RU2578071C1 - Ir-reflecting and transparent system of layers having colour stability, and method of making same manufacture, glass block - Google Patents

Abstract

FIELD: optics.

SUBSTANCE: invention relates to thermally treated system layers for glazing for protection against sun. Provided is information on a transparent infrared reflective layer system on a transparent, dielectric substrate SO, a method of its manufacture, and a glass unit for use in said system of layers. System includes a structure of main layer GA with a dielectric main layer GAG lying above structure of UFA functional layer with a metallic functional layer UFAF and a blocking layer UFAB and a structure of coating layer. Structure of intermediate layer ZA is deposited with such thickness that when viewing angle in range from 0 to ±75° relative to normal to substrate surface a * (Rg) and b * (Rg)-colour CIE L * a * b * system colour measurements of reflection from side of substrate are located in range of ≤ 0.

EFFECT: technical result is ensuring high transmission in visible range, low radiating capacity and wide reflection colour point stability.

16 cl, 13 dwg

Description

The invention relates, in General, to a heat-treatable, reflecting infrared (IR-), transparent layer system, which contains at least two metal IR-reflecting layers on a transparent, dielectric substrate, to a glass block when using such a layer system, and also to a method of manufacturing such a system of layers.

The invention relates, in particular, to such an IR-reflective layer system, which has various transparent and partially absorbent, functionally distinguishable layer structures. In this case, the structure of the layer should be understood as one or several separate layers located one above the other and intended for the functioning of the layer structure. Such a layer structure can include both homogeneous individual layers, and those that have a gradual change in composition along their layer thickness, the so-called gradient layers.

The functionally IR-reflecting layer system, which is referred to below only as a layer system, is distinguished by its low emissivity and the associated high reflectivity, as well as its low emissivity and transmission in the IR spectral range (wavelengths> 3 μm). At the same time, high transmittance in the visible light region should often be ensured. Thus, when passing from visible light to near infrared, there is a sharp drop in transmittance and a strong increase in reflection. Due to their emission characteristics, such layer systems are also called Low-E layer systems (hard-coated systems).

The IR-reflective layer systems with low emissivity and high IR-reflection also include the so-called Low-E-Sun-layer systems (coating with PVB film). They are used for glazing, also called glazing for protection from the sun, where the supply of energy through glazing predominates, and a small transmission of energy and the associated high selectivity of the glazing used is an advantage. In contrast, the Low-E layer systems described above are used in climatic regions with predominant energy loss through glazing. There, a high transmission of solar glazing energy is preferred, due to which solar energy is obtained. Along with the structure and materials of various IR-reflective layer systems, their installation location in architectural glazing and insulating glass blocks is also different.

FIG. 8A and FIG. 8B show double glazing with two window panes S, SO and an intermediate space SZ between both panes, as well as possible main coating positions. The positions are the surfaces of the window panes and are usually counted from the outside, on figa and figv shown using the arrow with a wavy line for the incidence of light. Thus, in the presence of two glasses, four positions are obtained, with the first outside and the fourth inside. With multilayer glazing, two other positions on glass are obtained accordingly. Due to its functioning and operability, a single Low-E layer system is normally located at position 3 (Fig. 8A), multi-layer - Low-E and Low-E-Sun layer systems are preferably located at position 2 (Fig. 8B). Similar layer systems can also be used in such glass blocks in which two glasses without an intermediate space are connected directly to each other by means of a connecting means (for example, film) (not shown). Also in these combined glass blocks, for example automobile glasses, respectively, with safe glazing, having a substrate coating are most often arranged so that the IR reflective coating lies between the substrates.

In Low-E-Sun layer systems, transmittance in the visible region is reduced compared to Low-E systems. Also here, the color tone of the layer system can be set directionally.

High reflection in the IR region in both applications is achieved, in general, by using one or more metal IR reflection layers, for example, silver, gold, copper or others. As a rule, the profile described above in the spectral characteristic of transmission and reflection with an increasing number of IR-reflecting layers becomes steeper, therefore with increasing use of layer systems with two or more IR-reflecting layers.

In general, the IR-reflecting system of layers, when looking upward from the substrate, first includes the structure of the base layer, which, in particular, serves to adhere the system to the substrate, chemical and / or mechanical resistance and / or to set the optical properties of the system, for example, bleaching or manifestations of color.

The structure of the base layer is followed by the structure of the functional layer, which includes an IR-reflective layer, and also optionally other layers that support this function and make it possible to influence the optical, chemical, mechanical and electrical properties.

The so-called Single-Low-E-system of layers, which includes only the structure of the functional layer, can be replenished by the inclusion of one or more structures of the functional layer (Double-, Triple-, or Multi-Low-E), which, using the structures of the binder or the intermediate layer are located on top of the first structure of the functional layer. The structures of the intermediate layer serve, in particular, to enlighten in the visible region due to the functional separation of both structures of the functional layer from each other and their mechanical connection on each other. Moreover, with an appropriate combination of materials, the mechanical stability of the layer system could also be achieved using the structure of the intermediate layer.

At the top, the IR-reflective layer system ends with a cover layer structure that includes at least a mechanically and / or chemically protective layer that stabilizes. It can itself or with the help of additional layers affect the optical performance of the layer system, for example, bleaching when using interference effects, so that, if necessary, the transmission can also be increased in combination with the antireflective main layer.

The purpose of the individual layers for the main, functional, covering or other layer structure should not be taken unambiguously in each case, since each layer affects both adjacent layers and the entire system. In general, the purpose of a layer is determined by its fundamental function. So, only those layers that primarily represent the intermediary between the substrate and another sequence of layers are assigned to the structure of the main layer. For example, with seed substrates or interface layers that lie directly below the structure of the functional layer, it is possible to have a positive effect on the adhesion or electrical and optical properties of the adjacent layer, in particular the IR reflective layer.

Other layers of the structure of the base layer may also affect the properties of the layer system as a whole, such as, for example, antireflection layers or protective layers. The structure of the functional layer, along with the IR-reflecting layer, also includes such layers as its functional layer, which directly affect its properties, such as blocking layers to suppress diffusion processes of neighboring layers in the functional layer. Layers of the structure of the covering layer complete the system of layers at the top and can, like the structure of the main layer, affect the entire system.

