A functional layer of Low-E coated glass, Low-E coated glass and its preparation method

Abstract

This invention relates to a functional layer for Low-E coated glass, Low-E coated glass, and a method for preparing the same. The functional layer comprises a high-entropy alloy substrate layer and a ceramic interface layer disposed above the high-entropy alloy substrate layer. The high-entropy alloy substrate layer contains a CuNiAlSiMnTa high-entropy alloy. The CuNiAlSiMnTa high-entropy alloy, by atomic percentage, comprises: Cu: 35%~50%, Ni: 15%~25%, Al: 10%~20%, Si: 5%~15%, Mn: 3%~8%, and Ta: 5%~12%, with the sum of each atomic percentage being 100%. The functional layer provided by this invention utilizes the synergistic effect of the high-entropy alloy substrate layer and the ceramic interface layer to achieve comprehensive performance optimization in terms of cost, weather resistance, temperability, and high performance.

Description

Technical Field

[0001] This invention relates to the field of building energy-saving glass technology, specifically to a functional layer of Low-E coated glass, Low-E coated glass and its preparation method. Background Technology

[0002] Low-emissivity (Low-E) glass, through the deposition of low-emissivity functional films on its surface, effectively reflects infrared radiation, making it a key material for building energy conservation. Its core performance depends on the infrared reflectivity of the functional layer, typically achieved using the precious metal silver (Ag) or its alloys.

[0003] Currently, the mainstream functional layer technologies for Low-E glass mainly include three technical solutions: silver (Ag) functional layers, copper (Cu) or simple alloy functional layers, and metal-free functional layers based on transparent conductive oxide (TCO). Among them, silver (Ag) functional layers are irreplaceable functional layer materials for high-performance Low-E glass due to silver's extremely high electrical conductivity and excellent optical properties. However, they have the following problems: (1) High cost, with drastic fluctuations in silver prices, affecting product costs and supply chain security; (2) Poor chemical stability, as silver readily reacts with sulfides in the air to form silver sulfide, leading to blackening of the film and performance degradation, i.e., the "black edge" problem; (3) Insufficient thermal stability, as silver atoms easily diffuse and agglomerate during the glass tempering process (600℃), resulting in a sharp increase in sheet resistance and deterioration of emissivity. This makes it difficult to temper high-performance double-silver / triple-silver Low-E glass, limiting its application range. To reduce costs, the industry has explored replacing silver with copper by using copper (Cu) or its simple alloy functional layers. Although the electrical conductivity of pure copper is close to that of silver, its chemical properties are extremely active and it oxidizes rapidly in the air, making it completely unusable directly. Although binary alloys such as copper-nickel (CuNi) can be used to improve corrosion resistance, there are still fundamental limitations: (1) the improvement in anti-oxidation and anti-sulfurization capabilities is limited, and the long-term durability cannot meet the requirements of harsh environments; (2) there is no essential improvement in high-temperature stability. Copper-based alloys will still undergo severe interdiffusion and recrystallization at tempering temperatures, resulting in small performance degradation and poor temperability. Metal-free functional layers based on transparent conductive oxides (TCO), such as indium tin oxide (ITO) and aluminum-doped zinc oxide (AZO), have stable chemical properties, but their infrared reflectance performance is limited by their carrier concentration and mobility, and their emissivity (usually >0.15) is much higher than that of silver-based thin films (which can be <0.03), which cannot meet the demand for ultimate thermal insulation performance in high-end energy-saving buildings.

[0004] Therefore, existing Low-E glass functional layer materials cannot achieve comprehensive optimization in terms of cost, weather resistance, temperability, and high performance. There is an urgent need to provide a functional material that can simultaneously achieve infrared performance close to that of silver, environmental stability surpassing that of copper alloys, and superior high-temperature processability. Summary of the Invention

[0005] To address the above problems, the present invention aims to provide a functional layer for Low-E coated glass, Low-E coated glass, and a method for preparing the same.

