RU2721607C2 - Niobium-nickel-titanium alloy barrier for coatings with low emissivity - Google Patents

Abstract

FIELD: chemical or physical processes.

SUBSTANCE: invention relates to formation of low-emission coatings on transparent substrates and can be used for glazing windows of buildings and vehicles. In particular, disclosed is a method of forming a low-emission panel, comprising: providing a glass substrate; formation directly on and in contact with glass substrate layer containing Si and Zr; forming on a glass substrate on top of at least a layer containing Si and Zr, a layer containing zinc oxide; forming on a glass substrate a first infrared reflecting (IR) layer containing silver, wherein a first infrared reflecting layer containing silver, is formed directly on and in contact with a layer containing zinc oxide; and forming on the glass substrate on top and directly in contact with the first infrared reflecting layer containing silver, the layer containing the alloy, including nickel, titanium and niobium, and formation on a glass substrate on top of at least a layer containing an alloy containing nickel, titanium and niobium, a layer containing tin oxide. Nb has maximum content of metal from any metal in said alloy. Percentage of nickel in alloy is from 5 to 15 wt %, percentage of titanium in alloy is from 30 to 50 wt %, and percentage of niobium in alloy ranges from 40 to 60 wt %.

EFFECT: technical result is providing low-emission panel with improved strength while maintaining or improving desired optical characteristics.

8 cl, 10 dwg

Description

CROSS RELATIONS TO RELATED APPLICATIONS

[0001] This is a partially continuing application of US Patent Application No. 13/797504, filed March 12, 2013, which is incorporated herein by reference for all purposes.

FIELD OF THE INVENTION

[0002] The present invention generally relates to films providing high throughput and low emissivity, and more particularly to such films deposited on transparent substrates.

BACKGROUND

[0003] Sunlight transmission glasses are commonly used in applications such as building glass windows and vehicle windows, usually offering high visible light transmittance and low emissivity. A high visible light transmittance may allow more sunlight to pass through the glass windows, thus being desirable in many window applications. Low emissivity can block infrared (IR) radiation to reduce undesired room heating.

[0004] In glasses with low emissivity, IR radiation is mainly reflected with minimal absorption and emission, thereby reducing heat transfer to and from a surface with low emissivity. Low emissivity panels or low emission panels are often formed by depositing a reflective layer (e.g. silver) on a substrate such as glass. The overall quality of the reflective layer, for example with regard to texturing and crystallographic orientation, is important to achieve the desired characteristics, such as high transmittance of visible light and low emissivity (i.e., high heat reflection). In order to provide adhesion as well as protection, several other layers are usually formed both below and above the reflective layer. These various layers typically include layers of a dielectric such as silicon nitride, tin oxide and zinc oxide to provide a barrier between the bag and the substrate and between the bag and the environment, and also act as optical fillers, and function as antireflection layers to improve optical characteristics of the panel.

[0005] One known way to achieve low emissivity is to form a relatively thick layer of silver. However, as the thickness of the silver layer increases, the transmittance of visible light of the reflective layer decreases, as does the production rate, while the overall production costs increase. Therefore, it is desirable to form the silver layer as thin as possible, while providing emissivity that is suitable for low emission applications.

SUMMARY OF THE INVENTION

[0006] In some embodiments, barrier structures and methods for forming barrier structures for an infrared reflective layer are provided for use in low emissivity coatings. These barrier structures may include a ternary alloy of titanium, nickel and niobium. The percentage of titanium may be from 5 to 15 wt.%. The percentage of Nickel may be from 30 to 50 wt.%. The percentage of niobium can be from 40 to 60 wt.%.

[0007] In some embodiments, barrier structures and methods for forming barrier structures for an infrared reflective layer are provided for use in low emissivity coatings. These barrier structures may include a triple alloy of nickel, titanium, and niobium. The percentage of Nickel may be from 5 to 15 wt.%. The percentage of titanium may be from 30 to 50 wt.%. The percentage of niobium can be from 40 to 60 wt.%.

[0008] In some embodiments, an infrared reflective layer is formed on the underlying layer, such as an anti-reflective (antireflection) layer or an germ layer. This underlying layer may include metal oxide materials such as zinc oxide, doped zinc oxide, tin oxide, doped tin oxide or an oxide alloy of zinc and tin.

[0009] In some embodiments, barrier structures can be optimized for both their optical and mechanical properties, including low absorption of visible light, high transmittance of visible light, strong reflection of infrared light, and high mechanical resistance and adhesion characteristics. For example, a high nickel and niobium content can improve the resistance of the coating layers, for example, by strengthening the interface with the silver layer. A ternary alloy may show better overall performance compared to nickel binary alloys and other composition ranges of ternary nickel alloys.

BRIEF DESCRIPTION OF THE DRAWINGS

[0010] In order to facilitate understanding, identical reference signs have been used to indicate identical elements wherever possible. The drawings are not drawn to scale, and the relative sizes of the various elements in the drawings are shown schematically and not necessarily to scale.

[0011] the Techniques of the present invention can be easily understood when considering the following detailed description together with the accompanying drawings, in which:

[0012] FIG. 1A illustrates an exemplary thin film coating in accordance with some embodiments.

[0013] FIG. 1B illustrates a low emission transparent panel 105 in accordance with some embodiments.

[0014] FIG. 2A to 2B illustrate physical vapor deposition (VOCF) coating systems in accordance with some embodiments.

[0015] FIG. 3 illustrates an exemplary in-line deposition system in accordance with some embodiments.

[0016] FIG. 4 illustrates the dependence of the specific surface resistance of a low emission packet having various barrier materials in accordance with some embodiments.

[0017] FIG. 5 illustrates a process flow diagram for spraying coating layers in accordance with some embodiments.

[0018] FIG. 6 illustrates a process flow diagram for spraying coating layers in accordance with some embodiments.

[0019] FIG. 7 shows a table of data regarding the effectiveness of various materials as barrier layers.

[0020] FIG. 8 illustrates a process flow diagram for spraying coating layers in accordance with some embodiments.