The corresponding sequence of individual layers and layer structures can be modified either within a single layer structure or a sequence of layer structures so that special requirements arising from the application or manufacturing process can be met.

Often during the manufacturing process of the layer system in the already applied sequence of layers, various temperature loads occur due to the energy supply associated with the deposition or various processing steps of the deposited layers. In addition, IR reflective layer systems for curing and / or deformation of the substrate can also be subjected to annealing processes. Depending on the application of the coated substrate, its system of layers during the annealing is in a different time regime of different climatic conditions.

Due to temperature loads, various processes occur that change the reflectivity of the functional layer and the transmission of the system of layers, for example, the diffusion of the components of the antireflective layer into the functional layer and vice versa and, as a result, the oxidation processes in the functional layer. To prevent such diffusion and oxidation processes, the structures of the functional layer on one or both sides of the functional layer have a blocking layer, which serves as a buffer for diffusing components. These blocking layers are structured and positioned accordingly to the resulting temperature load and protect the sensitive often very thin functional layer or functional layers from the influence of neighboring layers. By introducing one or more blocking layers, the oxidation of the IR reflecting layer of the layer system can be prevented, as well as the associated increase in the specific surface resistance of the layer or also strong changes in the hue of the layer system during the coating process itself or due to the annealing process.

At the same time, the blocking layers can also be used in order to establish the transmission of the layer system, in that one or more regularly lying below the functional layer of the blocking layers act as absorbent layers. On this basis, Low-E-Sun layer systems have, at least below the lowest, that is closest to the functional layer, a blocking layer comprising a metal or substoichiometric oxide, metal nitride or oxynitride or semiconductor or an alloy thereof. The location of the lower blocking layer often leads to the fact that the underlying seed substrate is absent in the structure of the main or intermediate layer.

As blocking layers of annealing layer systems, layers are known containing, in particular, nickel and / or chromium. Thus, in DE 03543178 A1, these blocking layers enclose IR-reflecting silver layers or protect them from at least one side. Blocking layers, however, lead to a decrease in transmittance and to the conductivity of the silver layer and thus to a decrease in IR reflection.

An IR-reflecting system of layers with two or more structures of a functional layer, which, with low emissivity and high transmittance in the visible region of the spectrum, is resistant to annealing and bending at high temperatures, in time and in geometric frames, for example, it is known from DE 102010008 518 A1. The layer system described in this publication, even after temperature loads, has unchanged optical properties, in particular, also from neutral to blue, the reflection color from the side of the substrate, which differs in negative, i.e. blue, b * (Rg) -modules of color in L * a * b * - color space.

In the usual way, the optical and thermal properties, such as color reflection and transmittance, respectively, surface resistivity and emissivity of a system of layers are established using completely special thicknesses of individual layers. While a Single-Low-E system can be made up of at most 4 to 7 separate layers, Doppel-Low-E already has 7 to 10 and Triple-Low-E already has 10 to 14 separate layers, depending on execution. The thickness of the silver layers determines to a large extent the specific surface resistance and thus the ability to emit in the IR region, but also the optical properties. The thicknesses of the base and covering layers, in contrast, are critical especially for the manifestation of color.

When developing these layer systems, it was found that the optical properties when controlling the thermal properties strongly depend on the viewing angle. Established during perpendicular viewing, that is, when the viewing angle is 0 ° relative to the normal to the surface of the substrate, the neutral or blue color of reflection from the sides of the substrate, even with a slightly larger viewing angle, can be reflected in red or purple. Neutral colors in CIE L * a * b * - in the color measurement system, the a * (Rg) and b * (Rg) -modules differ near zero, while blue colors are characterized by negative b * -modules and red, and also violet colors with positive a * -modules of color.

The objective of the invention is the creation of an IR-reflecting system of layers, in particular for architectural glass, which even under the demanding climatic conditions of heat treatment of the coated substrate and / or with the emergence of inhomogeneous properties of the substrate provides sufficient quality, for example, high transmittance in the visible region, as well as low emissivity and at the same time has a wide and independent from the viewing angle stability of the color point of the reflection of the system of layers from the sides of the substrate in neutral th to the bluish area L * a * b * - color space. The objective of the invention is also to create a method of manufacturing such a reflective layer system.

To solve the problem, an IR-reflecting layer system according to paragraph 1 and a method for its manufacture according to paragraph 10 of the claims are proposed. Preferred embodiments of the system of layers and the method of its manufacture are given in the respective dependent claims.

The IR-reflecting system of layers proposed in accordance with the invention has almost the entire, preferably the entire viewing area, reflection from the neutral side to the blue from the side of the substrate, color change to a reddish color space depending on the viewing angle does not occur. This property is achieved by varying the thickness of the layer, in comparison with the implementation of the thicknesses of the individual layers of the layer system of at least one structure of the intermediate layer, which is purely optimized in terms of color. The variation of the layer thickness is carried out in such a way that the a * (Rg) and b * (Rg) -modules of the color CIE L * a * b * - color measurement systems lie in the range ≤0.

The change in Δa * (Rg) and Δb * (Rg) of the color moduli is small and insignificant in this respect, since the values remain in the negative region, and according to the embodiment of the method proposed in accordance with the invention, the color reflection values from the substrate determined using a * ( Rg) and b * (Rg) -modules, according to the CIE L * a * b * -system of color measurements or a change in these values that occurs during the manufacturing of the layer system can be set, respectively adjusted using the sum of the thicknesses of the individual layers of the structure of the base layer and / or structure of the coating layer. Such adjustment of the a * (Rg) - and b * (Rg) -modules of color contributes to both a change in their average values and a change in the values of Δa * (Rg) and Δb * (Rg) through the viewing angle. The ability to adjust color modules also allows you to take into account and prevent a possible additional change in the appearance of color in the process of further processing the coated substrate, for example, due to heat treatment by annealing, bending, laminating, etc.

It turned out that even a slight change in the ratio of the thicknesses of the functional layers, without changing the overall thickness, in combination with the above measures or in itself alone makes it possible to save or return the reflection color modules from the substrate side.