[0006] To achieve this objective, the present invention employs the following technical solution: In a first aspect, the present invention provides a functional layer for Low-E coated glass, the functional layer comprising a high-entropy alloy body layer and a ceramic interface layer disposed above the high-entropy alloy body layer; The high-entropy alloy host layer contains CuNiAlSiMnTa high-entropy alloy; The CuNiAlSiMnTa high-entropy alloy comprises, by atomic percentage: Cu: 35%~50%, Ni: 15%~25%, Al: 10%~20%, Si: 5%~15%, Mn: 3%~8%, Ta: 5%~12%, and the sum of the atomic percentages is 100%.

[0007] High-entropy alloys are solid solutions formed by five or more principal elements. Their unique high-entropy effect, lattice distortion effect, hysteresis diffusion effect, and cocktail effect give them excellent properties such as high strength, high hardness, corrosion resistance, and resistance to high-temperature softening.

[0008] The functional layer provided by this invention employs a high-entropy alloy main layer and its composition is designed to fully utilize the inherent hysteresis diffusion effect and lattice distortion effect of the high-entropy alloy. Tantalum acts like countless microscopic "pins," locking grain boundaries, dislocations, and surrounding atoms, preventing the material from deforming, diffusing, or failing under extreme conditions. The functional layer provided by this invention exhibits slow atomic diffusion at high temperatures and structural stability. After tempering, its sheet resistance and emissivity show minimal changes, demonstrating excellent temperability. Simultaneously, the synergistic effect of multiple elements provides the functional layer with oxidation resistance, sulfide resistance, and corrosion resistance, significantly extending its service life. Furthermore, while achieving high environmental stability, the functional layer provided by this invention maintains high visible light transmittance and low infrared emissivity, meeting the requirements of high-end energy-efficient buildings.

[0009] Specifically, Cu in high-entropy alloys possesses low radiation, optical color adjustment, and good electrical conductivity; Ni significantly improves the hardness and wear resistance of the alloy layer, enhances the temperability of the glass, and reduces film damage; Al, Si, and other elements can form a dense passivation film on the surface, improving the weather resistance of the glass; Mn actively captures sulfur, effectively preventing Cu from being sulfided; Ta further blocks oxygen diffusion, protecting Cu from oxidation. By optimizing the proportions of these components to form a high-entropy alloy solid solution, the weather resistance, temperability, and optical properties of coated glass can be comprehensively improved, while reducing production costs.

[0010] In this invention, the Cu content in the CuNiAlSiMnTa high-entropy alloy is 35% to 50%, for example, it can be 35%, 38%, 40%, 42%, 45%, 48%, or 50%, but is not limited to the listed values; other unlisted values ​​within the range are also applicable. The Ni content is 15% to 25%, for example, it can be 15%, 18%, 20%, 22%, or 25%, but is not limited to the listed values; other unlisted values ​​within the range are also applicable. The Al content is 10% to 20%, for example, it can be 10%, 12%, 15%, 18%, or 20%, but is not limited to the listed values. The listed values ​​also apply to other values ​​not listed within the range; the Si percentage is 5% to 15%, for example, it can be 5%, 8%, 10%, 12% or 15%, but is not limited to the listed values, and other values ​​not listed within the range also apply; the Mn percentage is 3% to 8%, for example, it can be 3%, 5%, 6% or 8%, but is not limited to the listed values, and other values ​​not listed within the range also apply; the Ta percentage is 5% to 12%, for example, it can be 5%, 8%, 10% or 12%, but is not limited to the listed values, and other values ​​not listed within the range also apply.

[0011] Preferably, the thickness of the high-entropy alloy main layer is 8~20nm, for example, it can be 8nm, 9nm, 10nm, 11nm, 12nm, 13nm, 14nm, 15nm, 16nm, 17nm, 18nm, 19nm or 20nm, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0012] In this invention, by further optimizing and controlling the thickness of the high-entropy alloy main layer, the influence of the multi-metal components in the high-entropy alloy on the transmittance can be reduced, the transmittance can be improved, and the optical performance can be optimized.

[0013] Preferably, the ceramic interface layer is made of any one or a combination of at least two of tantalum nitride, tantalum oxide, or tantalum oxynitride.

[0014] In this invention, by setting a ceramic interface layer and designing its composition, the protective effect of components such as tantalum nitride, tantalum oxide, or tantalum oxynitride can be further enhanced, thereby improving the weather resistance of the coated glass.

