diffusion in the direction of the conductive metal layers, in this case the infrared radiation reflecting the silver layer, and should consist of another, less active metal, oxidized in order to minimize the final additional reduction in the coefficients of transparency and heat reflection. Similarly, in order to minimize the final additional decrease in the transmittance and heat reflection coefficients 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 contact layer preceding it, counting outward from the substrate. Based on the above criteria, the material of the first covering layer of the thin-film optical energy-saving coating of the product was selected aluminum oxide doped with zinc Zn-Al-O, corresponding to the above requirements.

In order to ensure the effect of spectral broadening, which makes it possible to achieve the desired shade of the external reflection of the product, while maintaining the effect of interference re-radiation between the metallic silver layers reflecting with respect to infrared radiation, the dual highly selective structure for constructing a thin-film coating of the product in the form of two consecutive series of layers “contact to silver layer - a layer of silver reflecting infrared radiation - a layer covering with respect to silver "is separated sufficiently lstym optically transparent dielectric layer, commonly called an intermediate, which, in general, the thickness is several tens of nanometers, depending on the degree of spectral broadening effect to be achieved. In the framework of the present invention, based on the following conditions, zinc oxide doped tin oxide Zn-Sn-O was selected as the material of the intermediate layer. The choice of zinc as the main metal component of the indicated oxide of the bimetallic alloy is due to the best adhesion of the resulting material to zinc-containing surrounding silver layers, i.e. the first covering layer containing aluminum oxide doped zinc Zn-Al-O from the side of the optically transparent glass substrate, and the second contact layer containing aluminum oxide doped zinc Zn-Al-O, on the other hand, the outer relative to the optically transparent glass substrate, the formation of zinc-zinc metal bonds. The use of a metal alloy oxide as an intermediate layer is due to a combination of two reasons: additional “crosslinking” on oxygen atoms during the formation of zinc-zinc metal bonds, which contributes to further improvement of the adhesive properties of this layer with the surrounding Zn-Al-O layers, as well as increased transparency of this layer with respect to electromagnetic radiation of the visible wavelength range when the oxide component is introduced into the composition of the layer. In turn, the use of the tin alloying component is associated with the need to additionally provide the RTD for the qualities of the zinc oxide intermediate layer based on the above thicknesses of this layer of a thin-film optical energy-saving coating of the product, which achieves the effect of spectral broadening of the entire resulting layer structure when external electromagnetic radiation passes through it.

As noted above, in order to realize the quality of the sun-protection properties of the product in relation to excess thermal sun exposure, along with contributing to the reduction of heat loss in cold weather, the layer structure of the thin-film coating of the product is performed according to the scheme of a highly selective platform with two layers reflecting infrared radiation and containing silver, separated by ceramic layers. For this reason, the chosen scheme for constructing a thin-film optical energy-saving coating of the product involves repeating the general structure of successively sequential materials in the case of reflecting infrared radiation layers containing Ag silver and surrounding dielectric layers. To minimize the effect of reducing the transmittance of the product due to an increase in the total aggregate thickness of the absorbing electromagnetic radiation in the visible wavelength range of the electrically conductive metal layers, the role of which in the layer structure of the thin-film hybrid energy-efficient optical coating of the product is two Ag reflecting infrared radiation silver layer, the second contact layer, the second infrared reflective layer and the second covering layer should consist of materials as close as possible to their ence refractive indices and extinction coefficients of the first contact layer, the first reflecting IR radiation of a first layer and a covering layer, respectively. In addition, the second contact coating layer should ensure reliable adhesion of the entire repeating structure of the second infrared reflective layer and the dielectric layers surrounding it — the second contact layer from the side of the optically transparent glass substrate and the second covering layer from the side opposite to the location of the optically transparent glass substrate — to the already deposited part of the structure of thin-film coating layers due to effective "crosslinking" on oxygen atoms during the formation of metal bonds - at ohms of either zinc or tin, which make up the bimetallic part of the dielectric intermediate layer of zinc oxide doped tin Zn-Sn-O, which is in direct contact with the second contact layer, due to which atoms of either zinc Zn or tin Sn should be part of the metal components of the second contact layer . Based on the above requirements for materials of a repeating structure — the second infrared reflecting layer and the second contact and second sheathing dielectric layers surrounding it — materials of the second contact, second infrared reflecting radiation and second sheathing materials were selected that comprise the following previously if you count from the side of the glass substrate, the layers of the first part of the repeating highly selective structure of a thin-film hybrid energy-saving coating - the first to tact, first reflecting infrared radiation and the first covering layer: as the material of the second contact layer, applied over and directly in contact with the intermediate layer previous to the surface of the glass substrate, containing zinc oxide doped with tin zinc Zn-Sn-O, aluminum oxide doped zinc Zn -Al-O; silver Ag is used as the material of the second then second infrared reflective layer; as the material of the next layer, which is the second covering layer, aluminum oxide doped with zinc Zn-Al-O is used.