The starting point for the manufacture of a color independent of the angle of manifestation is the desired manifestation of color during normal viewing, that is, parallel to the normal having a coating on the surface of the substrate, and it is of interest, in particular, reflection from the side of the substrate, since coated substrates are considered mainly from this side. Here, the term “independent of angle” should be understood that a * (Rg) - and b * (Rg) -modules of color in the indicated region of the viewing angle should not take any positive values.

The independence of the angle can be realized by the thickness of the structure of the intermediate layer for various materials and combinations of the layer thickness corresponding to the generic concept of an IR-reflecting layer system with at least two functional layer structures and also for such layer systems, the manufacture of which involves heat treatment or which are subjected to further processing by lamination to form a combined system. Thus, the layer system proposed in accordance with the invention and the method of its manufacture can be applied to widespread, thermally, mechanically and chemically resistant layer systems with the required high or directionally reduced transmission with little radiation ability, for example, for architectural glass.

The layer system corresponding to the generic term includes in its basic structure the structure of the base layer with at least one dielectric base layer. It consists of such a metal nitride, oxide or oxynitride, a semiconductor or a semiconductor alloy, which is suitable for reducing diffusion processes from a substrate to a layer system lying above it and here, in particular, to the structure of the functional layer.

The effect of materials commonly used for the structure of the base layer, or layer thicknesses, on independence from the angle of color development has not been established. The possible influence on the manifestation of color itself can, if necessary, be well adjusted using the thicknesses of the structure of the main and / or covering layer.

The base layer may contain, for example, silicon, for example, silicon nitride. It turned out that a good barrier effect with respect to the substrate is achieved, in particular, with the help of such layers, which along with special capture of ions have a dense structure. Other functionally and structurally comparable materials may also be used. The materials used depend significantly on the characteristics, namely, with respect to the expected diffusion processes, so that for the respective substrate-layer combinations and thermal requirements, suitable materials must be determined empirically. With respect to the diffusion of sodium ions from glass, it has been found, for example, that some metal oxides, such as tin oxide, zinc stannate or titanium oxide show only a negligible barrier effect.

Depending on the material used, the base layer can also be highly refractive. In this case, the base layer can simultaneously serve as enlightenment.

The region of strongly refracting properties of an individual layer should in no case be considered as usual with respect to the material layers used in the system, as well as the substrate absolutely, since the optical effect is mixed in, here, in particular, the antireflection effect in changing the optical thickness of neighboring layers.

Since in the case of the substrate we are talking about glass, its refractive index in the range of about 1.5 and several tenths above and below it should be considered as weakly refracting, while the refractive indices of silicon nitride or metal oxides are 2.0 and higher and therefore should be considered as highly refractive. Compared to a refractive index of 1.5 or lower, however, a refractive index of 1.8 or 1.9 may already be highly refractive. These boundaries, as presented, are focused on these materials. If the refractive indices of the applied materials are shifted, then the boundaries are also shifted.

The base layer, depending, for example, on the functionality of the layer system and the materials used, in an embodiment of the invention may also include a seed substrate, which positively affects the deposition and reflective properties of the IR-reflecting functional layer. With the seed substrate, the adhesion of the IR-reflecting functional layer deposited directly above the seed substrate can be improved and the surface resistivity can be reduced, and thus the IR-reflective properties can be improved. The seed substrate consists of a metal, or oxide, or metal nitride, or a metal compound, or a metal alloy and is made in the form of a seed layer, which thus affects the structure of the functional layer during deposition, so that the desired, low surface resistivity is achieved.

As described above, in another embodiment of the invention, the seed substrate is absent, for example, in the Low-E-Sun layer system, when the structure of the functional layer also has a blocking layer under the functional layer.

The structure of the functional layer located above the structure of the base layer includes a metal functional layer for reflecting infrared radiation, as well as a blocking layer of metal, a metal compound or metal alloy, or of an oxide, nitride or oxynitride thereof. It serves primarily to protect the functional layer with respect to oxidative and diffusion processes, which, for example, can occur in subsequent coating processes in the continuous manufacturing process of the layer system or during the annealing of the layer system. In addition, through its thickness and also stoichiometry, the transmission of the entire system of layers can vary. The blocking layer may be located below or above the functional layer or in both positions.

If, with the barrier effect of the base layer, sufficient stabilization of the layer system can already be achieved with respect to the thermal effects caused by the substrate, then in accordance with the invention for the highly transparent layer system the lower location of the blocking layer is not required. This possibility has a positive effect on transmittance in the visible region of the spectrum, however, without causing damage to thermal stability. Of the blocking layers located on both sides, only the upper one remains, which lies above the functional layer and protects against diffusion and related oxidative processes from the layers deposited above the functional layer. The effect on the independence of the angle of manifestation of color using such a modification proposed in accordance with the invention of the system, the layers were not installed. The possible influence on the manifestation of color itself can, if necessary, be well adjusted using the thicknesses of the structure of the main and / or covering layer.

The second and, however, each other structure of the functional layer is introduced under the final layer system of the structure of the covering layer. The separation between the two structures of the functional layer and, therefore, also their connection with each other is carried out using the structure of the intermediate layer, so that the sequence of layers includes the structure of the functional layer, above it the structure of the intermediate layer and another structure of the functional layer and, if necessary, other alternating structures of the intermediate and functional layers.

According to the invention, the structure of the intermediate layer includes one or more intermediate layers. Among the various dielectric materials of metal oxides, nitrides or oxynitrides, metal alloys or metal compounds or semiconductors or compounds thereof, it turned out to be favorable for thermal stability if, according to an embodiment of the invention, at least one of the individual layers of the structure of the intermediate layer contains mixed zinc oxide tin, for example, zinc stannate, which may contain nitrogen fractions. From this it follows that it is fundamentally possible to structure an intermediate layer of one layer, which contains a mixed zinc-tin oxide, for example, zinc stannate with nitrogen fractions as an option. The mixed zinc-tin oxide is preferably formed by stoichiometric, however, it can also be formed by substoichiometric, since the associated reduction in the transmission of the layer system can be tolerated or compensated by other measures. Zinc stannate is known as a compound of zinc and stannate, a salt of tin acid, and due to its constituents as zinc, tin and oxygen in the form of a vapor deposited layer, is also generally referred to as zinc-tin mixed oxide.