[0015] Preferably, the thickness of the ceramic interface layer is 2~10nm, for example, it can be 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm or 10nm, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0016] In this invention, by further controlling the thickness of the ceramic interface layer, the overall performance of the film layer can be further optimized, such as the film layer color and optical parameters, while improving the weather resistance and oxidation resistance of the film layer.

[0017] In a second aspect, the present invention provides a Low-E coated glass, the Low-E coated glass comprising a glass substrate and a composite film system disposed on the glass substrate; The composite film system includes the functional layer of Low-E coated glass as described in the first aspect of the present invention.

[0018] The coated glass provided by this invention, employing the aforementioned functional layer, can achieve comprehensive performance optimization in terms of cost, weather resistance, temperability, and high performance.

[0019] Preferably, the composite film system includes a first dielectric film system, the functional layer, and a second dielectric film system sequentially disposed from the surface of the glass substrate outwards.

[0020] Preferably, the first dielectric film system or the second dielectric film system each independently includes at least one dielectric layer.

[0021] Preferably, the dielectric layer is made of any one of silicon nitride, zinc oxide, tin oxide, titanium dioxide, or niobium oxide.

[0022] Preferably, the thickness of the first dielectric film system is 15~70nm, for example, it can be 15nm, 20nm, 30nm, 40nm, 50nm, 60nm or 70nm, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0023] Preferably, the thickness of the second dielectric film system is 30-100nm, for example, it can be 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm or 100nm, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0024] Thirdly, the present invention provides a method for preparing Low-E coated glass as described in the second aspect of the present invention, the method comprising the following steps: Preparation of high-entropy alloy host layer: High-entropy alloy host layer was deposited by magnetron sputtering in a vacuum environment; Preparation of ceramic interface layer: Maintaining a vacuum environment, a reactive gas is introduced to form a ceramic interface layer in situ on the high-entropy alloy host layer.

[0025] In this invention, during the preparation of the high-entropy alloy host layer, the target material can be selected and matched according to the composition of the target CuNiAlSiMnTa high-entropy alloy, including but not limited to any one or at least two combinations of CuNiAlSiMnTa alloy target, CuNi alloy target, AlSi alloy target, MnTa alloy target, Cu target, Ni target, Al target, Si target, Mn target or Ta target.

[0026] In this invention, the CuNiAlSiMnTa alloy target is an alloy target sintered according to the atomic percentage of CuNiAlSiMnTa high-entropy alloy in the high-entropy alloy host layer.

[0027] Preferably, during the process of depositing the high-entropy alloy host layer using magnetron sputtering, an inductively coupled plasma atomic emission spectrometer is used to monitor the spectral intensity of each characteristic element in the sputtering plasma online, thereby adjusting the sputtering power of the target material so that the composition of the high-entropy alloy host layer conforms to the designed atomic ratio.

[0028] Preferably, the method for forming the ceramic interface layer in situ includes reactive sputtering and / or plasma treatment.

[0029] Preferably, the preparation method further includes depositing a first dielectric film system on the surface of a glass substrate before preparing the high-entropy alloy host layer.

[0030] Preferably, the preparation method further includes depositing a second dielectric film system on the surface of the ceramic interface layer after preparing the ceramic interface layer.

[0031] In this invention, magnetron sputtering, reactive sputtering, and plasma treatment are all conventional preparation processes in the art. Those skilled in the art can adjust the process parameters as needed to obtain the desired film material and thickness. Exemplarily, the preparation method includes, but is not limited to, the following steps: S1, Substrate preparation: Transparent float glass is used, which is cleaned by Benteler, rinsed with deionized water, dried with nitrogen, and then sent into the vacuum coating chamber.

[0032] S2, Deposition equipment preparation: Use a multi-target magnetron co-sputtering system and select the required target material according to the material of the film.