DETAILED DESCRIPTION

[0021] The following is a detailed description of one or more embodiments together with the accompanying figures. This detailed description is provided in connection with such embodiments, but is not limited to any specific example. Scope is limited only by the claims, and numerous alternatives, modifications, and equivalents are covered. In the following description, numerous specific details are set forth in order to provide a thorough understanding. These details are given for the purpose of example, and the described techniques can be practiced in accordance with the claims without some or all of these specific details. For clarity of description, that technical material that is known in the technical fields related to the options for implementation is not described in detail in order to avoid unnecessarily complicating the description.

[0022] In some embodiments, methods and devices for manufacturing coated panels are disclosed. Coated panels may include coating layers formed thereon, such as a thin infrared reflective layer with a low resistivity, having a conductive material such as silver. The infrared reflective layer may include a conductive material, with a percentage of reflectance proportional to the conductivity. Thus, a metal layer, for example silver, can be used as a reflective infrared layer in coatings with low emissivity (emissivity). To maintain the conductivity of the infrared reflective layer, for example, a silver layer, for example, against oxidation from the deposition of subsequent layers or from subsequent high-temperature annealing, a barrier layer can be formed on the silver layer.

[0023] In some embodiments, methods and devices for manufacturing low emissivity coated panels are disclosed, which include depositing a barrier layer on a conductive layer such as silver, under conditions such that the resistivity of silver and, therefore, the emissivity of the panels coated, were optimal. For example, a low resistance silver layer or a low emissivity panel can be obtained by protecting with a barrier layer including an alloy of titanium, niobium and nickel.

[0024] Titanium can be used as a barrier to silver in coatings with low emissivity, partly due to its high affinity for oxygen, i.e. the attraction of oxygen, which prevents the oxidation of the silver layer. Low emissivity coatings using a titanium barrier can have excellent transmittance of visible light along with a minimum reflectance of infrared light. However, low emissivity coatings using a titanium barrier may have poor mechanical resistance, probably due to poor adhesion to the silver layer.

[0025] Nickel may be added to the titanium barrier layer to modify the characteristics of the barrier. In general, titanium-nickel alloys can improve corrosion resistance to acidic or alkaline solutions, while providing protection during high temperature oxidation. Nickel-containing alloys have been reported to have sufficient adhesion to the IR reflective layer, resulting in improved overall chemical and mechanical resistance.

[0026] In some embodiments, various nickel alloys have been evaluated, including binary nickel alloys (eg, nickel-chromium and nickel-titanium), and ternary nickel alloys (eg, nickel-titanium-niobium). Typically, different double nickel alloys may exhibit different efficiencies under different requirements. For example, nickel-titanium can provide a slight improvement in light transmission with minimal improvement in mechanical resistance. A higher nickel content in the titanium-nickel alloy may slightly improve silver adhesion. For example, 80 wt.% Nickel in titanium-nickel alloys may show better adhesion than titanium-nickel alloys having 50 wt.% Nickel. On the contrary, nickel-chromium can provide a significant improvement in mechanical resistance, but with poorer optical properties.

[0027] In some embodiments, nickel, titanium, and niobium ternary alloys can exhibit better overall performance, for example, better mechanical resistance than titanium, with improved adhesion to the silver layer. Ternary alloys of nickel, titanium and niobium can also provide a similar or slight improvement in optical properties, for example, a decrease in emissivity and absorption along with an increase in light transmittance. For example, resistance measurements indicate that ternary alloys provide better barrier protection than titanium and binary alloys, such as NiTi or NiCr.

[0028] It appears that literature suggests that niobium in titanium alloys may segregate at the interface, which may be useful for improving silver adhesion. However, not all ternary alloys of titanium, nickel, and niobium can exhibit good optical, electrical, and mechanical characteristics.

[0029] In some embodiments, ternary alloys of titanium, nickel and niobium are disclosed with various composition ranges that can provide excellent overall performance, including good optical properties along with good mechanical properties. For example, to improve mechanical resistance, without affecting the optical or electrical properties, a high percentage of niobium can be used, for example, between 40 and 80 wt.%. Similarly, to improve mechanical resistance, without affecting the optical or electrical properties, a relatively high percentage of nickel can be used, for example, higher than titanium, but lower than niobium, such as from 30 to 50 wt.%. The percentage of titanium may be low, for example, from 5 to 15 wt.%, To provide the desired optical properties. As an example, a ternary alloy having 50% by weight of niobium, 40% by weight of nickel and 10% by weight of titanium may exhibit better overall performance compared to titanium alloys and titanium-nickel alloys.

[0030] In some embodiments, ternary alloys of titanium, nickel, and niobium are disclosed with different composition ranges that can provide, for example, the desired (ie, relatively low) absorption, resistance, and emissivity. These alloys may include a high percentage of niobium, for example, between 40 and 60 wt.%, To improve mechanical resistance, without affecting the optical or electrical properties. A relatively high percentage of titanium can be used, for example, higher than nickel, but lower than niobium, such as from 30 to 50 wt.%. The percentage of nickel may be low, for example, from 5 to 15 wt.%. For example, a ternary alloy may include 50 wt.% Niobium, 40 wt.% Titanium and 10 wt.% Nickel.

[0031] In some embodiments, the barrier layer may include ternary oxide alloys of titanium, nickel, and niobium. The oxide alloy barrier may be a stoichiometric oxide, for example, containing enough oxygen to oxidize the ternary alloy. The oxide alloy barrier may be a suboxide alloy, for example, the number of oxygen atoms in the oxide alloy may be less than the stoichiometric ratio.

[0032] The barrier layer can improve low emissivity coated panels, for example, by reducing absorption in the visible region, for example, by providing high transmittance of visible light, minimizing or completely blocking the possibility of reactions with Ag, which can prevent color degradation of the coated system, leading to a neutral color of the panels and improving adhesion between Ag and the upper barrier layer.