Alternatively, an intermediate layer structure consisting of several layers can be used, all of which individual layers contain tin. Using the tin content prescribed for each intermediate layer, regions with different tin components, which may also include gradient-shaped transitions from one layer to another, also appear in the intermediate layers that are different from each other, when looking at the thickness of the structure of the middle layer.

As described above, a layer containing a mixed zinc-tin oxide, for example zinc stannate, optionally also with nitrogen fractions, has special, mechanically stabilizing properties, which according to the invention are also used for the structure of the intermediate layer. This, due to the connecting function, is an advantage for the structure of the intermediate layer, as well as for its combination with a layer differing in tin content.

Preferably, for the reflection properties of the intermediate layer deposited over the structure of the intermediate layer, the functional layer is if, as described above in connection with the seed substrate of the base layer structure, the structure of the intermediate layer ends with the seed substrate.

Regardless of the structure of the structure of the intermediate layer in the form of a structure of one layer or several layers, as described above, it is possible to establish independence from the angle using their thickness. This can be done by varying the thickness of one or more individual layers. The essential is the sum of the thicknesses of the individual layers. It was found that already increasing the thickness of the structure of the intermediate layer from 2 to 13%, preferably from 3 to 8%, in comparison with only the color-optimized system of layers contributes to the required independence from the angle. But depending on the structure of the layer system and the materials used, the thickness change can also take other values, and due to the interference effect and high transparency of the dielectric layers, even a larger increase in thickness does not have any negative effect on the transparency of the layer system.

According to the description of the lower structure of the functional layer, the structure of the intermediate layer is followed by the second structure of the functional layer. Proposed in accordance with the invention, the layer system at the top ends with the structure of the coating layer with at least one dielectric coating layer.

The influence of materials usually used for the structure of the functional, intermediate and covering layers of materials or layer thicknesses on independence from the angle of manifestation of color has not been established. The possible influence on the manifestation of color itself, if necessary, can be well adjusted using the thicknesses of the structure of the main and / or covering layer.

The structure of the coating layer can be performed, for example, from two layers, and in the first, lower layer contain mixed zinc-tin oxide, for example zinc stannate, as an option with nitrogen fractions. It can overlap, for example, with a highly refractive and containing silicon oxide, nitride or oxy nitride coating layer. Since the first covering layer, along with its optical action, has a mechanically stabilizing effect on neighboring layers, a strong, stable and stabilizing transmission, as well as a color point of the end of the layer system, are achieved with this layer.

Alternatively or additionally, when using silicon nitride as the second coating layer in combination with a layer containing mixed zinc-tin oxide, for example zinc stannate, optionally with nitrogen fractions, coating layers of different thicknesses can be used. The layer system proposed in accordance with the invention also in the other described layer structures may contain other individual layers in order to adapt to special mechanical, chemical, thermal or optical requirements.

The described structure of individual layer structures, as well as their modifications, can equally be used in an IR-reflecting layer system, which includes two or more two structures of a functional layer.

It is also possible to establish the independence of the angle of color manifestation through the thickness of one or several structures of the intermediate layer for this embodiment of the layer system proposed in accordance with the invention, as described above in connection with Double-Low-E.

It turned out that changing the thickness of the structure of the intermediate layer closest to the substrate to independence on the angle has the strongest effect, so that only its thickness is set in the execution of the invention.

The production of the layer system proposed in accordance with the invention is carried out in a continuous coating unit by means of subsequent deposition of the individual layers from the gas phase on the substrate, respectively, of the already deposited layers of the layer system. The deposition is carried out for one or more layers using DC or MF-magnetron sputtering, which, in particular, is also used for active cathodic sputtering and due to the energy balance of the coating material creates layers with the desired structure. Using the common PVD method, layers of the desired thickness and quality can be reproducibly produced. A gradation of layer thicknesses may also be realized to achieve independence from the angle with the required accuracy.

In this case, different coating methods can also be combined with each other in order to optimize different layers with respect to properties and effective deposition. For example, it may be advantageous if the lowest and highest layers of the layer system, which, among other things, serve as their mechanical and chemical protection, are not manufactured using PVD, but using a CVD or plasma CVD process.

A manufacturing method, as described above, may include other processing steps for a partially or fully coated substrate.

Determination of the layer thicknesses of the structures of the intermediate layer required for independence from the angle can be carried out using ex situ measurements of color modules having a coating of substrates, or determined before the manufacture of a coated substrate by simulation. Suitable simulation programs for this are known to those skilled in the art. Since, for metrological or computer related measurements, the layer thicknesses are repelled by the a * (Rg) and b * (Rg) color modules of the preferred color manifestation, and the increase in the total thickness by values in the range from 2 to 13%, preferably from 3, is studied up to 8%, costs can be significantly reduced, since this range is sufficient for the layer systems corresponding to the generic concept.

In a comparable manner, changes in the color manifestation due to a change in the thickness of one or more structures of the intermediate layer and / or due to individual manufacturing steps can also be established and corrected using the thickness of the structure of the main and / or covering layer.

The layer system proposed in accordance with the invention is explained in more detail below with reference to exemplary embodiments.

 In the drawings show:

FIG. 1 is a sequence of layers of a Double-Low-E-layer system;

FIG. 2 is a sequence of layers of a Double-Low-E-Sun layer system;

FIG. 3 is a sequence of layers of a Triple-Low-E-layer system;

FIG. 4A and FIG. 4B - image of the dependence on the angle of the a * (Rg) - and b * (Rg) -modules of the reflection color on the substrate side of individual glasses (A) and insulating glass block (B) for only the Double-Low-E layer system optimized in terms of color ;

FIG. 5A and FIG. 5B is an image of the dependence on the angle of the a * (Rg) - and b * (Rg) -modules of the reflection color from the substrate side of the individual glasses (A) and insulating glass block (B) for the system optimized in terms of color and angle Double-Low-E - layers; and

FIG. 6A and FIG. 6B is an image of the dependence on the angle of the a * (Rg) and b * (Rg) -modules of the reflection color on the substrate side of individual glasses (A) and insulating glass block (B) for the Double-Low-E-Sun-system optimized in terms of angle layers;

FIG. 7A and FIG. 7B is an image of the dependence on the angle of the a * (Rg) and b * (Rg) -modules of the reflection color on the substrate side of the individual glasses (A) and insulating glass block (B) for the Triple-Low-E system optimized in terms of color and angle layers;

FIG. 8A and FIG. 8B is a sectional view of an arrangement of coated glass substrates in various insulating glass blocks.