[0033] S3, Deposition process: S31, Preparation of the first dielectric film system: Deposition is carried out under a gas pressure of 0.2~0.5Pa. The atmosphere, target material, sputtering power and sputtering time are selected according to the material and thickness of the target first dielectric film system to obtain the first dielectric film system of the required thickness. S32, Preparation of high-entropy alloy host layer: In a pure argon atmosphere, the argon flow rate is 700~800 sccm, the sputtering power is set to 1~10kW, the working pressure is 0.2~0.7Pa, the substrate temperature is 30~100℃, and the plasma emission spectrometer is started to monitor the intensity of characteristic spectral lines of Cu, Ni, Al, Si, Mn, and Ta in real time online. When the intensity of a certain element deviates from the preset value, the system fine-tunes the sputtering power of the target area to achieve dynamic stability of composition and meet the designed atomic ratio. Sputtering is ≤1min, and a high-entropy alloy host layer is deposited. S33, Preparation of ceramic interface layer: After depositing the high-entropy alloy host layer, without disrupting the vacuum environment, one or more of argon, nitrogen or oxygen are introduced into the chamber in front of the same target site at a pressure of 0.2~0.5 Pa. The sputtering mode is switched to pulse mode to bombard and react the surface of the newly deposited high-entropy alloy host layer with plasma at a power of 0.1~1 kW for a time of ≤1 min, thereby forming a ceramic interface layer in situ. S34, Preparation of the second dielectric film system: Deposition is carried out under a pressure of 0.2~0.5 Pa. The atmosphere, target material, sputtering power and sputtering time are selected according to the material and thickness of the target second dielectric film system to obtain the second dielectric film system of the required thickness.

[0034] Compared with the prior art, the present invention has the following beneficial effects: (1) The functional layer provided by the present invention adopts the synergistic effect of high-entropy alloy main layer and ceramic interface layer, which can give full play to the hysteresis diffusion effect and lattice distortion effect of high-entropy alloy. At high temperature, atomic diffusion is slow and the structure is stable. After tempering treatment, its sheet resistance and emissivity change little, and it has good temperability. At the same time, the multi-element synergistic cocktail effect makes the functional layer have anti-oxidation, anti-sulfurization and corrosion resistance, and significantly extends its service life. At the same time, the functional layer provided by the present invention can still maintain high visible light transmittance and low infrared emissivity while obtaining high environmental stability, which meets the requirements of high-end energy-saving buildings.

[0035] (2) The Low-E coated glass provided by the present invention, using the aforementioned functional layer, can achieve comprehensive performance optimization in terms of cost, weather resistance, temperability, and high performance. Under optimal conditions, the Low-E coated glass provided by the present invention has the following initial optical properties: visible light transmittance of ≥53.0% and emissivity of ≤0.120. After tempering, the visible light transmittance reaches ≥55.0% and emissivity reaches ≤0.100. Adhesion test shows no peeling, and neutral salt spray test shows no corrosion after 100 hours.

[0036] (3) The preparation method provided by the present invention can achieve accurate and uniform deposition of coating components, laying the foundation for industrial production. Detailed Implementation

[0037] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0038] The numerical range described in this invention includes not only the point values ​​listed above, but also any point values ​​within the numerical ranges not listed above. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific point values ​​included in the range.

[0039] Example 1 This embodiment provides a functional layer for Low-E coated glass, comprising a high-entropy alloy substrate layer and a ceramic interface layer disposed above the high-entropy alloy substrate layer. The high-entropy alloy substrate layer contains a CuNiAlSiMnTa high-entropy alloy, which, by atomic percentage, comprises: Cu: 40%, Ni: 20%, Al: 15%, Si: 10%, Mn: 5%, and Ta: 10%. The thickness of the high-entropy alloy substrate layer is 12 nm. The ceramic interface layer is composed of tantalum nitride and has a thickness of 3 nm.

[0040] This embodiment provides a Low-E coated glass, comprising a Si3N4 layer (thickness 50nm), a ZnO layer (thickness 15nm), the aforementioned functional layer (thickness 15nm), and a Si3N4 layer (thickness 45nm) sequentially disposed from the surface of the glass substrate outward.

[0041] This embodiment provides a method for preparing the above-mentioned Low-E coated glass, which employs a multi-target magnetron co-sputtering system. The preparation method includes the following steps: S1, Substrate preparation: 6mm thick transparent float glass is used. After Benteler cleaning, deionized water rinsing, and nitrogen drying, it is sent into the vacuum coating chamber.