[0033] In some embodiments, methods and devices for manufacturing low emissivity panels are disclosed that include a thin infrared reflective layer with low resistivity including a conductive material such as silver, gold or copper. This thin layer of silver can be thinner than 15 nm, for example, 7 or 8 nm. The silver layer may have a low roughness, and is preferably deposited on the germ layer, also having a low roughness. Low emissivity panels may have improved overall quality of the infrared reflective layer with respect to conductivity, physical roughness, and thickness. For example, the methods can provide improved conductivity of the reflective layer, so that the thickness of the reflective layer can be reduced while providing the desired low emissivity.

[0034] Typically, the reflective layer preferably has a low surface resistance, since low surface resistance is associated with low emissivity. In addition, the reflective layer is preferably thin to provide high light transmission in the visible region. Thus, in some embodiments, methods and devices are disclosed for depositing a thin and highly conductive reflective layer providing a coating layer with a high transmittance of visible light and low emissivity in the infrared region. These methods can also maximize the production volume, productivity and efficiency of the production process used to form the panels with low emissivity.

[0035] In some embodiments, enhanced coated transparent panels are disclosed, such as coated glass that has acceptable visible light transmission and IR reflection. Also disclosed are methods of manufacturing these improved transparent coated panels that contain specific layers in a coating package.

[0036] These coated transparent panels may include a glass substrate or any other transparent substrate, such as those made from organic polymers. Coated transparent panels can be used in window applications, such as windows for vehicles and for buildings, glass roofs or glass doors, both in monolithic glazing and in multilayer glazing with or without a plastic intermediate layer or gas-tight sealed intermediate space.

[0037] FIG. 1A illustrates an exemplary thin film coating in accordance with some embodiments. The barrier layer 115 is located on the infrared reflective layer 113, such as a silver layer, which is located on the substrate 110, with the formation of a transparent panel 100 with a coating that has high light transmission in the visible region and low infrared radiation.

[0038] Layer 115 can be deposited by spraying using various processes and equipment, for example, targets can be sprayed with direct current (DC), pulsed direct current, alternating current (AC), radio frequency (RF), or by any other suitable conditions. In some embodiments, methods are disclosed for physically depositing the coating from the vapor phase to deposit the layer 115 with minimal effect on the infrared reflective layer 113.

[0039] The infrared reflective layer may include a conductive material with a percentage of reflectance proportional to the conductivity. Typically, metals are used as infrared reflective layers, with silver providing a reflectance of 95 to 99%, and gold 98-99% in the infrared region. Thus, a metal layer, for example silver, can be used as an infrared reflective layer in low emissivity coatings. The deposition of the silver layer can be optimized to obtain a high conductivity, for example, by minimizing impurities in the silver layer.

[0040] In order to keep the silver layer as clean as possible, the layer located directly on top of the silver layer (for example, the barrier layer) is very important in protecting silver from oxidation, such as during the deposition process accompanied by oxygen during the deposition of subsequent layers . In addition, this barrier layer can prevent the silver layer from reacting with oxygen diffusing during the glass tempering process or during long-term use when part of the glass may be exposed to moisture or the environment.

[0041] In order to maintain the conductivity of the infrared reflective layer, for example a silver layer, for example, against oxidation from the deposition of subsequent layers or from subsequent high-temperature annealing, a barrier layer may be formed on the silver layer. This barrier layer may be a barrier to oxygen diffusion, protecting the silver layer from oxygen diffusing through the barrier to react with the silver layer.

[0042] In addition to the barrier property for oxygen diffusion, the barrier layer may have other desirable properties. For example, since the barrier layer is placed directly on the silver layer, low or zero solubility of the barrier material in silver is desirable in order to minimize the possibility of a reaction between the barrier layer and silver at the interface. The reaction between the barrier layer and silver can introduce impurities into the silver layer, potentially reducing conductivity.

[0043] Additionally, in the manufacture of low emissivity coated panels, high temperature processes can be used, for example, to anneal deposited films or to temper a glass substrate. These high temperature processes can have a negative effect on a low emissivity coating, such as a change in structure or optical properties, for example, refractive index n or absorption coefficient k of the coating films. Thus, thermal stability with respect to optical properties is desired, for example, the barrier material may have a low absorption coefficient, for example, low absorption in the visible region, both in metal form and in oxide form.

[0044] In some embodiments, barrier structures and methods for forming them are disclosed for an infrared reflective layer used in low emissivity coatings. These barrier structures can be formed on the infrared reflective layer to protect the infrared reflective layer from diffusion of impurities, together with a demonstration of good adhesion and good optical properties, for example, during the manufacturing process.

[0045] The barrier structure may include a ternary alloy of titanium, nickel and niobium. To improve the mechanical resistance properties without affecting the optical properties, a high percentage of niobium and a low percentage of nickel, for example, lower than niobium, can be used. To provide a barrier to oxygen diffusion to the underlying silver layer, a low percentage of nickel can be used, for example, lower than niobium and titanium.

[0046] In some embodiments, methods for forming a layer 115 on a coated article with a high transmittance and low emissivity having a substrate and a smooth metal reflective film including one of silver, gold or copper are disclosed. In some embodiments, other layers may be included, such as an oxide layer, a germ layer, a conductive layer, an antireflection layer, or a protective layer.

[0047] In some embodiments, coating packets are disclosed comprising several layers for various functional purposes. For example, these coating packets may contain a germ layer to facilitate deposition of the reflective layer, an oxygen diffusion layer located on the reflective layer to prevent oxidation of the reflective layer, a protective layer on the substrate to prevent physical or chemical wear, or an antireflection layer to reduce the reflection of visible light. These coating packets may contain several reflective layers to improve IR emissivity.

[0048] FIG. 1B illustrates a low emission transparent panel 105 in accordance with some embodiments. The low emissivity transparent panel may include a glass substrate 120 and a (low emission) low emissivity bag 190 formed on top of the glass substrate 120. The glass substrate 120 in some embodiments is made of glass, such as borosilicate glass, and has a thickness, for example, from 1 to 10 millimeters (mm). The substrate 120 may be square or rectangular and about 0.5-2 m in size. In some embodiments, the substrate 120 may be made, for example, of plastic or polycarbonate.