FIG. 1 represents an IR-reflective layer system according to the invention with two structures of a functional layer FA (Double-Low-E), the individual layers described below being deposited one after another on an SO substrate in a continuous coating plant using DC or MF - magnetron sputtering.

On a SO substrate, in an embodiment of float glass with a refractive index of about 1.52, a GAG core layer with a thickness of 10 to 40 nm, preferably 15 to 35 nm, which serves as a barrier and antireflection layer and is composed of nitride, is first located silicon, for example Si ₃ N ₄ , which has a small proportion of aluminum, a few percent, here it is preferably at about eight percent by weight. The GAG core layer of the embodiment has a refractive index of 2.12 ± 0.05. The layer is actively sprayed in the presence of nitrogen as the gas component of the reaction in the working atmosphere of argon with a Si-Al anticathode with 6-10% of aluminum. Alternatively, the layer can also be deposited without a fraction of aluminum and / or in a different gaseous reaction atmosphere, or can be made using PECVD.

In an embodiment, the structure of the base layer GA further includes a GAK seed substrate with a thickness of less than or equal to 15 nm, preferably ≤10 nm. It consists of zinc-alumina, which is sprayed with a Zn: Al anticathode with about 2% of aluminum or ceramic zinc-alumina anticathode. Alternatively, the layer can also be deposited without a fraction of aluminum or a ceramic zinc oxide anticathode (the so-called internal zinc oxide). Alternatively, the structure of the GA base layer beneath the GAK seed substrate may have another base layer consisting, for example, of titanium oxide or niobium oxide, which would benefit from a higher refractive index and its wavelength dependence compared to the main GAG layer.

On top of the structure of the GA base layer, a first, lower structure of the UFA functional layer is deposited. It includes, directly above the GAK seed substrate, a lower functional UFAF layer as an IR reflective layer and has a thickness of 5 to 15 nm, preferably 7 to 13 nm. In an embodiment, silver is used. But other materials with an IR-reflecting property can also be used, such as gold or other noble metal or alloys thereof, a semiprecious metal or tantalum.

Above it is a lower UFAB blocking layer with a thickness of only a few nanometers, preferably less than 5 nm. Various materials can be considered for the blocking layer, in addition to the nitride layers indicated as known nickel-chromium or nickel-chromium oxide, respectively, other materials can also be used, for example, to affect the optical and / or electrical properties of the layer system. For example, a zirconium oxide layer of various stoichiometry is suitable to increase the transmission of the layer system in comparison with the use of a nickel-chromium oxide layer and to reduce the specific surface resistance of the layer system. A further increase in transmission and a decrease in specific surface resistance would be possible with a blocking layer with x <1 without an additional oxygen inlet deposited from a ceramic ZnO _x : AL anticathode with 2% aluminum. As described above, titanium oxide TiO _x with x≤2 or a layer of niobium oxide Nb _x O _y with y / x <2.5 are also possible as a blocking material, the latter being deposited from the ceramic anticathode without an additional oxygen inlet in the form of a substoichiometric layer . Thus, the deposited layer contains more oxygen than could be realized by deposition from a metal anticathode, as a result of which a substantially lower absorption is obtained, which from the very beginning leads to higher transmittance associated with a lower increase in transmittance during thermal exposure, for example, due to the annealing process .

In addition, stoichiometric and substoichiometric chromium nitride containing molybdenum material or stainless steel nitride SST _x N _y can be used for the blocking layer, and with these materials a reduction in the transmission of the layer system in the visible region can be achieved, for example, for use in Low-E-Sun -system of layers. This reduces the visible transmittance with increasing, also different from the above, thicknesses of the blocking layer, which, due to the use of these materials in one or more blocking layers of a system including several structures of the functional layer, can be established even more directionally. In addition, when using these materials, layer stability also arises with respect to annealing processes, since it is not so easily oxidized and does not recrystallize at the required small layer thicknesses.

On top of the lower structure of the functional UFA layer, the structure of the intermediate ZA layer is deposited. It consists in an embodiment of two layers, one intermediate ZAZ layer and a ZAK seed substrate deposited above it. The ZAZ intermediate layer consists of zinc stannate with a thickness of 50 to 80 nm, preferably 60 to 75 nm. It is sprayed from the anticathode with zinc stannate, which contains 50% zinc and 50% tin, actively in the presence of oxygen in the working gas argon.

The seed substrate ZAK of the structure of the intermediate layer ZA matches in the exemplary embodiment regarding the function, material, range of layer thickness and deposition with that structure of the base layer GA, so that there can be referenced there. Alternatively, other materials for one or more separate layers can also be used if they fulfill the described functions. Alternatively, instead of a single intermediate layer, several dielectric layers with different compositions can also be deposited.

On top of the structure of the intermediate layer ZA, the upper structure of the OFA functional layer is deposited, which, as described in connection with the lower structure of the UFA functional layer, includes the upper OFAF functional layer and the upper OFAB blocking layer. The upper structure of the OFA functional layer adjoins directly to the seed substrate ZAK of the structure of the intermediate layer ZA and corresponds in composition to the lower one, so reference is made to this part in this part. As an alternative, other materials can be used, for example, various materials are possible for the lower and upper blocking layer of UFAB and OFAB.

The upper OFAF functional layer as an IR reflective layer has a thickness of 10 to 20 nm, preferably 12 to 18 nm. In an embodiment, silver is used. But it is possible to use other materials with an IR-reflecting property, such as gold or other noble metal or alloys from them, a semi-noble metal or tantalum. The thickness ranges of the upper OFAB blocking layer correspond to the ranges of the lower structure of the UFA functional layer.