[0042] S2, Deposition Equipment Preparation: Use a horizontal magnetron sputtering deposition production line equipped with four rectangular rotating targets. The target configuration is as follows: Target 1: Si target (for reactive sputtering of Si3N4); Target 2: Zn target (for reactive sputtering of ZnO); Target 3: Cu 40 Ni 20 Al 15 Si 10 Mn5Ta 10 Hexa-element alloy sintered target (dimensions: length × width × thickness = approximately 3000 mm × approximately 160 mm × approximately 10 mm); Target position 4: Si target (for reactive sputtering of Si3N4).

[0043] S3, Deposition process: S31, Preparation of the first dielectric film system (Si3N4 layer and ZnO layer): The glass substrate first passes through target 1, and in a mixed atmosphere of argon and nitrogen, the argon flow rate is 600 sccm, the nitrogen flow rate is 800 sccm, the gas pressure is 0.4 Pa, the sputtering power is 10 kW, and the sputtering time is 5 min, and a Si3N4 layer is deposited first. After passing through target 2, in a mixed atmosphere of argon and oxygen, with an argon flow rate of 600 sccm, an oxygen flow rate of 800 sccm, a gas pressure of 0.4 Pa, a sputtering power of 3 kW, and a sputtering time of 2 min, a ZnO layer was deposited. S32, Preparation of the high-entropy alloy host layer: The glass substrate is placed into target position 3. In a pure argon atmosphere, the argon flow rate is 600 sccm, the sputtering power is set to 3 kW, the working pressure is 0.3 Pa, and the substrate temperature is 60 ℃. The plasma emission spectrometer is started to monitor the intensity of characteristic spectral lines of Cu, Ni, Al, Si, Mn, and Ta in real time. When the intensity of a certain element deviates from the preset value, the system fine-tunes the sputtering power of the target area to achieve dynamic stability of composition and meet the designed atomic ratio. After sputtering for 16 s, a high-entropy alloy host layer is deposited. S33, Preparation of ceramic interface layer: After depositing the high-entropy alloy substrate layer, without disrupting the vacuum environment, argon and nitrogen are introduced into the chamber in front of the same target position. The argon flow rate is 600 sccm, the nitrogen flow rate is 800 sccm, the working pressure is 0.3 Pa, and the sputtering mode is switched to pulse mode to bombard and react the surface of the high-entropy alloy substrate layer with plasma at a power of 1 kW for 30 s, forming a ceramic interface layer in situ. S34, Preparation of the second dielectric film system (Si3N4 layer): The glass substrate is then conveyed to target 4. In a mixed atmosphere of argon and nitrogen, the argon flow rate is 600 sccm, the nitrogen flow rate is 800 sccm, the gas pressure is 0.4 Pa, the sputtering power is 20 kW, and the sputtering time is 5 min to deposit a Si3N4 layer.

[0044] Example 2 This embodiment provides a functional layer for Low-E coated glass. The only difference from Embodiment 1 is that the CuNiAlSiMnTa high-entropy alloy in the main high-entropy alloy layer comprises, by atomic percentage: Cu: 35%, Ni: 25%, Al: 10%, Si: 15%, Mn: 3%, Ta: 12%, with a thickness of 8nm.

[0045] This embodiment also provides a Low-E coated glass and its preparation method. The difference between the preparation method and that in Embodiment 1 is that the target material at target site 3 in step S32 is replaced with Cu. 35Ni 25 Alloy target and Al 10 Si 15 Mn3Ta 12 The alloy target was sputtered in a pure argon atmosphere with an argon flow rate of 600 sccm, a sputtering power of 1 kW, a working pressure of 0.2 Pa, and a substrate temperature of 60 °C. The plasma emission spectrometer was activated to monitor the intensity of characteristic spectral lines of Cu, Ni, Al, Si, Mn, and Ta in real time. When the intensity of a certain element deviated from the preset value, the system fine-tuned the sputtering power of the target to achieve dynamic stability of the composition and meet the designed atomic ratio. Sputtering lasted for 40 seconds, and the thickness of the deposited high-entropy alloy host layer was controlled to be 8 nm.

[0046] Example 3 This embodiment provides a functional layer for Low-E coated glass. The only difference from Embodiment 1 is that the CuNiAlSiMnTa high-entropy alloy in the main high-entropy alloy layer comprises, by atomic percentage: Cu: 50%, Ni: 15%, Al: 20%, Si: 5%, Mn: 5%, Ta: 5%, with a thickness of 20nm.