[0049] The low emission package 190 includes a lower protective layer 130, a lower oxide layer 140, a germ layer 150, a reflection layer 154, a barrier layer 156, an upper oxide layer 160, an optical filler layer 170 and an upper protective layer 180. Some layers may be optional. and other layers may be added, such as intermediate layers or adhesive layers. Below are details of the functionality provided by each of the layers 130-180.

[0050] The various layers in the low emission stack 190 can be formed sequentially (i.e., from bottom to top) on the glass substrate 120 using a process tool for physical vapor deposition (VOF) and / or reactive (or plasma enhanced) sputtering. In some embodiments, a low emission bag 190 is formed on the entire glass substrate 120. However, in other embodiments, a low emission bag 190 can be formed only on isolated portions of the glass substrate 120.

[0051] The lower protective layer 130 is formed on the upper surface of the glass substrate 120. The lower protective layer 130 may contain silicon nitride, silicon oxynitride or other nitride material, such as, for example, SiZrN, to protect other layers in the package 190 from diffusion from the substrate 120 or to improve the properties of reducing turbidity. In some embodiments, the lower protective layer 130 is made of silicon nitride and has a thickness of, for example, from about 10 nm to 50 nm, such as 25 nm.

[0052] The lower oxide layer 140 is formed on the lower protective layer 130 and on top of the glass substrate 120. The lower oxide layer is preferably a metal oxide or metal alloy layer and can function as an antireflection layer. The lower metal oxide layer 140 can improve the crystallinity of the reflective layer 154, for example, by improving the crystallinity of the germ layer for the reflective layer, as described in more detail below.

[0053] Layer 150 can be used to provide a germ layer for an IR reflective film, for example, a zinc oxide layer deposited before a silver reflective layer is deposited can provide a silver layer with a lower resistivity, which can improve its reflective characteristics. The germ layer may comprise a metal, such as titanium, zirconium and / or hafnium, or a metal alloy, such as zinc oxide, nickel oxide, chromium-nickel oxide, nickel alloy oxides, chromium oxides, or chromium alloy oxides.

[0054] In some embodiments, the germ layer 150 may be made of metal, such as titanium, zirconium and / or hafnium, and has a thickness of, for example, 50 angstroms or less. Typically, the germ layers are relatively thin layers of materials formed on the surface (for example, the substrate) to facilitate the specific characterization of the subsequent layer formed over this surface (for example, on the germ layer). For example, to affect the crystalline structure (or crystallographic orientation) of a subsequent layer, germ layers can be used, which is sometimes referred to as “pattern assembly”. More specifically, the interaction of the material of the subsequent layer with the crystalline structure of the germ layer causes the crystalline structure of the subsequent layer to form in a specific orientation.

[0055] For example, to promote the growth of the reflective layer in a particular crystallographic orientation, a metallic germ layer is used. In some embodiments, the implementation of the metal germ layer is a material with a hexagonal crystal structure and is formed with a crystallographic orientation (002), which promotes the growth of the reflective layer in orientation (111), when the reflective layer has a face-centered cubic crystal structure (for example, silver), which is preferred for low-emission panel applications.

[0056] In some embodiments, the crystallographic orientation can be determined using X-ray diffraction (XRD), which is based on observing the intensity of scattered X-rays incident on a layer, such as a silver layer or a germ layer, depending on the characteristics of the X-rays, such like angles of incidence and scattering. For example, the germinal layer of zinc oxide can exhibit a pronounced peak (002) and higher orders in the θ - 2θ diffraction pattern. This suggests that zinc oxide crystallites are present with corresponding planes oriented parallel to the surface of the substrate.

[0057] In some embodiments, the terms “silver layer having a crystallographic orientation (111)” or “germinal layer of zinc oxide having a crystallographic orientation (002)” mean that there is a crystallographic orientation (111) for the silver layer or a crystallographic orientation ( 002) for the germinal layer of zinc oxide, respectively. The crystallographic orientation can be determined, for example, by observing pronounced crystallographic peaks in an XRD study.

[0058] In some embodiments, the germ layer 150 may be continuous and cover the entire substrate. Alternatively, the germ layer 150 may be intermittently formed. The germ layer can be distributed on the surface of the substrate so that each of the regions of the germ layer is spaced from other regions of the germ layer on the surface of the substrate and does not completely cover the surface of the substrate. For example, the thickness of the germ layer 150 may be a monolayer or less, such as from 2.0 to 4.0 angstroms, and the separation between sections of this layer may result from the formation of such a thin germ layer (i.e., such a thin layer may not form a continuous layer) .

[0059] A reflective layer 154 is formed on the germ layer 150. The IR reflective layer may be a metal reflective film, such as a silver, gold or copper film. Typically, an infrared reflective film contains a good electrical conductor blocking the passage of thermal energy. In some embodiments, the reflection layer 154 is made of silver and has a thickness of, for example, 100 angstroms. Since the reflection layer 154 is formed on the germ layer 150, for example, due to the crystallographic orientation (002) of the germ layer 150, the growth of the silver reflection layer 154 in the crystalline orientation (111) is supported, which provides a low surface resistance, resulting in a low emissivity of the panel.

[0060] Due to the pronounced textured orientation (111) of the reflection layer 154 caused by the germ layer 150, the conductivity and emissivity of the reflection layer 154 are improved. As a result, a thinner reflection layer 154 can be formed that still provides sufficient reflectance and visible light transmittance. Additionally, the reduced thickness of the reflective layer 154 allows the use of less material in each panel produced, thereby improving productivity and production efficiency, increasing the useful life of the target (e.g. silver) used to form the reflective layer 154, and reducing overall manufacturing costs.

[0061] Additionally, the germ layer 150 may provide a barrier between the metal oxide layer 140 and the reflection layer 154, reducing the likelihood of any reaction of the material of the reflection layer 154 and oxygen in the lower metal oxide layer 140, especially during subsequent heating processes. As a result, the resistivity of the reflective layer 154 can be reduced, thereby increasing the efficiency of the reflective layer 154 by lowering the emissivity.