The IR reflective layer system at the top ends with the structure of the overlay layer DA. It includes a first covering layer DA1, which is deposited on the upper blocking layer OFAB. It consists of zinc stannate, has a thickness of 10 to 20 nm, preferably 12 to 18 nm, and is deposited in an atmosphere containing oxygen or containing oxygen and nitrogen from a zinc-tin anticathode that contains 50% zinc and 50% tin. Moreover, when the composition of the reaction gas with a ratio of volume fractions of nitrogen to oxygen is less than or equal to 0.2, it is possible that, despite the proportion of nitrogen in the atmosphere of the reaction gas, there will be no nitrogen in the first covering layer DA1. This also applies to the structure layers of the intermediate ZA layer containing zinc stannate.

As an alternative, the zinc stannate of the overburden DA1 may also have a small amount of nitrogen, and other ratios of the zinc / tin mixture may be established if the function described above remains intact as the overburden.

Above the first coating layer DA1, a second silicon-aluminum nitride coating layer DA2 is deposited with a thickness of 10 to 30 nm, preferably 15 to 25 nm. This is comparable with the main layer of GAG with Si: A1 anticathode with 6-10% aluminum content. Also, the refractive index is comparable to the refractive index of the main GAG layer. Alternatively, the layer may also be deposited without a fraction of aluminum and / or in another atmosphere of the reaction gas. For the case when color correction is required for the manifestation of color reflection, in which the coating layer is also involved, the thickness may take other values than those indicated here.

Thus, the following composition of the layer system is obtained, if you look up from the SO substrate:

GAG Si ₃ N ₄ with 6-10% Al;

GAK ZnO with about 2% Al;

UFAF Ag;

UFAB Nb _x O _y with y / x <2.5;

ZAZ Zinc Stannate;

ZAK ZnO with about 2% Al;

OFAF Ag;

OFAB Nb _x O _y with y / x <2.5;

DA1 Zinc stannate;

DA2 Si ₃ N ₄ with 6-10% Al.

The insulating glass block with this layer system in position 2 has a neutral to slightly blue reflection color, the color modules of which in the CIE L * a * b * color measurement system with a perpendicular direction of view (the direction of view in Fig. 1 is shown by an arrow), then is the angle of view α equal to 0 °, take the values a * (Rg) = - 2 and b * (Rg) = - 5.

FIG. 2 represents a Double-Low-E-Sun layer system, which differs in structure, materials and layer thicknesses of the blocking layer and the seed substrate from the layer system of FIG. one.

The main structure is as follows:

GAG Si ₃ M ₄ (as an option with 6-10% A1);

UFAB Chromium Nitride;

UFAF Ag;

UFAB Nickel Chromium Nitride;

ZAZ Zinc Stannate;

ZAK ZnO with about 2% Al;

OFAF Ag;

OFAB Substoichiometric Nickel-Chromium Oxide;

DA1 Zinc stannate;

DA2 Si ₃ N ₄ (as an option with 6-10% Al).

Accordingly, the structure of the base layer GA includes only the first base layer GAG, which can be deposited with a thickness of 25 to 45 nm, and here, as in the layer system according to FIG. 1, this thickness can take other values, you need to adjust the color of the manifestation of color when reflected.

Directly on top of the structure of the base layer GA is the first blocking layer of the lower structure of the UFA functional layer. Due to its purpose, it must also be designated as the lower blocking layer. In an embodiment, it is deposited from stoichiometric or substoichiometric chromium nitride with a thickness of less than 10 nm, and to set the desired transmission of the Low-E-Sun layer system, as described above, other layer thicknesses and compositions, respectively oxygen and nitrogen fractions, are also possible. Such a transmission setting using the lower blocking layer can also be applied to the Single-Low-E-Sun layer system.

On top of the lower functional layer of the UFAF, referred to in the description of FIG. 1, a second lower nickel-chromium nitride blocking layer is deposited with a thickness comparable to the first lower UFAB blocking layer. And this second lower UFAB blocking layer, like the upper OFAB upper blocking layer, can be modified due to its absorption properties to set transmission properties.

Further, the layer system shown in FIG. 2 differs from the layer system shown in FIG. 1, the material of the upper OFAB blocking layer, which consists of a nickel-chromium substoichiometric oxide and has a thickness of less than 5 nm, preferably less than 1 nm.

But in another embodiment of the Double-Low-E-Sun layer system, the upper OFAB blocking layer may also consist of the same material as the blocking layer of the layer system shown in FIG. 1. This has the advantage that the appearance of color and especially the increase in transmission due to annealing becomes even less.

In the remaining parts of the layer system, reference is made to the description of FIG. one.

FIG. 3 represents a Triple-Low-E-layer system that has three functional layer structures, namely the lower structure of the UFA functional layer, the middle MFA, and the upper OFA. As set forth in connection with FIG. 1, the structures of the functional layer of the UFA, MFA, OFA are connected to each other using the structures of the intermediate layer ZA. The average structure of the MFA functional layer, as well as the intended structure of the intermediate layer ZA lying above it, correspond to the material of the lower structure of the functional layer UFA and the structure of the intermediate layer ZA lying above it. Layers differ from each other in their thickness. Thus, the middle functional layer of MFAF is several nanometers thicker than the lower functional layer of UFAF and the intermediate ZAZ layer lying on top of the middle structure of the functional layer of MFA is several nanometers smaller than the lower intermediate layer of ZAZ.

The layer system ends with the SO substrate again with the structure of the base layer GA and on the other side with the structure of the covering layer, to which reference is made to the above discussion. Thus, the following structure is obtained:

GAG Si ₃ N ₄ with 6-10% Al;

GAK ZnO with about 2% Al;

UFAF Ag;

UFAB Nb _x O _y with x / y <2.5%;

ZAZ Zinc Stannate;

ZAK ZnO with about 2% Al;

MFAF Ag;

MFAB Nb _x O _y with x / x <2.5%;

ZAZ Zinc Stannate;

ZAK ZnO with about 2% Al;

OFAF Ag;

OFAB Nb _x O _y with x / y <2.5%;

DA1 Zinc stannate;

DA2 Si ₃ N ₄ with 6-10% Al.

All described layer systems according to FIG. 1, FIG. 2 and FIG. 3 have, in conjunction with a glass substrate SO, for the viewing angle α in the range from -80 to + 80 ° relative to the normal to the surface of the substrate N, negative a * (Rg) and b * (Rg) color modules for reflection from the side of the substrate (cf. Fig. 5A, 6A and 7A).