To protect the entire structure of the previously described layers of thin-film optical energy-saving coating of the product, an outer layer containing Zn-Sn-O zinc doped tin oxide is applied on top of them. The choice of Zn-Sn-O as the material of the outer layer is based on the following requirements related to the functional qualities of this layer. This layer must have the properties of preventing crack propagation (PRT) with respect to the second, external to the surface of the optically transparent glass substrate of the product reflecting infrared radiation silver layer, and accordingly consist of metal oxides or metal alloys selected from the group consisting of Ti, Si , Zn, Sn, In, Zr, Al, Cr, Nb, Mo, Hf, Ta, and W. The choice of zinc as the main metal component of this bimetallic oxide oxide is due to the best adhesion of the resulting material to zinc-containing Covering the second layer of the second silver layer reflecting infrared radiation, due to the formation of zinc-zinc metallic bonds. Finally, the outer layer must, along with the above requirements, have a refractive index n of the order of 1.9 to 2.1 so as not to have a negative minimizing effect on the quality of the “bleaching effect” exhibited by the first layer adjacent to the surface of the glass substrate of the product containing titanium dioxide TiO _2, due to the fact that the absorption of light in the thin film layer of TiO ₂ is very small compared with translucent layers subsequently deposited metal thin film, during the passage of the electromagnetic radiation Ia visible wavelength range through the entire thickness of the thin-film layered structure of a hybrid energy efficient coating articles supported on an optically transparent glass substrate. Based on the totality of all the above requirements for the material of the outer protective layer of the thin-film optical energy-saving coating of the product, Zn-Sn-O zinc oxide doped with tin was chosen as the material of the outer layer as the only material that simultaneously meets all the requirements presented.

The choice of the thickness of the intermediate layer containing zinc oxide doped with tin Zn-Sn-O, component from 50 to 75 nm, is determined by two basic conditions: the thickness of this layer should, on the one hand, be at least a multiple of a quarter of the wavelength in the middle peak zone of the infrared part of the solar spectrum, so that it is possible to provide the effect of interference attenuation during re-emission between the zinc oxide-doped tin oxide separated by an intermediate layer reflecting infrared radiation loyami silver Ag, leading to a sharp decrease in product passing electromagnetic radiation at the transition from the visible to the near infrared zone of the solar radiation spectrum and, as a result, reduce the solar radiation direct transmission coefficient T _sol to a value less than 44%. On the other hand, the thickness of the intermediate layer should be no more than half the value that is a multiple of at least one of the radiation wavelengths of the visible spectral range corresponding to the color perception of human vision, characterized along the a * color differentiation axis of the green / red quasi-coordinate grid of the international CEILAB standard ( D65 / 10 °) value lying in the range from +6.8 to +10.8 relative units, to provide a bronze color reflecting the surface of the glass substrate from the side opposite to the side on which w energy efficient coated thin film optical coating. Based on these two conflicting requirements, a range of acceptable values for the thickness of the intermediate layer containing zinc doped tin oxide Zn-Sn-O, ranging from 50 to 75 nm, was determined.

