RU2696748C1 - Article with a hybrid highly absorbent energy-saving coating on a glass substrate - Google Patents

Abstract

FIELD: manufacturing technology.

SUBSTANCE: invention relates to energy-saving coatings on glass substrates. Multilayer coating on glass contains following layers in order of distance from glass: titanium dioxide layer TiO₂, a contact layer of zinc oxide, alloyed with aluminum, Zn-Al-O, a first infrared-reflecting layer and containing silver Ag, a first cover layer of zinc oxide, aluminum-doped, Zn-Al-O, an intermediate layer of tin-doped zinc oxide, Zn-Sn-O, a second infrared-reflecting layer and containing silver Ag, a second cover layer of aluminum-doped zinc oxide, Zn-Al-O, an outer layer of tin-doped zinc oxide, Zn-Sn-O. Thickness of intermediate layer Zn-Sn-O ranges from 82 nm to 90 nm, thickness of titanium dioxide TiO₂ – from 12 nm to 18 nm. Ratio of thickness of TiO₂ layer to thickness of external protective layer Zn-Sn-O is in limit from 0.3 to 0.5. Aggregate thickness of two infrared-reflecting layers containing silver Ag is such that the resulting surface ohmic resistance of the article with the hybrid energy-saving coating does not exceed 3 Ohm/square. Ratio of the thickness of the first layer which reflects infrared radiation to the thickness of the second layer which reflects infrared radiation ranges from 0.3 to 0.7. Ratio of the thickness of the first covering layer to the thickness of the first contact layer and the ratio of the thickness of the second cover layer to the thickness of the second contact layer are equal and lie within range of 0.45 to 1.15.

EFFECT: technical result is aimed at increasing the level of absorption of electromagnetic radiation of visible wavelength range along with hybrid properties of energy-saving coating on glass substrates, which are expressed in combined combination of the following properties: sun-protective properties in relation to excessive heat solar exposure, energy efficiency properties in terms of reducing radiative heat losses during cold weather, low level of direct transmission of ultraviolet radiation of the near long-wave UV part of the spectrum of solar radiation and neutral gray 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 deposited.

1 cl, 3 dwg, 2 tbl

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 along with increased absorption of radiation of the visible wavelength range.

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, electrically 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 complete 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 transmission 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 view of the energy efficiency of air conditioning in hot weather.

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 decrease in the intensity of excess direct thermal solar radiation entering the room, such products, however, are similar to low-emission thin-film products deposition on a glass substrate does not demonstrate a satisfactory absorption level of the excess incoming electromagnetic flux from radiation of the visible wavelength range, which affects the decrease in the comfort of their use as part of exterior translucent structures during daylight hours, especially in countries with a sunny climate and a long daylight hours. As a result of this, when using these products as part of translucent exterior building structures, there remains a need to use opaque exterior and interior overlapping light curtains, such as blinds, shutters, curtains, etc., if necessary, blocking excess incoming sunlight, which eliminates the potential the possibility of providing additional savings in energy spent on 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 Recreatives Products 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; No. 2642751; No. 2642753; No. 2648769 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 a so-called “neutral gray” tint of the external reflection of the surface of the glass substrate from the side opposite to the deposited energy-efficient thin-film optical coating, perceived by the human organs of vision as a greenish-blue tint, similar to the tint that was not exposed to thin-film layers of molten glass, shifted towards more saturated blue than mixed turquoise tones, and characterized by the following parameter E tint in reflection color quasicoordinates a * / b * international standard CEILAB (D65 / 10 ^°): a * from -4 to +3 and b * from -12 to -2.