[0062] The barrier layer 156 formed on the reflection layer 154 can protect the reflection layer 154 from oxidation. For example, the barrier may be a diffusion barrier that stops the diffusion of oxygen into the silver layer from the upper oxide layer 160. The barrier layer 156 may include titanium, nickel, and niobium. In some embodiments, the implementation of the barrier layer 156 may include titanium, nickel, niobium and oxygen.

[0063] The upper oxide layer formed on the barrier layer 156 can function as an antireflection film package including a single layer or several layers for various functional purposes. The antireflection layer 160 serves to reduce the reflection of visible light and is selected based on the transmittance, refractive index, adhesion, chemical resistance and heat resistance. In some embodiments, the antireflection layer 160 comprises tin oxide, providing high heat resistance properties. The antireflection layer 160 may also include titanium dioxide, silicon nitride, silicon dioxide, silicon oxynitride, niobium oxide, SiZrN, tin oxide, zinc oxide or any other suitable dielectric material.

[0064] The optical filler layer 170 can be used to provide a suitable thickness for the low emission bag, for example, to provide an antireflection performance. The optical filler layer preferably has a high transmittance of visible light. In some embodiments, the optical filler layer 170 is made of tin oxide and has a thickness of, for example, 100 angstroms. The optical filler layer can be used to adjust the optical properties of the low emission panel 105. For example, the thickness and refractive index of the optical filler layer can be used to increase the layer thickness to several wavelengths of incoming light, effectively reducing light reflectance and improving light transmission in the visible region.

[0065] The upper protective layer 180 can be used to protect the entire package of films, for example, to protect the panel from physical or chemical wear. The upper protective layer 180 may be an external protective layer, such as silicon nitride, silicon oxynitride, titanium oxide, tin oxide, zinc oxide, niobium oxide or SiZrN.

[0066] In some embodiments, adhesive layers may be used to provide adhesion between the layers. The adhesive layers can be made of a metal alloy, such as nickel-titanium, and have a thickness of, for example, 30 angstroms.

[0067] Depending on the materials used, some of the layers of the low emission stack 190 may have some common elements. An example of such a package can use zinc-based material in oxide dielectric layers 140 and 160. As a result, a relatively small number of different targets can be used to form the low-emission package 190.

[0068] In some embodiments, the coating may comprise a double or triple layer stack having multiple IR reflective layers. In some embodiments, these layers can be formed using plasma enhanced or reactive sputtering in which a carrier gas (e.g. argon) is used to knock out ions from the target that then pass through a mixture of carrier gas and reactive gas (e.g. oxygen) or plasma before precipitation.

[0069] In some embodiments, the effects of the deposition of layers on a conductive silver layer on the quality of this conductive silver layer are disclosed. Since it is desirable that the conductive layer of silver be thin, for example, less than 20 nm, to ensure a high transmittance of visible light, the deposition of a subsequent layer, such as a barrier layer or an antireflection layer, can affect the quality of the conductive silver layer.

[0070] In some embodiments, spray deposition processes are disclosed that can be applied to a barrier layer deposited on a conductive layer. For example, the barrier layer can protect the infrared reflective layer from oxidation. The oxide layer may function as an antireflection layer. The materials of the barrier layer can reduce the reaction for the underlying conductive layer, such as oxidation, preventing deterioration in emissivity and resistivity.

[0071] In some embodiments, deposition processes and coated articles made by this process using a layer comprising an alloy of a material with a high affinity for oxygen and a material with a low affinity for oxygen during spray deposition, for example, to obtain layers, are disclosed. with higher quality coatings and coated panels.

[0072] In some embodiments, the alloy barrier layer can be sprayed from a doped target, or simultaneously sprayed from different elementary targets onto the same substrate. This process can be performed in pure Ar (which will precipitate a clean metal barrier layer) or can include oxygen to make the film slightly oxidized.

[0073] FIG. 2A to 2B illustrate physical vapor deposition (VOCF) systems in accordance with some embodiments. In FIG. 2A, the PFGF system 200, also commonly referred to as a spray system or a spray deposition system, includes a housing that restricts or encloses a process chamber 240, a substrate 230, a target assembly 210, and reaction materials supplied from an external source 220. During deposition, the target is bombarded by argon ions, which releases particles sprayed towards the substrate 230. The spray system 200 may deposit a surface layer on the entire surface of the substrate 230, forming a deposited layer that covers the entire substrate, for example, that region of the substrate that can be reached by atomized particles, formed from the node 210 of the target.

[0074] The materials used in target 210 may, for example, include tin, zinc, magnesium, aluminum, lanthanum, yttrium, titanium, antimony, strontium, bismuth, niobium, silicon, silver, nickel, chromium, copper, gold, or any their combination (that is, a single target can be made of an alloy of several metals). Additionally, materials used in the targets may include oxygen, nitrogen, or a combination of oxygen and nitrogen in order to form the oxides, nitrides, and oxynitrides of the metals described above. Additionally, although only one target node 210 is shown, additional target nodes may be used. In fact, various combinations of targets can be used to form, for example, the above dielectric layers. For example, in some embodiments in which the barrier material is a titanium-nickel-niobium alloy, titanium, nickel and niobium can be provided with separate targets of titanium, nickel and niobium, or they can be provided with a single target of titanium-nickel-niobium alloy. For example, the target assembly 210 may comprise a silver target and, together with argon ions, deposit a layer on the substrate 230. The target assembly 210 may include a target of a metal or metal alloy such as tin, zinc or a tin-zinc alloy, and together with reactive oxygen species to spray a layer of a metal oxide or an alloy of metal oxides.

[0075] The spray deposition system 200 may include other components, such as a substrate base for supporting the substrate. The substrate base may include a vacuum holder, an electrostatic holder, or other known mechanisms. The base of the substrate can be configured to rotate about its axis perpendicular to the surface of the substrate. In addition, the substrate base can move in the vertical direction or in the horizontal direction. It should be borne in mind that rotation and movement in the vertical direction or horizontal direction can be achieved using known drive mechanisms, which include magnetic drives, linear drives, worm screws, spindles, a differential-pumped rotary feed drive, etc.