[0047] This embodiment also provides a Low-E coated glass and its preparation method. The difference between the preparation method and that in Embodiment 1 is that the target material at target site 3 in step S32 is replaced with Cu. 50 Ni 15 Al 20 The Si5Mn5Ta5 hexa-element alloy sintering target was sputtered in a pure argon atmosphere with an argon flow rate of 600 sccm, a sputtering power of 1 kW, a working pressure of 0.5 Pa, and a substrate temperature of 60 °C. The plasma emission spectrometer was activated to monitor the intensity of characteristic spectral lines of Cu, Ni, Al, Si, Mn, and Ta in real time. When the intensity of a certain element deviated from the preset value, the system fine-tuned the sputtering power of the target material to achieve dynamic stability of the composition and meet the designed atomic ratio. Sputtering was performed for 1 minute, and the thickness of the deposited high-entropy alloy host layer was controlled to be 20 nm.

[0048] Example 4 This embodiment provides a functional layer for Low-E coated glass. The only difference from Embodiment 1 is that the ceramic interface layer is composed of tantalum oxide and has a thickness of 2 nm.

[0049] This embodiment also provides a Low-E coated glass and its preparation method. The difference between the preparation method and that in Embodiment 1 is only that in step S33: after depositing the high-entropy alloy host layer, without disrupting the vacuum environment, argon and oxygen are introduced into the chamber in front of the same target position. The argon flow rate is 600 sccm, the oxygen flow rate is 50 sccm, the working pressure is 0.2 Pa, and the sputtering mode is switched to pulse mode to bombard and react the surface of the high-entropy alloy host layer with plasma. The power is 0.4 kW and the time is 10 s, forming a ceramic interface layer with a thickness of 2 nm in situ.

[0050] Example 5 This embodiment provides a functional layer for Low-E coated glass. The only difference from Embodiment 1 is that the ceramic interface layer is composed of tantalum oxynitride and has a thickness of 10 nm.

[0051] This embodiment also provides a Low-E coated glass and its preparation method. The difference between the preparation method and that in Embodiment 1 is only in step S33: after depositing the high-entropy alloy host layer, without disrupting the vacuum environment, argon, nitrogen and oxygen are introduced into the chamber in front of the same target position. The argon flow rate is 600 sccm, the nitrogen flow rate is 50 sccm, the oxygen flow rate is 50 sccm, the working pressure is 0.22 Pa, and the sputtering mode is switched to pulse mode to bombard and react the surface of the high-entropy alloy host layer with plasma. The power is 0.6 kW and the time is 15 s, forming a ceramic interface layer with a thickness of 10 nm in situ.

[0052] Example 6 This embodiment provides a functional layer for Low-E coated glass, which differs from Embodiment 1 only in that the thickness of the high-entropy alloy main layer is 5 nm.

[0053] This embodiment also provides a Low-E coated glass and its preparation method. The difference between the preparation method and that in Embodiment 1 is that the sputtering time and power are adjusted in step S32 to control the thickness of the high-entropy alloy host layer to 5 nm.

[0054] Example 7 This embodiment provides a functional layer for Low-E coated glass, which differs from Embodiment 1 only in that the thickness of the high-entropy alloy main layer is 25 nm.

[0055] This embodiment also provides a Low-E coated glass and its preparation method. The difference between the preparation method and that in Embodiment 1 is that the sputtering time and power are adjusted in step S32 to control the thickness of the high-entropy alloy host layer to be 25 nm.

[0056] Comparative Example 1 This comparative example provides a functional layer for Low-E coated glass. The only difference from Example 1 is that the CuNiAlSiMnTa high-entropy alloy in the high-entropy alloy body layer, by atomic percentage, includes: Cu: 40%, Ni: 10%, Al: 15%, Si: 20%, Mn: 10%, Ta: 5%, and the thickness is the same as the high-entropy alloy body layer in Example 1.