Currently, in this area there is a need for a product coated on a glass substrate with an increased level of absorption with respect to electromagnetic radiation of the visible wavelength range, and also, along with this, hybrid qualities, expressed in the total implementation in it of a combination of specified sun-protection properties in relation to excess thermal solar exposure, energy efficiency qualities from the point of view of reducing radiative heat loss in cold weather, reduced direct pass Nia longwave ultraviolet radiation near UV portion of the solar spectrum, and the desired neutral gray 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 the features is RF patent No. 2636995, which describes a product with a hybrid coating on a glass substrate that shows energy efficiency in terms of reducing radiative heat loss in cold weather and reducing the level of direct transmission of ultraviolet radiation from the near long-wave UV part of the spectrum solar radiation compared to a transparent glass substrate without an additional thin-film energy-saving optical coating, including yuschee multilayer coating comprising directly contacting each other layers in the following order from the glass substrate: a first layer adjacent to the surface of the glass substrate comprises titanium dioxide TiO _2, the subsequent layer being first contact layer which comprises an oxide, aluminum-doped zinc Zn-Al -O, followed by a layer containing silver Ag, which is the first layer reflecting infrared radiation, the next layer, which contains aluminum oxide doped zinc Zn-Al-O, is the first a top layer, followed by an intermediate layer containing zinc-doped tin oxide Zn-Sn-O, the next layer is the second contact layer and contains zinc-doped zinc oxide Zn-Al-O, followed by a layer containing silver Ag, which is the second layer reflecting infrared radiation, the next layer, which contains aluminum oxide doped zinc Zn-Al-O, is the second covering layer, then the outer layer to protect the entire previously listed layer structure containing zinc doped tin oxide Zn-Sn-O, the thickness of the intermediate layer containing zinc doped tin oxide Zn-Sn-O is from 45 nm to 60 nm, and the thickness of the layer containing titanium dioxide TiO ₂ is from 14 nm to 20 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 0.4 to 0.6, in addition, the total thickness of two layers reflecting infrared radiation containing silver Ag is such that the resulting surface ohmic resistance of the product with a hybrid energy-saving coating does not exceed 4 Ohm / sq, 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 radiation containing silver Ag is from 0.8 to 1.1, while 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 thickness of the second coating layer, which is doped with aluminum th aluminum zinc Zn-Al-O, the thickness of the second contact layer comprising zinc oxide, aluminum-doped Zn-Al-O, equal and not more than 0.375.

This product, however, does not have a high level of absorption with respect to electromagnetic radiation in the visible wavelength range and the desired neutral-gray 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 technical result of the present invention is aimed at providing an increased level of absorption of electromagnetic radiation in the visible wavelength range along with the hybrid qualities of an energy-saving coating on glass substrates, which are expressed, in turn, in the combined combination of the following properties: sun protection with respect to excess thermal sun exposure, characterized by a coefficient direct solar radiation transmittance T _sol, constitute not more than 50%, energy to within qualities and the 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 3 Ohm / sq, a reduced 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 additional thin-film energy-saving optical coating characterized by ultraviolet transmittance Vågå radiation T _uv, constitute not more than 30%, and neutral gray reflection surface of the glass substrate on the side opposite the side on which the deposited thin-film energy-efficient optical coating, characterized by the following parameters reflection tint color quasicoordinates a * / b * international standard CEILAB (D65 / 10 ^°): a * from -4 to +3 and b * from -12 to -2, and the integral value of the absorption product a must be at least 10% at broadening the absorption band maximum in the visible light region to RANGES but from no more than 550 nm to not less than 900 nm.

The technical result is achieved by the fact that the proposed product with a hybrid highly absorbing energy-saving coating on a glass substrate, comprising 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 silver Ag, 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 Zn-Sn-O zinc doped tin oxide, the thickness of the intermediate layer containing Zn-Sn-O zinc doped tin oxide is from 82 nm to 90 nm, and the thickness the TiO ₂ titanium dioxide containing layer is from 12 nm to 18 nm, while the ratio of the thickness of the TiO ₂ titanium dioxide layer to the thickness of the outer protective layer containing zinc doped tin oxide Zn-Sn-O is in the range of 0 , 3 to 0.5, in addition, the total thickness of the two reflect their infrared radiation of layers containing silver Ag is such that the resulting surface ohmic resistance of a product with a hybrid energy-saving coating does not exceed 3 Ohm / sq, 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 radiation containing silver Ag ranges from 0.3 to 0.7, with the ratio of the thickness of the first covering layer, which contains zinc-doped zinc oxide Zn-Al-O, to the thickness of the first contact layer, s 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 Zn-Al-O aluminum oxide, are equal and are in the range of 0.45 to 1.15.