[0076] In some embodiments, the substrate base includes an electrode that is connected to a power source, for example, to supply RF bias or DC bias to the substrate, or to provide a plasma medium in the process chamber 240. Target assembly 210 may include an electrode that is connected to a power source to create a plasma in the process chamber. The node 210 of the target is preferably oriented in the direction of the substrate 230.

[0077] The spray deposition system 200 may also include a power source coupled to the target electrode. This power source supplies voltage to the electrodes, causing the material, in at least some embodiments, to be sprayed from the target. During spraying, inert gases such as argon or krypton can be introduced into the process chamber 240 through a gas inlet 220. In embodiments using reactive sputtering, reactive gases, such as oxygen and / or nitrogen, can also be introduced that interact with particles emitted from the targets to form oxides, nitrides and / or oxynitrides on the substrate.

[0078] The spray deposition system 200 may also include a control system (not shown) having, for example, a processor and a memory that is operatively connected to other components and configured to control their operation to perform the methods described herein.

[0079] In some embodiments, methods and devices are disclosed for creating layers above a thin silver layer with low resistance, including controlling ion energy on a substrate so that deposition is performed at low ion energy, which can reduce damage to the underlying silver layer.

[0080] FIG. 2B shows a sputtering system with simultaneously sputtered targets in accordance with some embodiments. Spray deposition chamber 205 may include two targets 212 and 214 located in a plasma medium 245 containing reactants supplied from an external source 225. Targets 212 and 214 may include a first alloy barrier element, for example, Ta, Nb, Zr, Hf, Mn, Y, Si, and Ti, and a second alloy barrier element, for example, Pd, Ru, Ni, Co, Mo, and W, together with optional reactive oxygen species to deposit the alloy of the barrier layer on the substrate 230. This configuration serves as an example , and other atomization system configurations may be used, such as a single target configuration containing alloy material.

[0081] In some embodiments, methods and devices for manufacturing low emissivity panels are disclosed, including forming an infrared reflective layer below or above a barrier structure that includes a ternary alloy of titanium, nickel and niobium. These panels can exhibit optimal infrared reflectance, thermal stability, and durability, for example, due to a barrier layer protecting the infrared reflective layer without compromising low emissivity coatings.

[0082] In some embodiments, methods are disclosed for manufacturing low emissivity panels in large area coating devices. A transport mechanism may be provided for moving the substrate beneath one or more sputtering targets to deposit a conductive underlying layer before depositing a barrier layer and an antireflection layer together with other layers, such as a surface protective layer.

[0083] In some embodiments, in-line deposition systems are disclosed, including a transport mechanism for moving substrates between the deposition stations.

[0084] FIG. 3 illustrates an exemplary in-line deposition system in accordance with some embodiments. A transport mechanism 370, such as a conveyor belt or multiple rollers, can transfer the substrate 330 between different spray deposition stations. For example, a substrate may be placed at station # 1 having a target node 310A, then transferred to station # 2 having a target node 310B, and then transferred to station # 3 having a target node 310C. Station # 1 having a target 310A may be a silver deposition station sputtering an infrared reflective layer containing silver. Station # 2 having target 310B may be a barrier deposition station sputtering a metal alloy containing titanium, nickel and niobium. As shown, station # 2 includes a single target 310B. However, other configurations may be used, such as a simultaneous spray system using two different targets. Station # 3 having a target 310C may be used to deposit other layers, such as an antireflection layer or a protective layer.

[0085] In some embodiments, specific percentages of titanium, nickel, and niobium are provided to achieve excellent performance for all properties, including optical and mechanical properties. A high percentage of niobium can be used to improve mechanical properties, including adhesion, thermal stability, and panel resistance. For example, a content of more than 40 wt.% Niobium can be used to obtain the desired mechanical resistance, for example, comparable to NiCr alloy barriers and much better than titanium barriers. A niobium content below 60 wt.% Can be used so as not to impair optical efficiency, for example, to maintain a similar or better transmittance of visible light with low reflection or absorption. A low percentage of titanium can be used, for example, to provide barrier properties for oxygen diffusion. For example, a content of more than 5 wt.% Titanium can be used to provide a good oxygen barrier. A titanium content below 15 wt.% Can be used, which can still provide excellent barrier protection. The average percentage of nickel, for example, lower than niobium and higher than titanium, can be used to further improve the mechanical properties and maintain the properties of the oxygen barrier. For example, a nickel content of 30 to 50 wt.% Can improve the properties of both titanium and niobium without any deterioration. In some embodiments, the implementation of the thickness of the barrier may be from 0.3 to 8 nm, for example, from 0.5 to 5 nm.

[0086] In some embodiments, specific percentages of nickel, titanium, and niobium are proposed to achieve excellent performance, at least with respect to absorption, resistance, and emissivity (i.e., their relatively low values). For example, a content of more than 40 wt.% Niobium can be used to obtain the desired mechanical resistance, for example, comparable to NiCr alloy barriers and much better than titanium barriers. A niobium content below 60 wt.% Can be used so as not to impair optical efficiency, for example, to maintain a similar or better transmittance of visible light with low reflection or absorption. A low percentage of nickel (for example, from 5 wt.% To 15 wt.%) Can be used with an average percentage of titanium (for example, lower than niobium and higher than nickel, for example, from 30 wt.% To 50 wt.%). In some embodiments, the implementation of the thickness of the barrier may be from 0.3 to 8 nm, for example, from 0.5 to 5 nm.

[0087] FIG. 4 illustrates the surface resistance dependence of a low emission stack having various barrier materials, in accordance with some embodiments. Surface resistance can provide an estimate of optical properties with lower surface resistance values for the same silver layer thickness, which correlates with higher transmittance and lower reflection. The low-emission packets used in the measurement of surface resistance include a barrier layer on an 8 nm silver layer, which is located on a 10 nm germinal layer of ZnO. Barrier materials include titanium, a nickel-titanium alloy containing 20 wt.% Titanium and 80 wt.% Nickel, and a titanium-nickel-niobium alloy with 10 wt.% Nickel, 40 wt.% Titanium and 50 wt.% Niobium. The thickness of the barriers is in the range from 0.3 nm to 7 nm, for example, from 1.5 nm to 4.5 nm.