In turn, the choice of the thickness of the first layer adjacent to the substrate surface containing titanium dioxide TiO ₂ , component from 25 to 37 nm, is also determined by two basic conditions: on the one hand, the thickness of this layer should not be less than the maximum permissible boundary value, starting from which "enlightenment effect" provided by the layer material, expressed to a degree sufficient to provide the entire set of layers with the corresponding thicknesses of the thin-film optical hybrid energy-efficient coating on glass hydrochloric translucent substrate layer, characterized by visible light transmittance T _vis, of not less than 60%. On the other hand, the thickness of the first layer containing titanium dioxide TiO ₂ adjacent to the surface of the substrate should not exceed the maximum permissible value at 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 will prevail over the PRT qualities of the layer, which will lead to cracking of the infrared-reflecting layers containing silver Ag, and, in the general case, subsequent mechanical degradation and the subsequent partial or full delamination at the entire set of thin film layers of the optical hybrid energy-saving coating from the surface of the glass substrate. Based on these two conflicting requirements, we determined the range of acceptable thicknesses of the first layer adjacent to the substrate surface containing titanium dioxide TiO ₂ , ranging from 25 to 37 nm.

The ratio of the thickness of the layer containing titanium dioxide TiO ₂ to the thickness of the outer protective layer containing zinc doped tin oxide Zn-Sn-O should be in the range from 0.6 to 1.3. As it was experimentally established, when the ratio of these layers is less than 0.6 (with a thickness of the first layer adjacent to the substrate surface containing titanium dioxide TiO ₂ corresponding to a range whose boundaries and reasons for their choice are indicated above), the thickness of the outer protective layer containing zinc oxide, tin-doped Zn-Sn-O, reaches the maximum permissible value, which starts to be observed violation "bleaching effect" layer of titanium dioxide TiO ₂ due to the "parasitic" interference radiation attenuation Ia wavelengths corresponding band during the passage of the material layer of tin oxide doped with zinc Zn-Sn-O is too thick. At the same time, it was experimentally established that when the ratio of the thickness of the layer containing titanium dioxide TiO ₂ to the thickness of the outer protective layer containing zinc doped tin oxide Zn-Sn-O exceeding the value of 1.3 (with the thickness of the first substrate adjacent to the surface a layer containing titanium dioxide TiO ₂ corresponding to a range whose boundaries and reasons for their choice are indicated above), the thickness of the outer protective layer containing zinc doped tin oxide Zn-Sn-O becomes too small to provide qualities above chemical chemomechanical protection in relation to the second reflecting infrared radiation Ag silver layer, which, first of all, is expressed in its insufficient barrier properties in relation to aggressive acidic environment.

, и только в этом случае реализуется совокупный баланс между излучательной способностью изделия, с коэффициентом излучательной способности ε, не превышающим 6%, и величиной коэффициента прямого пропускания солнечного излучения T_sol, составляющего не более 44%, в результате чего изделие обладает гибридными качествами, выражающимися в одновременном совокупном проявлении солнцезащитных свойств по отношению к избыточному тепловому солнечному воздействию и качеств энергоэффективности с точки зрения снижения излучательных теплопотерь в холодное время. При этом отношение толщины первого слоя, отражающего ИК-излучение, содержащего серебро Ag, к толщине второго слоя, отражающего ИК-излучение, содержащего серебро Ag, должно быть в диапазоне от 1,1 до 1,4. Нижний из указанных пределов связан с тем, что, как было экспериментально показано, только при значениях отношения между толщиной первого слоя, отражающего ИК-излучение, содержащего серебро Ag, и толщиной второго слоя, отражающего ИК-излучение, содержащего серебро Ag, больше 1,1 противофазное резонансное затухание на длинах волн ближней ультрафиолетовой области будет обеспечивать заявленное в техническом результате настоящего изобретения снижение уровня прямого пропускания ультрафиолетового излучения ближней длинноволновой УФ-части спектра солнечного излучения по сравнению с прозрачной стеклянной подложкой без дополнительного тонкопленочного энергосберегающего оптического покрытия, характеризуемое коэффициентом пропускания ультрафиолетового излучения T_uv, составляющим менее 70%. 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 1,4 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 квазикоординой сетки международного стандарта CEILAB (D65/10°) значением, лежащим в пределе от +17,6 до +21,6 относительных единиц, для обеспечения бронзового цвета отражения поверхности стеклянной подложки со стороны, противоположной стороне, на которую нанесено тонкопленочное энергоэффективное оптическое покрытие.The total thickness of the two infrared reflective layers of the thin-film optical hybrid energy-saving coating of the product containing Ag silver is adjusted so that the surface ohmic resistance of the product does not exceed 4