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.

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 characteristics, shown by the final 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 substrate surface. 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. Typically, 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 the thin-film coating, not exceeding 3 ohms / sq. 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 extinction coefficient of the deposited layer k in the range from 1.39 * 10 ^-5 at a wavelength of 550 nm to 1.11 * 10 ^-9 at a wavelength of 900 nm , which, in turn, ensures the occurrence of the necessary interference effects when electromagnetic radiation passes through a complete set of thin-film layers of a multilayer coating of a product, including, in this case, IR-reflecting Ag silver layers, as a result of which it becomes possible it is possible to achieve distortion of the split beam when passing through the metal barrier layer, which contributes to obtaining the desired absorption level of the product, characterized by the integral absorption of product A of at least 10% when the absorption maximum band in the visible region is broadened to a range from no more than 550 nm to at least 900 nm, according to the technical result of the present invention. 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 for Using it as a layer is generally 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.

In this case, the deposition of a subsequent layer containing aluminum oxide doped 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 Zn-Al-O zinc oxide doped with 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 silver. This, in turn, contributes, along with providing stable contact between the first layer of titanium dioxide TiO ₂ adjacent to the surface of the glass substrate, and the electrically conductive metallic silver layer Ag, which is the first infrared reflective layer, the possibility of achieving energy-efficient qualities of the product from the point of view 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 higher than 3 Ohm / sq, due to the structural uniformity of the reflecting IR radiation of the electrically conductive silver Ag layer due to the concomitant minimization of parasitic resistance at the boundaries of crystalline conglomerates of a thin film silver layer catalyzed by a 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 reflecting contact layer as a thin film layer of aluminum oxide doped with zinc Zn-Al-O from the entire group of the listed materials allows, in addition to achieving the indicated qualities, to prevent extinction of the electrically conductive metal coating layers, as a result, it becomes achievable to provide a higher level of integral absorption of the product with respect to the wavelengths of the visible part of the solar electromagnetic spectrum, due to the broadening of individual absorption intensities in the near infrared wavelength range in the direction of the higher frequency range of the visible part of the spectrum on the electrically conductive metal layers, while maintaining the product’s qualities, expressed in the combined combination of the following properties: sun protection properties in relation to excessive thermal solar exposure and, at the same time, energy efficiency qualities with t chki of reducing radiative heat loss in cold weather.

The subsequent infrared reflecting layer contains Ag silver. In this invention, Ag metallic silver was selected as the material for the infrared reflecting layers due to the combination of the absorption and reflection qualities of electromagnetic radiation of the middle and far wavelength ranges 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, 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 the reflection coefficient in and infrared spectrum. 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 coefficient of heat reflection of the product, this layer should consist of a material that is as close as possible in its refractive index to the previous contact layer, counting from the substrate to the outside. 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 this bimetallic oxide 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 the desirable quality of additional “crosslinking” on oxygen atoms during the formation of zinc-zinc metal bonds, which contributes to a further improvement in the adhesion properties of this layer with the surrounding Zn-Al-O layers. 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 thicknesses of the above-mentioned thin-film optical energy-saving coatings of the product, which achieve 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 with respect to excessive 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 carried out 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 sequentially successive materials in the case of layers containing Ag silver reflecting infrared radiation and surrounding dielectric layers. To minimize the effects of parasitic interference processes at the boundaries of the individual layers of the multilayer thin-film structure of the described product by increasing the total number of individual functional layers, the second contact layer, the second infrared reflective layer and the second covering layer should consist of materials that are as close as possible to their refractive indices indices and extinction coefficients for the first contact layer, the first infrared reflective layer and the first covering layer ootvetstvenno.