[0088] As shown, the ternary alloy of titanium, nickel and niobium has lower surface resistance, for example, better optical efficiency, for all thicknesses compared to the titanium alloy and the double titanium-nickel alloy. In this specific example, the barrier may have optimal efficiency at a thickness of about 2 nm, for example, from 1.5 to 2.7 nm.

[0089] FIG. 5 illustrates a process flow diagram for spraying coating layers in accordance with some embodiments. After a conductive layer, such as a silver layer, is formed on the substrate, a barrier layer can be deposited onto the conductive layer by sputtering. The barrier layer may include a ternary alloy of titanium, nickel and niobium, including ternary metal alloys, for example, consisting of metal components - titanium, nickel and niobium, and ternary oxide alloys, for example, containing titanium, nickel, niobium and oxygen.

[0090] In operation 500, a substrate is provided. The substrate may be a transparent substrate, such as a glass substrate or a polymer substrate. Other substrates may also be used. In operation 510, a first layer is formed on the substrate. The first layer may act as an infrared reflective layer. The first layer may include a conductive material or metallic material, such as silver. The thickness of the first layer may be less than or equal to about 20 nm, or may be less than or equal to about 10 nm.

[0091] In operation 520, a second layer is deposited on the first layer. The second layer may act as a barrier layer. The second layer may include an alloy of titanium, nickel and niobium. The percentage of titanium can be from 5 to 15 wt.%, The percentage of nickel can be from 30 to 50 wt.% (Or from 35 to 45 wt.%), And the percentage of niobium can be from 40 to 60 wt.% ( or from 45 to 55 wt.%).

[0092] In some embodiments, the second layer may include an alloy of nickel, titanium, and niobium. The percentage of nickel can be from 5 to 15 wt.%, The percentage of titanium can be from 30 to 50 wt.% (Or from 35 to 45 wt.%), And the percentage of niobium can be from 40 to 60 wt.% ( or from 45 to 55 wt.%).

[0093] In some embodiments, the second layer may also include oxygen to form an oxide alloy. The second layer can be deposited as a triple metal alloy or a triple oxide alloy. A ternary metal alloy can be oxidized, for example, by deposition of a subsequent layer, becoming a ternary oxide layer. The triple oxide alloy may also be further oxidized. After the entire package has been deposited and / or heat treated, the second layer may remain a triple metal alloy or may become a triple oxide or triple suboxide for a better emissivity characteristic.

[0094] In some embodiments, an underlying layer may be formed under the first layer, such as a germ layer of ZnO for the silver layer. The germ layer can improve the crystalline orientation of silver, leading to better conductivity. In some embodiments, other layers may be formed on the second layer.

[0095] FIG. 6 illustrates a process flow diagram for spraying coating layers in accordance with some embodiments. After a conductive layer, such as a silver layer, is formed on the substrate, a barrier layer can be deposited onto the conductive layer by sputtering. This barrier layer may include a ternary alloy of titanium, nickel and niobium.

[0096] In operation 600, a substrate is provided. The substrate may be a transparent substrate, such as a glass substrate or a polymer substrate. Other substrates may also be used. In operation 610, a metal oxide layer is formed on the substrate. The metal oxide layer may function as a germ layer for the subsequent layer. For example, the metal oxide layer may have a crystalline orientation that promotes the crystalline orientation of the first layer then deposited.

[0097] In some embodiments, the metal oxide layer may include a germ layer having a crystalline orientation that promotes the crystalline orientation of the (111) silver layer. For example, a metal oxide layer may include ZnO having a (002) crystalline orientation, which can serve as a template for growing a silver layer with an (111) orientation. The thickness of the metal oxide layer may be less than or equal to about 20 nm, or may be less than or equal to about 10 nm.

[0098] In operation 620, a first layer is formed on the metal oxide layer. The first layer may act as an infrared reflective layer. The first layer may include a conductive material or metallic material, such as silver. The thickness of the first layer may be less than or equal to about 20 nm, or may be less than or equal to about 10 nm.

[0099] In operation 630, a second layer is deposited on the first spray layer. The second layer may be a barrier layer. The second layer may include an alloy of titanium, nickel and niobium. The percentage of titanium can be from 5 to 15 wt.%, The percentage of nickel can be from 30 to 50 wt.% (Or from 35 to 45 wt.%), And the percentage of niobium can be from 40 to 60 wt.% ( or from 45 to 55 wt.%).

[00100] In some embodiments, the second layer may include an alloy of nickel, titanium, and niobium. The percentage of nickel can be from 5 to 15 wt.%, The percentage of titanium can be from 30 to 50 wt.% (Or from 35 to 45 wt.%), And the percentage of niobium can be from 40 to 60 wt.% ( or from 45 to 55 wt.%).

[00101] In some embodiments, the second layer may also include oxygen to form an oxide alloy. The second layer can be deposited as a triple metal alloy or a triple oxide alloy. A ternary metal alloy can be oxidized, for example, by deposition of a subsequent layer, becoming a ternary oxide layer. The triple oxide alloy may also be further oxidized. After the entire package has been deposited and / or heat treated, the second layer may remain a triple metal alloy or may become a triple oxide or triple suboxide for a better emissivity characteristic. In some embodiments, other layers may be included.

[00102] In some embodiments, the barrier layer (for example, the barrier layer 115 in FIG. 1A and / or the barrier layer 156 in FIG. 1B) comprises (for example, consists of) a triple alloy that includes less nickel than titanium and niobium ( for example, from 5 to 15 wt.% nickel, from 30 to 50 wt.% titanium and from 40 to 60 wt.% niobium). The effectiveness of the resulting barrier layer can vary depending (at least in part) on, for example, the amount of niobium compared to the amount of nickel and / or titanium.

[00103] FIG. 7 illustrates data related to the effectiveness of various materials for use in barrier layers. The materials presented include an alloy of nickel and chromium (i.e. 80 wt.% Nickel and 20 wt.% Chromium), an alloy of nickel and titanium and various alloys of nickel, titanium and niobium (i.e., with metal ratios of 15:60:25, 10:40 : 50 and 5:20:75). Of particular interest in FIG. 7 represents the efficiency of an alloy of nickel, titanium and niobium with a ratio of 10:40:50 compared to other materials, in particular other materials of nickel, titanium and niobium.