, and only in this case, a total balance is realized between the emissivity of the product, with the emissivity coefficient ε not exceeding 6%, and the direct transmittance of solar radiation T _{sol of} not more than 44%, as a result of which the product has hybrid qualities, expressed in the simultaneous combined manifestation of sun-protection properties in relation to excessive thermal solar exposure and energy efficiency qualities in terms of reducing radiative heat losses in the cold one time. The ratio of the thickness of the first layer reflecting infrared radiation containing silver Ag to the thickness of the second layer reflecting infrared radiation containing silver Ag should be in the range from 1.1 to 1.4. The lower of these limits is due to the fact that, as was experimentally shown, only when the ratio between the thickness of the first layer reflecting infrared radiation containing silver Ag and the thickness of the second layer reflecting infrared radiation containing silver Ag is greater than 1, 1 antiphase resonant attenuation at the wavelengths of the near ultraviolet region will provide the claimed in the technical result of the present invention, a decrease in the level of direct transmission of ultraviolet radiation of the near long-wave UV part c ktra sunlight compared to a transparent glass substrate without an additional energy-saving thin film optical coating, characterized by the ultraviolet radiation transmittance T _uv, of less than 70%. At the same time, the ratio of the thickness of the first layer reflecting infrared radiation containing silver Ag to the thickness of the second layer reflecting infrared radiation containing silver Ag should not exceed 1.4 so that the interference resonant peak in the visible part spectrum of electromagnetic radiation, when re-emitted between the silver layers of a highly selective product platform with two layers reflecting infrared radiation, the layers were observed at a wavelength of not more than half a multiple of at least one of the radiation wavelengths a wide range of the spectrum corresponding to the color perception of human vision, characterized by the b * axis of color differentiation of the yellow / blue quasi-coordinate grid of the international CEILAB standard (D65 / 10 °) with a value lying in the range from +17.6 to +21.6 relative units, for providing a bronze color reflecting the surface of the glass substrate from the side opposite to the side on which the thin film energy-efficient optical coating is applied.

In this case, the ratio of the thickness of the first covering layer, which contains Zn-Al-O zinc oxide, to the thickness of the first contact layer, containing Zn-Al-O zinc oxide, and the ratio of the thickness of the second covering layer, which contains aluminum oxide zinc Zn-Al-O, to the thickness of the second contact layer containing aluminum oxide doped zinc Zn-Al-O, must be equal to each other so that spurious additional residual re-emission between these two functional groups of layers The high-selective platform of the product with two thin-film layers reflecting IR radiation did not exert a bias effect on the balance of position in color coordinates of the quasi-coordinate grid of the international standard CEILAB (D65 / 10 °) a * and b *, achieved by adjusting the ratio of thicknesses reflecting the IR radiation of thin-film coating layers containing silver Ag, and the thickness of the intermediate layer containing zinc doped tin oxide Zn-Sn-O, within the limits indicated and explained above, which provides a bronze color reflecting the surface of the stack on the opposite side to which the thin-film, energy-efficient optical coating is applied. In addition, it was empirically revealed that equal ratios of the thickness of the first covering layer, which contains Zn-Al-O zinc oxide, to the thickness of the first contact layer containing Zn-Al-O zinc oxide, and the thickness of the second covering layer, which contains Zn-Al-O zinc oxide doped with aluminum, to the thickness of the second contact layer containing Zn-Al-O zinc-doped zinc oxide, must not exceed the value 0.585, in order to also exclude the influence of parasitic additional residual radiation between these two functional groups of layers of a highly selective product platform with two thin-film layers reflecting IR radiation on the effect of spectral broadening from an intermediate layer containing zinc doped tin oxide Zn-Sn-O.