However, in particular, it is of interest to show the color of the coated substrate in the case of use, that is, in a state integrated in the insulating glass block. Also, all the layer systems described here for the viewing angle α in the range from -80 to + 80 ° relative to the normal to the substrate surface N have negative a * (Rg) and b * (Rg) color modules for external reflection (cf. Fig. 5B, 6B, 7B).

In FIG. 4A and FIG. 4B shows the dependence on the angle a * (Rg) and b * (Rg) -modules of color, having a separate glass coating (Fig. 4A) and made of insulating glass block (Fig. 4B) with a layer system according to Fig. 1 in position 2 (Fig. 8 B) for the case that the desired color development was obtained without taking into account the viewing angle. It can be seen that a * (Rg) already at a deviation of about 40 ° from the vertical direction of the gaze has shifted to positive values and thus to red. A comparison of the curves for single glass and insulating glass block shows this.

In order to create the independence of the sign angle of the a * (Rg) and b * (Rg) color modules, proposed in accordance with the invention, and thereby optimize the color desired from neutral to blue, the intermediate layer ZAZ and the seed substrate ZAK of the structure of the intermediate layer ZA are deposited with such layer thicknesses that the thickness of the entire structure of the intermediate layer ZA is 5 to 10% greater than that with which the values shown in FIG. 4A. Due to this increase, the a * (Rg) and b * (Rg) color modules receive values that are less than or equal to zero over the entire angle range up to 90 ° (Fig. 4B). The initial color manifestation of a color-optimized layer system can be maintained by reducing the structure thickness of the base GA layer by 25-35% while increasing the structure thickness of the coating layer DA by 1-5%. This gives a whole decrease in the sum of the dielectric layers of the structures of the main, intermediate and covering layers of GA, ZA, DA from 5 to 7%.

The initial thicknesses of FIG. 4A, for preferred color development, can be determined by application of a test coating or by computational modeling before the actual production of a layer system. In a comparable way, alternatively, in terms of increasing the thicknesses of the layers, also by means of a series of experiments, in which case, again, coating and computational modeling, the thicknesses of individual layers can change so, in particular, increase until the angular stability a * (Rg) - and b * (Rg) -modules of color.

Color coated glass according to FIG. 5a is shown in the insulating glass block of FIG. 5 B. Although the installation effect in the insulating glass block contributes to the flattening of the curves, the a * (Rg) and b * (Rg) color modules, as before, show negative values.

Dependence on the angle of neutral to blue color development of the Double-Low-E-Sun-layer system according to FIG. 2 can be set as described above in connection with the Double-Low-E-layer system. In FIG. 6A and 6B show the external and thus obtained in the installed state a * (Rg) - b * (Rg) -modules of the color of an individual glass (Fig. 6A) and an insulating glass block made of it (Fig. 6B) with application coatings in position 2 in the range of viewing angle α to 90 °.

Dependence on the angle of neutral to blue color manifestation of the Triple-Low-E-layer system according to FIG. 3 can be set in a similar manner as described above in connection with Double-Low-E, wherein here the structure of the intermediate layer ZA of the purely color-optimized layer system has been increased by 3-5%. In FIG. 7A and FIG. 7B shows the a * (Rg) and b * (Rg) -modules of the color of an individual glass (Fig. 7A) and insulating glass block made of it, which are thus obtained from the side of the substrate and thereby external in the installation state (Fig. 7B) by coating at position 2 in the viewing angle range α to 90. The initial color development of the layer-optimized purely color system of layers can be maintained by increasing the thickness of the structure of the base layer GA by 20 to 22% while increasing the thickness of the structure of the coating layer DA by 9 to eleven%. This gives a general increase in the sum of the dielectric layers of the structure of the main, intermediate and covering layers of GA, ZA, DA from 6 to 8%.

For the manufacture of an SO coated substrate, after deposition, it can be annealed, bent, or laminated in the form of a multilayer double-glazed window or built into various positions of insulating glass blocks.

Depending on the properties of the layer system that are specifically required, the reflection color, transmittance and emissivity, for example, can accept changes in the layer thickness of the structure of the intermediate layer or structures of the intermediate layer to reduce the dependence on the angle of the reflection color from the side of the substrate, also larger or smaller values. But in each case according to the invention, an increase in the thickness of the intermediate layer is necessary. But the changes in the layer thicknesses of the structures of the main and covering layers GA and DA, necessary for color adjustment, can have different proportions and signs depending on the properties of the layer system (see above) that are absolutely specific (see table 1 and 5).

If necessary, in addition, the thicknesses of the silver layer must be adapted accordingly to its thickness ratio in order to achieve the required angle dependence.

To depend on the angle, the optical effects of the interference of certain combinations of color moduli with the specifically required transmittance and emissivity must be taken into account.

List of items

SO Substrate GA Base layer structure Gag Main layer Gak Seed substrate UFA The lower structure of the functional layer UFAF Bottom functional layer Ufab Bottom blocking layer Mfa The average structure of the functional layer MFAF Middle functional layer Mfab Middle blocking layer OFA The upper structure of the functional layer OFAF Top functional layer ORAV Top blocking layer Za The structure of the intermediate layer Zaz Intermediate layer Zak Seed substrate DA Coating Structure DA1 First coating layer DA2 Second coating layer N Normal to substrate surface BUT Viewing angle.