In addition, the second contact layer of the coating should ensure reliable adhesion of the entire repeating structure of the second infrared reflective layer and the surrounding dielectric layers — 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 already deposited part of the structure of thin-film coating layers due to effective “crosslinking” on oxygen atoms in the formation of metal bonds - at either zinc or tin constituting the bimetallic part of the dielectric intermediate oxide layer of zinc 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 product reflecting infrared radiation silver layer, and, accordingly, should 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 the second covering layer of the second silver layer, reflecting infrared radiation, due to the formation of zinc-zinc metal bonds. Finally, the outer layer must, along with the above requirements, have an extinction coefficient k of at least 1 * 10 ^-4 in the wavelength range from 550 nm to 900 nm so as not to cause parasitic effects on the secondary resonance absorption peaks formed during the course interference effects provided by the first layer adjacent to the surface of the glass substrate of the product and containing titanium dioxide TiO ₂ during the passage of electromagnetic radiation of the visible wavelength range through the entire thickness of the thin-film layer structures of a hybrid highly absorbing energy-efficient coating of a product deposited 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, the oxide of zinc doped tin Zn-Sn-O 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-doped tin oxide Zn-Sn-O, ranging from 82 nm to 90 nm, is determined by two basic conditions: the thickness of this layer should, on the one hand, be not less than a multiple of a quarter of the wavelength per the middle of the peak zone of the infrared part of the spectrum of solar radiation, so that it is possible to ensure the effect of interference attenuation during re-radiation between the separated intermediate zinc oxide doped tin oxide layer reflecting infrared e layers of silver Ag, resulting in a sharp change in the degree of 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 coefficient of direct solar radiation transmittance T _sol to a value less than 50%. 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 within the range from -4 to +3 relative units, to provide a neutral gray glass reflection by the surface of the substrate opposite the side on otorrhea energy efficient coated thin film optical coating, perceived human organs of both greenish-blue shade, a similar hue not subjected to application of thin film layers of glass, biased towards a more saturated blue rather than mixed turquoise colors ,. Based on these two conflicting requirements, we determined the range of acceptable values for the thickness of the intermediate layer containing zinc doped tin oxide Zn-Sn-O, ranging from 82 nm to 90 nm.

In turn, the choice of the thickness of the first layer adjacent to the substrate surface containing titanium dioxide TiO ₂ , ranging from 12 nm to 18 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 the occurrence of interference effects manifested by the material of the layer and expressed to a degree sufficient to provide the entire set of layers with the corresponding thicknesses of the thin-film optical hybrid highly absorbing non-efficient coating on a glass substrate of the absorption level of electromagnetic radiation in the visible wavelength range, characterized by the integral absorption of the product A of at least 10% when the absorption maximum band in the visible region is broadened to a range from not more than 550 nm to not less than 900 nm according to the technical result of the present invention. 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 12 nm to 18 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 0.3 to 0.5. As it was experimentally established, when the ratio of these layers is less than 0.3 (with the 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 oxide Zn-Sn-O doped with zinc reaches the maximum permissible value, at which the effect of parasitic effect on the secondary resonant absorption peaks formed during the course of interference begins to be observed the processes provided by the first layer adjacent to the surface of the glass substrate of the product and containing titanium dioxide TiO ₂ during the passage of electromagnetic radiation of the visible wavelength range through the entire thickness of the thin film layer structure of the hybrid highly absorbing energy-efficient coating of the product deposited on an optically transparent glass substrate, including material Zn-Sn-O zinc doped tin oxide layer 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 0.5 (for 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 ensure the quality of reliable chemomechanical protection with respect to the second layer of silver Ag reflecting infrared radiation, which, first of all, is expressed in its insufficient barrier properties with respect to the aggressive acidic environment.