In this particular case, it is proposed to connect the glass substrate with a multilayer coating deposited on its surface with at least one additional transparent substrate, which faces the outer coating layer containing zinc doped tin oxide Zn-Sn-O. This solution can further improve the chemomechanical stability of the product as a whole, since the entire structure of the thin-film layers of the optical hybrid energy-saving coating on the primary glass substrate is then protected from negative external influences and contact with the external environment by the thickness of an additional transparent substrate or the thickness of the first of a group of additional transparent substrates directly in contact with the surface external to the primary glass substrate in external thin-film layer containing zinc doped tin oxide Zn-Sn-O. In this case, the 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 is maintained.

The table below provides an example of a specific implementation of the proposed product. Within the framework of the above example, a thin-film electrically conductive optical hybrid energy-saving coating of bronze color was obtained by layer-by-layer deposition on the surface of a glass substrate using physical vapor deposition of individual layers from an argon plasma of a magnetron discharge. In the case of dielectric oxygen-containing layers, deposition was carried out by sputtering metal targets in the presence of a reaction gas component, and the stoichiometric ratio of the deposited layers, where necessary, was controlled using a self-stabilizing system for detecting characteristic radiation of a plasma discharge with feedback on a PID controller. The work was carried out in an industrial installation for in-line ion-plasma deposition of thin-film coatings from magnetron discharge plasma onto Von Ardenne GC330H glass.

As can be seen from the table, the obtained layer thicknesses and their ratios satisfy the limits indicated in the claims.

The colorimetry of the product 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 (D65 / 10 °), shown in FIG. 1, gives the following values for color quasicoordinates: the position along the color differentiation axis of the green / red quasicoordinate grid a * is 9.34; the position along the axis of color differentiation of the yellow / blue quasi-coordinate grid b * is equal to 19.11, which corresponds to a saturated bronze hue of external reflection.

The transmission spectrum of the obtained product in the UV / VIZ / IR wavelength range of electromagnetic radiation of 250-2500 nm is shown in FIG. 2. The spectrum exhibits a sharp decrease in intensity along the spectral transmittance curve of the product when moving from the visible wavelength range to the near infrared range of thermal solar radiation in the region of the order of 1000 nm, which is typical for highly selective products of thin-film deposition of energy-efficient coatings on glass with two reflective IR radiation by layers, due to which it is possible to effectively prevent the transmission of excess thermal solar radiation at wavelengths of more than 1200 nm. Along with this, the transmission spectrum of the product reaches saturation with an asymptotic tendency of intensity to zero along the abscissa, which indicates the quality of energy efficiency from the point of view of reducing radiative heat loss in cold weather. At the same time, a sharp decrease in intensity along the spectral transmittance curve of the product is also observed on the left boundary of the visible range, in the region of the near long-wave ultraviolet range, which also confirms the hybrid property of the product to reduce the level of direct transmission of ultraviolet radiation from the near long-wave UV part of the solar radiation spectrum compared to a transparent glass substrate without an additional thin-film energy-saving optical coating. Numerical determination of the integral parameters of the obtained spectrum gives the following set of characteristic values for the analyzed product: direct transmittance of solar radiation T _sol equal to 39%, transmittance of visible radiation T _vis equal to 74%, transmittance of ultraviolet radiation T _{uv of} 33%.