[0057] This comparative example also provides a Low-E coated glass and its preparation method. The difference between the preparation method and Example 1 is that the target material at target site 3 in step S32 is replaced with Cu. 40 Ni 10 Al 15 Si 20 Mn 10 The Ta5 hexa-element alloy sintering target was used in a pure argon atmosphere with an argon flow rate of 600 sccm, a sputtering power of 1 kW, a working pressure of 0.7 Pa, and a substrate temperature of 100 °C. The plasma emission spectrometer was activated to monitor the intensity of characteristic spectral lines of Cu, Ni, Al, Si, Mn, and Ta in real time. When the intensity of a certain element deviated from the preset value, the system fine-tuned the sputtering power of the target material to achieve dynamic stability of the composition and meet the designed atomic ratio. The sputtering time was adjusted, and the thickness of the deposited high-entropy alloy main layer was controlled in the same way as in Example 1.

[0058] Comparative Example 2 This comparative example also provides a Low-E coated glass, which differs from Example 1 only in that the high-entropy alloy main body layer is replaced with a Cu layer, and the thickness is the same as that of the high-entropy alloy main body layer in Example 1.

[0059] This comparative example also provides a Low-E coated glass and its preparation method. The difference between the preparation method and Example 1 is that the target material of target position 3 in step S32 is replaced with a Cu target. In a pure argon atmosphere, the argon flow rate is 600 sccm, the sputtering power is set to 2 kW, the working pressure is 0.4 Pa, the substrate temperature is 80 °C, the sputtering time is adjusted, and the thickness of the deposited Cu layer is controlled to be the same as that of the high-entropy alloy main layer in Example 1.

[0060] Comparative Example 3 This comparative example also provides a conventional silver-based Low-E coated glass, the only difference from Example 1 being that the high-entropy alloy main layer is replaced with an Ag layer, with the same thickness as the high-entropy alloy main layer in Example 1; and the ceramic interface layer is replaced with a NiCr layer, with the same thickness as the ceramic interface layer in Example 1.

[0061] This comparative example also provides a Low-E coated glass and its preparation method. The difference between the preparation method and Example 1 is that the target material of target site 3 in step S32 is replaced with an Ag target. In a pure argon atmosphere, the argon flow rate is 600 sccm, the sputtering power is set to 3 kW, the working pressure is 0.4 Pa, the substrate temperature is 60°C, and the sputtering time is adjusted to control the thickness of the deposited Ag layer to be the same as that of the high-entropy alloy main layer in Example 1. In step S33, a NiCr target is used. In a pure argon atmosphere, the argon flow rate is 600 sccm, the sputtering power is set to 0.5 kW, the working pressure is 0.4 Pa, the substrate temperature is 70°C, and the sputtering time is adjusted to control the thickness of the deposited NiCr layer to be the same as that of the ceramic interface layer in Example 1.

[0062] [Performance Testing] The Low-E coated glass obtained in the above embodiments and comparative examples was subjected to performance tests.

[0063] [Initial Optical Performance Test] Visible light transmittance was measured using a spectrophotometer; emissivity ε was measured using an emissivity meter, and the results are shown in Table 1.

[0064] [Temperable Testing] The samples were subjected to simulated tempering treatment at 680℃ in an air atmosphere (heated for 5 min, then air-cooled). The visible light transmittance and emissivity ε of the tempered samples were measured, and the results are shown in Table 1.

[0065] Corrosion Resistance Test Neutral salt spray test: After 100 hours of testing in a 1% sodium chloride salt spray, the presence or absence of corrosion was observed. The results are shown in Table 1.

[0066] Adhesion According to GB / T 9286-2021, adhesion was tested using a 100-cross pattern. The results are shown in Table 1. The rating standards range from 0 to 5: Level 0 indicates that the cut edges are completely smooth with no peeling and excellent adhesion; Level 1 indicates that there is a small amount of peeling at the intersections, with a peeling area ≤5%; Level 2 indicates that the peeling area is 5-15%; Level 3 indicates that the peeling area is 15-35%; Level 4 indicates that the peeling area is 35-65%; and Level 5 indicates that there is a large area of ​​peeling, exceeding 65%, and extremely poor adhesion.

[0067] Table 1 The following points can be observed from the data in Table 1: (1) As can be seen from the data of Examples 1 to 5, under better conditions, the initial optical properties of the Low-E coated glass provided by the present invention are as follows: the visible light transmittance reaches more than 53.0% and the emissivity reaches less than 0.120. After tempering, the visible light transmittance reaches more than 55.0% and the emissivity reaches less than 0.100. The adhesion test shows no peeling and the neutral salt spray test shows no corrosion after 100 hours.