не превышающим 4%, и величиной коэффициента прямого пропускания солнечного излучения T_sol, составляющего не более 50%, 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 0,3 до 0,7. 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 0,3 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 30%. 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 0,7 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 -12 до -2 относительных единиц, для обеспечения нейтрально-серого 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 3 Ohm / sq, and only in this case the aggregate balance between the emissivity of the product, with the emissivity abilities

not exceeding 4%, and the value of the direct transmittance of solar radiation T _{sol of} not more than 50%, as a result of which the product has hybrid qualities, expressed in the simultaneous combined manifestation of sun protection with respect to excessive thermal solar exposure and energy efficiency qualities in terms of reducing radiative heat loss in cold weather. In this case, 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 0.3 to 0.7. 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 IR radiation containing silver Ag and the thickness of the second layer reflecting IR radiation containing silver Ag is greater than 0.3 antiphase resonant attenuation at the wavelengths of the near ultraviolet region will provide for the claimed direct technical transmission of the present invention to reduce the level of direct transmission of ultraviolet radiation of the near long-wave UV part of 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 30%. 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 0.7 so that the interference resonance peak falling on the visible part of the electromagnetic spectrum radiation, when re-emitting between 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 of -12 to -2 relative units, to ensure a neutral gray color 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.

At the same time, 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 alloy Zn-Al-O zinc, to the thickness of the second contact layer containing aluminum doped zinc oxide Zn-Al-O, must be equal to each other so that spurious additional residual re-emission between these two functional groups of layers ysokoselektivnoy platform products with two reflecting IR thin-film layers had no biasing effect on the position of balance on color coordinates kvazikoordinoy grid CEILAB international standard (D65 / 10 ^°) a * and b *, achieved alignment thickness ratio reflecting IR thin film layer coating, containing silver Ag, and the thickness of the intermediate layer containing zinc doped tin oxide Zn-Sn-O within the limits specified and explained above, which provides a neutral gray color reflection surface of the glass substrate from the side opposite to the side on which the thin-film energy-efficient optical coating is applied, perceived by the human organs of vision as a greenish-blue tint, similar to the tint of the non-applying thin-film layers of glass melt, shifted towards more saturated blue than mixed turquoise tones . 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-doped zinc oxide, the thickness of the second contact layer containing Zn-Al-O zinc-doped zinc oxide must be in the range of 0.45 to 1.15, in order to also eliminate the influence of parasitic additional residual on re-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, which is shown to be empirically revealed with respect to the spectral absorption curve of the described product in the case of going beyond the boundaries of the specified range as the upper limit - which leads to an excessive contribution to the light transmission of the entire set of thin-film layers coating, and the lower limit - which leads to the loss of the effect of broadening of the band of the maximum absorption of the product at the right border, lying in the limit of at least 900 nm.

Moreover, 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, which faces the outer coating layer containing zinc doped tin oxide Zn-Sn-O. This solution allows to further increase 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, in this case, 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 groups of additional transparent substrates directly in contact with the surface external to the primary glass substrate an outer thin film layer containing zinc doped tin oxide Zn-Sn-O. At the same time, 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. In the framework of the given example, a thin-film electrically conductive optical hybrid highly absorbing energy-saving coating was applied layer by layer on the surface of the glass substrate by physical vapor-phase 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 feedback radiation characteristic radiation plasma recording system 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 absorption spectrum of the obtained product in the wavelength range of electromagnetic radiation from 280 nm to 1200 nm is shown in FIG. 1. The spectrum exhibits a peak of broadening of the absorption maximum band in the region of visible light over the full range from 537 nm to 918 nm. A numerical determination of the integral absorption value of an exemplary product obtained from the absorption spectrum for the wavelength range of visible light gives an A value of 11.58%.

The transmission spectrum of the obtained product in the UV / VIZ / IR wavelength range of electromagnetic radiation of 280-2500 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 47.51% and transmittance of ultraviolet radiation T _{uv of} 27.38%.

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 2.18 Ohm / sq. 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 £ value of 0.023 for the realized product, which corresponds to the indicated technical result.

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. 3) gives the following values for color quasi coordinates: position along the axis of color differentiation, the green / red quasi-coordinate grid a * is -1.47; the position along the axis of color differentiation of the yellow / blue quasi-coordinate grid b * is -8.17.