. При этом прямое определение соответствующего коэффициента излучательной способности изделия, как интегрального параметра результирующего FT-IR спектра, дает для реализованного изделия значение ε, равное 0,02, что соответствует указанному техническому результату.To determine the numerical normalization of the energy efficiency qualities from the point of view of reducing radiative heat losses in the cold period of the product, non-contact stratometry of the coating surface was used, followed by far infrared spectroscopy on an Fourier transform IR spectrophotometer (FT-IR). According to the results of stratometric measurements, the surface ohmic resistance of the thin-film coating of the product was 1.94

. In this case, a direct determination of the corresponding emissivity coefficient of the product as an integral parameter of the resulting FT-IR spectrum gives a ε value of 0.02 for the realized product, which corresponds to the indicated technical result.

As another example of a specific implementation of the proposed product, a thin-film electrically conductive optical hybrid energy-saving coating was applied layer-by-layer to the surface of a glass substrate of sheet metal silicate “float” glass M1 with a thickness of 4 mm by physical vapor-phase deposition of individual layers from an argon plasma of a magnetron discharge, and the thickness of the individual layers within the error of the selected method of thin-film deposition were equal to the thicknesses of the corresponding layers from the above of the above example of a specific implementation of the proposed product, however, the mutual partial concentration of the metal components of bimetallic alloys of materials of the corresponding layers varied: for aluminum oxides doped with zinc Zn-Al-O, constituting the material of the first and second contact layers, as well as the first and second covering layers, a range of from 10 to 90% wt Al; for zinc-doped tin oxides Zn-Sn-O constituting the material of the intermediate and external protective layers, in the range from 40 to 60% wt Zn, and adjustment of the mutual partial concentration of metal components of bimetallic alloys of materials of the corresponding layers was carried out by varying the supplied plasma ignition power during sputtering each of the metal components from an individual cathode sputtering target. In this case, similarly to the previous example of a specific implementation of the proposed product, cited above, in the case of dielectric oxygen-containing layers, deposition was carried out by sputtering metal targets in the presence of a reaction gas component, and the stoichiometric ratio of the deposited layers, where necessary, was controlled using a self-stabilizing system for detecting characteristic radiation of a plasma discharge with feedback on the PID controller. The work was carried out in an industrial installation for in-line ion-plasma deposition of thin-film coatings from magnetron discharge plasma onto Von Ardenne GC330H glass.

The obtained samples were characterized by UV / VIS / IR and FT-IR spectrophotometry, non-contact stratometry and colorimetry in the reflection from the side of the substrate, the opposite side to which the thin-film energy-efficient optical coating was applied, in the a * / b * plane of the international CEILAB standard (D65 / 10 °), similarly to the example above, with the subsequent calculation of the integral characteristic values of the corresponding obtained spectra. The range of their values obtained for a series of samples of this example of a specific implementation of the proposed product is presented in the table below. The resulting ranges of values also correspond to the declared limits.

In addition, the combination of the product with a hybrid energy-saving coating on a glass substrate with an additional transparent substrate, which faces the outer coating layer containing zinc oxide doped with tin 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 preservation of the ranges of the resulting characteristic values obtained by characterizing the product achieved during the experiments and noted in the table above methods of UV / VIZ / IR and FT-IR spectrophotometry, non-contact stratometry and colorimetry in reflection from the side of the substrate, the opposite side to which the thin-film energy-efficient optical coating is applied, in the a * / b * plane of the international CEILAB standard (D65 / 10 ° ) In this case, the fixation of the connected product substrates was carried out by a rigid aluminum frame with its subsequent filling along the edge with a polymer compound to seal the glass units along the entire end surface of the combined substrates.