[0068] (2) As can be seen from the comparison between Example 1 and Examples 6-7, by further controlling the thickness of the high-entropy alloy main layer, the present invention can further ensure visible light transmittance, emissivity and sheet resistance, and ensure good optical performance and corrosion resistance.

[0069] (3) As can be seen from the comparison between Example 1 and Comparative Examples 1 to 3, the difference between the present invention and Comparative Example 1 is that the proportion of each element in the high-entropy alloy main layer is reasonably controlled. The difference between the present invention and 2 to 3 is that a specific high-entropy alloy main layer and ceramic interface layer are used to replace the existing conventional Cu or Ag functional layer and NiCr dielectric layer. The Low-E coated glass provided by the present invention can ensure that the optical performance changes little before and after tempering when the initial optical performance is similar, and has strong adhesion and strong corrosion resistance in neutral salt spray test.

[0070] In summary, the functional layer provided by this invention utilizes a high-entropy alloy main layer and a ceramic interface layer in synergy, which can achieve comprehensive performance optimization in terms of cost, weather resistance, temperability, and high performance.

[0071] The above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A functional layer for Low-E coated glass, characterized in that, The functional layer includes a high-entropy alloy main body layer and a ceramic interface layer disposed above the high-entropy alloy main body layer; The high-entropy alloy host layer contains CuNiAlSiMnTa high-entropy alloy; The CuNiAlSiMnTa high-entropy alloy comprises, by atomic percentage: Cu: 35%~50%, Ni: 15%~25%, Al: 10%~20%, Si: 5%~15%, Mn: 3%~8%, Ta: 5%~12%, and the sum of the atomic percentages is 100%.

2. The functional layer according to claim 1, characterized in that, The thickness of the high-entropy alloy host layer is 8~20nm.

3. The functional layer according to claim 1 or 2, characterized in that, The ceramic interface layer is made of any one or a combination of at least two of tantalum nitride, tantalum oxide, or tantalum oxynitride.

4. The functional layer according to any one of claims 1 to 3, characterized in that, The thickness of the ceramic interface layer is 2~10nm.

5. A Low-E coated glass, characterized in that, The Low-E coated glass includes a glass substrate and a composite film system disposed on the glass substrate; The composite film system includes the functional layer of the Low-E coated glass as described in any one of claims 1 to 4.

6. The Low-E coated glass according to claim 5, characterized in that, The composite film system includes a first dielectric film system, the functional layer, and a second dielectric film system sequentially disposed from the surface of the glass substrate outwards. The first dielectric film system or the second dielectric film system each independently includes at least one dielectric layer; The dielectric layer is made of any one of silicon nitride, zinc oxide, tin oxide, titanium dioxide, or niobium oxide. The thickness of the first dielectric film system is 15-70 nm; The thickness of the second dielectric film system is 30-100 nm.

7. A method for preparing Low-E coated glass as described in claim 5 or 6, characterized in that, The preparation method includes the following steps: Preparation of high-entropy alloy host layer: High-entropy alloy host layer was deposited by magnetron sputtering in a vacuum environment; Preparation of ceramic interface layer: Maintaining a vacuum environment, a reactive gas is introduced to form a ceramic interface layer in situ on the high-entropy alloy host layer.

8. The preparation method according to claim 7, characterized in that, During the process of depositing a high-entropy alloy host layer using magnetron sputtering, an inductively coupled plasma atomic emission spectrometer is used to monitor the spectral intensity of each characteristic element in the sputtering plasma online, thereby adjusting the sputtering power of the target material so that the composition of the high-entropy alloy host layer conforms to the designed atomic ratio.

9. The preparation method according to claim 7 or 8, characterized in that, The method for forming the ceramic interface layer in situ includes reactive sputtering and / or plasma treatment.

10. The preparation method according to any one of claims 7 to 9, characterized in that, The preparation method further includes depositing a first dielectric film system on the surface of a glass substrate before preparing the high-entropy alloy host layer; And / or, the preparation method further includes depositing a second dielectric film system on the surface of the ceramic interface layer after preparing the ceramic interface layer.

Images