Claims (16)

1. The system of layers reflecting infrared radiation on a transparent substrate (S0) with the following transparent layer structures, if you look up from the substrate (S0):
- the structure (GA) of the base layer with a dielectric base layer (GAG) with a thickness in the range from 10 to 40 nm, preferably from 15 to 35 nm, containing silicon nitride or silicon-aluminum nitride to reduce diffusion processes from the substrate (S0) to the located above it is the structure (UFA, MFA, OFA) of the functional layer,
- the lower structure (UFA) of the functional layer with a metal functional layer (UFAF), which has a thickness in the range from 5 to 15 nm, preferably from 7 to 13 nm and consists of silver, gold, another noble metal or an alloy of them, a semiprecious metal or tantalum to reflect infrared radiation, and with at least one blocking layer (UFAB), which has a thickness of several nanometers, preferably less than 5 nm, and consists of nickel chromium, nickel chromium oxide, nickel chromium nitride, oxide zirconium of various stoichiometry zinc oxide with about 2% aluminum, titanium oxide TiO _x with x≤2, substoichiometric niobium oxide Nb _x O _y with y / x <2.5, chromium nitride containing molybdenum material or stainless steel nitride SST _x N _y for protection functional layer (UFAF) in relation to oxidative or diffusion processes,
- at least one structure (ZA) of the intermediate layer, which separates another structure (MFA, OFA) of the functional layer from the underlying structure (UFA, MFA) of the functional layer and includes an intermediate layer (ZAZ), as well as a seed substrate (ZAK ) structure (ZA) of the intermediate layer,
- at least one other functional structure layer (MFA, OFA) of the functional layer with a metal functional layer (MFAF, OFAF) lying above the lower structure (UFA) of the functional layer with a thickness in the range from 10 to 20 nm, preferably from 12 to 18 nm, which consists of silver, gold, other noble metal or alloys thereof, a semi-noble metal or tantalum to reflect infrared radiation and with at least one blocking layer MFAB, OFAB), which consists of nickel chromium, nickel chromium oxide, nickel chromium nitride zirconium oxide spill stoichiometry, zinc oxide with about 2% aluminum, titanium oxide TiO _x with x≤2, substoichiometric niobium oxide NB _x O _y with y / x <2.5, chromium nitride containing molybdenum material or stainless steel nitride SST _x N _y to protect another functional layer (MFAF, OFAF) against oxidative and diffusion processes and
- a structure (DA) of the coating layer with a dielectric coating layer (DA1, DA2) containing a metal nitride, oxide or oxy nitride, a semiconductor or a semiconductor alloy, characterized in that at least one structure (ZA) of the intermediate layer has such a thickness that at an viewing angle in the range from 0 to ± 75 °, relative to the normal to the surface of the substrate, the a * (Rg) and b * (Rg) color modules of the CIE L * a * b * color measurement system of reflection on the substrate side ranging from ≤0. 2. The system according to claim 1, characterized in that the structure (ZA) of the intermediate layer includes an intermediate layer (ZAZ) of zinc stannate with a thickness in the range from 50 to 85 nm, preferably from 60 to 75 nm, and also a seed substrate (ZAK ) structure (ZA) of the intermediate layer with a thickness of ≤15 nm, preferably ≤10 nm, of zinc oxide-aluminum, 3. The system according to claim 1, characterized in that the structure (DA) of the coating layer includes a dielectric coating layer (DA1) containing zinc-tin oxide with a thickness in the range from 10 to 20 nm, preferably from 12 to 18 nm, and a coating layer (DA2) comprising silicon nitride or silicon-aluminum nitride or silicon oxynitride, with a thickness in the range from 10 to 30 nm, preferably from 15 to 25 nm, 4. The system according to claim 1, characterized in that the indicated a * (Rg) - and b * (Rg) -modules of color at an viewing angle in the range from 0 to ± 90 ° lie in the range from ≤0. 5. The system according to claim 1, characterized in that it includes at least three structures (UFA, MFA, OFA) of the functional layer with corresponding structures (ZA) of the intermediate layer lying between them, the sum of the thicknesses of the individual layers being closer to the intermediate layer structure substrate is greater than the sum of the thicknesses of the individual layers of at least one intermediate layer structure (ZA) more remote from the substrate. 6. The system according to claim 1, characterized in that at least one structure (UFA, MFA, OFA) of the functional layer under the functional layer (UFAF, MFAF, OFAF) does not have any blocking layer (UFAB, MFAB, OFAB) . 7. The system according to any one of paragraphs. 1-6, characterized in that the structure (GA) of the base layer includes a seed substrate (GAK). 8. The system of claim 1, wherein the at least one structure (UFA, MFA, OFA) of the functional layer has a blocking layer (UFAB, MFAB, OFAB) under the functional layer (UFAF, MFAF, OFAF), and the underlying structure (GA) of the base layer and / or the structure (ZA) of the intermediate layer does not include any seed substrate (GAK, ZAK). 9. The system according to any one of paragraphs. 1-6, characterized in that at least one middle or upper blocking layer (MFAB, OFAB) contains substoichiometric niobium oxide. 10. The system according to any one of paragraphs. 1-6, characterized in that immediately below at least one functional layer (UFAF, MFAF, OFAF) a seed substrate (UFAK, MFAK, OFAK) is deposited from a metal or from a metal oxide or nitride or a metal compound or metal alloy for changes in the specific surface resistance of the functional layer (UFAF, MFAF, OFAF). 11. A method of manufacturing an infrared reflective layer system according to any one of the preceding paragraphs, in which coatings are applied one after another on a transparent substrate (SO) such that transparent layer structures with their layers are deposited in vacuum according to any one of claims. 1-10. 12. The method according to p. 11, characterized in that the system of layers is deposited with at least three structures (UFA, MFA, OFA) of the functional layer with the respective structures (ZA) of the intermediate layer lying between them, and the specified dependence on the viewing angle the a * (Rg) - and b * (Rg) -modules of color are set using the sum of the thicknesses of the individual layers closer to the substrate structure (ZA) of the intermediate layer. 13. The method according to p. 11 or 12, characterized in that the color reflection values from the side of the CIE L * a * b * color measurement system or the displacement of these values that occurs during the manufacture of the layer system is set or adjusted using the sum of the thicknesses of the individual layers structure (GA) of the base layer and / or structure (DA) of the covering layer. 14. The method according to p. 11, characterized in that at least one blocking layer (UFAB, MFAB, OFAB) is deposited from a ceramic containing substoichiometric antioxidant niobium oxide by ion sputtering in a working atmosphere to which no oxygen is added . 15. The method according to p. 11, characterized in that the sum of the thicknesses of the individual layers to be deposited, at least the structure (ZA) of the intermediate layer, is determined by first determining it for the desired reflection value in CIE L * a * b * -system of color measurements at a perpendicular viewing angle and then precipitated with a layer thickness increased by 2-13%. 16. Glass block with at least two glass substrates (S, S0), which are connected with or without distance to each other using means for connecting glass substrates (S, S0), characterized in that one of the glass substrates (S, S0) has a layer system according to any one of paragraphs. 1-10.

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