, повышенной светопрозрачности по отношению к длинам волн видимой части солнечного электромагнитного спектра, характеризуемой коэффициентом пропускания видимого излучения T_vis, составляющим не менее 60% и сниженного уровня прямого пропускания ультрафиолетового излучения ближней длинноволновой УФ-части спектра солнечного излучения по сравнению с прозрачной стеклянной подложкой без дополнительного тонкопленочного энергосберегающего оптического покрытия, характеризуемого коэффициентом пропускания ультрафиолетового излучения T_uv, составляющим не более 70%.Thus, based on the foregoing, the presented product demonstrates a saturated bronze color of reflection of the surface of the glass substrate from the side opposite to the side on which a thin-film energy-efficient optical coating is applied, characterized by the following reflection hue parameters in color quasicoordinates a * / b * of the international standard CEILAB (D65 / 10 °): a * from +6.8 to +10.8, and b * from +17.6 to +21.6, along with a full range of hybrid qualities of an energy-saving coating on glass substrates, expressed in co a combination of the following properties: sun protection with respect to excess thermal solar exposure, characterized by a direct transmittance of solar radiation T _{sol of} not more than 44%, energy efficiency qualities from the point of view of reducing radiative heat loss in cold time, corresponding to the value of the emissivity of the product given by the surface ohmic resistance of a thin-film coating not exceeding 4

, increased translucency with respect to the wavelengths of the visible part of the solar electromagnetic spectrum, characterized by a transmittance of visible radiation of T _{vis of} at least 60% and a reduced level of direct transmission of ultraviolet radiation from the near long-wave UV portion of the solar spectrum compared to a transparent glass substrate without additional thin-film energy-saving optical coating, characterized by a transmittance of ultraviolet radiation T _uv , s leaving no more than 70%.

Claims (2)

1. The bronze color product with a hybrid energy-saving coating on a glass substrate, comprising a multilayer coating, characterized in that the multilayer coating contains directly contacting layers in the following order from the surface of the glass substrate: the first layer adjacent to the surface of the glass substrate contains titanium dioxide TiO _2, subsequent layer, which is the first contact layer, which comprises aluminum-doped zinc oxide, Zn-Al-O, followed by a layer containing silver Ag, being the first layer reflecting infrared radiation, the next layer, which contains Zn-Al-O zinc oxide, is the first covering layer, followed by the intermediate layer containing Zn-Sn-O zinc-oxide, and the next layer is the second contact layer and contains Zn-Al-O zinc oxide doped with aluminum, followed by a layer containing silver Ag, which is the second infrared reflective layer, the next layer which contains Zn-Al-O zinc oxide, is the second layer, then an outer layer follows to protect the entire previously listed layer structure containing zinc doped tin oxide Zn-Sn-O, while the thickness of the intermediate layer containing zinc doped tin oxide Zn-Sn-O is from 50 to 75 nm, and the thickness of the layer containing titanium dioxide TiO ₂ is from 25 to 37 nm, while the ratio of the thickness of the layer containing titanium dioxide TiO ₂ to the thickness of the outer protective layer containing zinc doped tin oxide Zn-Sn-O is in the range from 0.6 to 1.3, in addition, the total thickness of two from infrared-reflecting layers containing silver Ag, such that the resulting surface ohmic resistance of the product with a hybrid energy-saving coating does not exceed 4

moreover, the ratio of the thickness of the first layer reflecting infrared radiation containing silver Ag to the thickness of the second layer reflecting infrared radiation containing silver Ag is from 1.1 to 1.4, while the ratio of the thickness of the first covering layer that contains doped oxide Zn-Al-O zinc aluminum to the thickness of the first contact layer containing Zn-Al-O zinc oxide and the ratio of the thickness of the second covering layer, which contains Zn-Al-O zinc oxide, to the thickness of the second contact layer containing aluminum oxide doped with zinc Zn-Al-O, are equal and are not more than 0.585. 2. The bronze-colored product with a hybrid energy-saving coating on a glass substrate according to claim 1, characterized in that the glass substrate with a multilayer coating deposited on its surface is connected to at least one additional transparent substrate that faces the outer coating layer containing doped oxide zinc tin Zn-Sn-O.

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