[00104] For example, when a relatively low amount of niobium is used (eg, 15 wt.% Nickel, 60 wt.% Titanium and 25 wt.% Niobium), this layer may exhibit relatively poor absorption (ie, absorption in the visible range of Avis, absorption in abs.% at a wavelength of 400 nm, 550 nm and 1000 nm), but suitable resistance (i.e., Rs) and emissivity (i.e., ε), at least comparable to nickel-chromium and nickel-titanium alloys. On the other hand, when a relatively large amount of niobium is used (for example, 5 wt.% Nickel, 20 wt.% Titanium and 75 wt.% Niobium), the absorption is suitable, but the resistance and emissivity are relatively poor. As shown, the efficiency is optimized (at least relatively) when using 50 wt.% Niobium (for example, 10 wt.% Nickel, 40 wt.% Titanium and 50 wt.% Niobium), since all of the absorption, resistance and emissivity are suitable (i.e. relatively low).

[00105] FIG. 8 illustrates a process flow diagram for spraying coating layers in accordance with some embodiments. After a conductive layer, such as a silver layer, is formed on the substrate, a barrier layer can be deposited onto the conductive layer by sputtering. The barrier layer may include a ternary alloy of titanium, nickel and niobium, including ternary metal alloys, for example, consisting of metal components - titanium, nickel and niobium, and ternary oxide alloys, for example, containing nickel, titanium, niobium and oxygen.

[00106] In operation 800, a substrate is provided. The substrate may be a transparent substrate, such as a glass substrate or a polymer substrate. Other substrates may also be used. In operation 810, a first layer is formed on the substrate. The first layer may act as an infrared reflective layer. The first layer may include a conductive material or metallic material, such as silver. The thickness of the first layer may be less than or equal to about 20 nm, or may be less than or equal to about 10 nm.

[00107] In operation 820, a second layer is deposited on the first spray layer. The second layer may act as a barrier layer. The second layer may include an alloy of nickel, titanium and niobium. The percentage of nickel can be from 5 to 15 wt.% (For example, 10 wt.% Or about 10 wt.%), The percentage of titanium can be from 30 to 50 wt.% (For example, 40 wt.% Or about 40 wt. %), and the percentage of niobium can be from 40 to 60 wt.% (for example, 50 wt.% or about 50 wt.%).

[00108] In some embodiments, the second layer may also include oxygen to form an oxide alloy. The second layer can be deposited as a triple metal alloy or a triple oxide alloy. A ternary metal alloy can be oxidized, for example, by deposition of a subsequent layer, becoming a ternary oxide layer. The triple oxide alloy may also be further oxidized. After the entire package has been deposited and / or heat treated, the second layer may remain a triple metal alloy or may become a triple oxide or triple suboxide for a better emissivity characteristic.

[00109] In some embodiments, at least some of the other layers shown and described above with reference to FIG. 1B can also be formed over the substrate to form a transparent panel with low emissivity. For example, in some embodiments, an underlying layer may be formed under the first layer, such as a germ layer of ZnO for a silver layer. The germ layer can improve the crystalline orientation of silver, leading to better conductivity. In some embodiments, other layers may be formed on the second layer.

[00110] Although the foregoing examples have been described with some details for purposes of clarity, the invention is not limited to these details. There are many alternative ways of carrying out the invention. The disclosed examples are illustrative and not restrictive.

Claims (22)

1. A method of forming a low emission panel, comprising: providing a glass substrate; forming directly on and in contact with the glass substrate a layer containing Si and Zr; forming on a glass substrate over at least a layer containing Si and Zr, a layer containing zinc oxide; forming on the glass substrate a first infrared reflecting (IR) layer containing silver, wherein the first infrared reflecting layer containing silver is formed directly on and in contact with the layer containing zinc oxide; and the formation on a glass substrate on top of and directly in contact with the first IR reflecting layer containing silver, a layer containing an alloy comprising nickel, titanium and niobium, with Nb having the highest metal content of any metal in said alloy; wherein the percentage of nickel in the alloy is from 5 to 15 wt.%, the percentage of titanium in the alloy is from 30 to 50 wt.%, and the percentage of niobium in the alloy is from 40 to 60 wt.%; and the formation on a glass substrate over at least a layer containing an alloy comprising nickel, titanium and niobium, a layer containing tin oxide. 2. The method according to p. 1, wherein the thickness of the layer containing the alloy comprising nickel, titanium and niobium is from 0.3 nm to 7 nm. 3. The method according to p. 1, wherein the layer containing the alloy, comprising nickel, titanium and niobium, further comprises oxygen. 4. The method of claim 1, wherein the thickness of said IR reflective layer is less than 15 nm. 5. A method of forming a low emission panel, comprising: providing a transparent glass substrate; forming directly on and in contact with the glass substrate a layer containing Si and Zr; forming over at least a layer containing Si and Zr, a layer containing zinc oxide; forming an IR reflecting layer containing silver on top of the transparent substrate, wherein the IR reflecting layer containing silver is placed on top and directly in contact with said zinc oxide containing layer; the formation on top and directly in contact with the infrared reflective layer containing silver, a layer containing an alloy comprising nickel, titanium and niobium, while niobium has the highest metal content of any metal in said alloy; wherein the percentage of nickel in the alloy is from 5 to 15 wt.%, the percentage of titanium in the alloy is from 30 to 50 wt.%, and the percentage of niobium in the alloy is from 40 to 60 wt.%; and the formation on a glass substrate over at least a layer containing an alloy comprising nickel, titanium and niobium, a layer containing tin oxide. 6. The method according to p. 5, wherein the thickness of the layer containing the alloy comprising nickel, titanium and niobium is from 0.3 nm to 7 nm. 7. The method according to p. 5, wherein the layer containing an alloy comprising nickel, titanium and niobium is oxidized. 8. The method according to p. 1, wherein said alloy consists essentially of Nb, Ti and Ni.

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