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 on the surface of a glass substrate of sheet silicate “float” glass M1 with a thickness of 4 mm by physical vapor-phase deposition of individual layers from argon plasma of a magnetron discharge, and the thickness of individual layers were equal within the error of the selected thin-film deposition method 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 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 10% to 60% wt A1; for zinc-doped tin oxides Zn-Sn-O constituting the material of the intermediate and external protective layers, in the range from 30% to 50% 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 in during the sputtering of each of the metal components from an individual cathode sputtering target. In this case, similarly to the previous example of the specific implementation of the proposed product given 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, contactless stratometry and colorimetry in 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.

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 resulting characteristic values obtained by characterizing the products obtained during the experiments and noted in the table above E UV / VIZ / IR and FT-IR spectrophotometry, colorimetry and contactless stratometrii in the reflection from the substrate side opposite to the side on which the thin film coated optical energy efficient coating in the plane a * / b * international standard CEILAB (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.

Thus, based on the foregoing, the presented product with a hybrid highly absorbing energy-saving coating on a glass substrate provides an increased level of absorption of electromagnetic radiation in the visible wavelength range, along with hybrid qualities of an energy-saving coating on glass substrates, which, in turn, are in combination with the following properties: in relation to excess thermal sun exposure, characterized by a coefficient of direct prop Scania sunlight T _sol, constitute not more than 50%, energy qualities in terms of reducing radiative heat loss in the cold, the corresponding value of the emissivity of the product, defined by the surface ohmic resistance of the thin film coating is not greater than 3 ohms / sq, a reduced level of direct UV transmittance near long-wave UV part of the solar radiation spectrum compared to a transparent glass substrate without additional thin-film energy a protective optical coating, characterized by a transmittance of ultraviolet radiation T _{uv of} not more than 30%, and a neutral gray reflection color 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 * international standard CEILAB (D65 / 10 ^°): a * from -4 to +3 and b * from -12 to -2, and the integral value of absorption articles a has structure ive not less than 10% at broadening the absorption band maximum in the visible light to the range of not more than 550 nm to not less than 900 nm.

Claims (2)

1. Product with a hybrid highly absorbing energy-saving coating on a glass substrate, comprising a multilayer coating containing 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 containing titanium dioxide TiO ₂ , the next layer, which is the first a contact layer that contains Zn-Al-O zinc oxide doped with aluminum, followed by a layer containing silver Ag, which is the first layer reflecting infrared and radiation, the next layer, which contains Zn-Al-O zinc oxide, is the first covering layer, followed by an intermediate layer containing Zn-Sn-O zinc-oxide, the next layer is the second contact layer and contains aluminum alloy zinc Zn-Al-O, followed by a layer containing silver Ag, which is the second layer reflecting infrared radiation, the next layer, which contains aluminum oxide doped zinc Zn-Al-O, is the second covering layer, then the next outer layer to protect the entire previously listed layer structure containing zinc doped tin oxide Zn-Sn-O, characterized in that the thickness of the intermediate layer containing zinc doped tin oxide Zn-Sn-O is from 82 nm to 90 nm, and the layer thickness containing titanium dioxide TiO ₂ ranges from 12 nm to 18 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 0.3 up to 0.5, in addition, the total thickness of two reflecting infrared the radiation of layers containing silver Ag is such that the resulting surface ohmic resistance of a product with a hybrid energy-saving coating does not exceed 3 Ohms / square, and the ratio of the thickness of the first layer reflecting infrared radiation containing silver Ag to the thickness of the second layer reflecting infrared radiation, containing silver Ag ranges from 0.3 to 0.7, with the ratio of the thickness of the first covering layer, which contains aluminum oxide doped zinc Zn-Al-O, to the thickness of the first contact layer containing its 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 Zn-Al-O aluminum oxide, are equal and are in the range of 0.45 to 1.15. 2. A product with a hybrid highly absorbing 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 zinc doped oxide tin Zn-Sn-O.

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