Low-radiation high-transmittance coated tempered glass and production process thereof

Abstract

The present application relates to a kind of low radiation high light transmission coated toughened glass and its production process, belong to glass product technical field.The glass includes glass substrate and functional film system deposited on its surface, by setting silicon-aluminum-nitrogen composite gradient medium layer between first silver layer and third silver layer, by linearly increasing nitrogen flow rate, its composition gradually changes from metal conductive state to nitrogen insulating state, and is doped with zirconium stable structure, so that the sheet resistance between two silver layers is regulated at 1.0×10 4 ‑5.0×10 5 Ω / □, realize hemispherical emissivity ε≤0.019, its outermost layer is zirconium oxide / silicon oxide stack with fixed optical thickness, used to offset the 550 nm reflection peak caused by internal gradient layer, so as to synergistically improve visible light transmittance ≥89.0%.The present application process is clear, solves the contradiction between high light transmission and low radiation under the condition of simplifying layer number, and product can be tempered in different places.

Description

Technical Field

[0001] This invention belongs to the field of glass product technology, and relates to a low-emissivity, high-transmittance coated tempered glass and its production process. Background Technology

[0002] Low-emissivity (Low-E) coated glass is a key material for building energy conservation. It achieves this by depositing multiple functional films on the glass surface, selectively reflecting mid- and far-infrared rays while ensuring high visible light transmittance, thus significantly reducing building heating and cooling energy consumption. Among these, triple-silver low-emissivity coated glass incorporates three independent silver (Ag) functional layers into the film system, enhancing its reflectivity in the far-infrared band and achieving a low hemispherical emissivity, resulting in superior thermal insulation performance.

[0003] However, in improving the performance of triple-silver low-emissivity glass, there is an inherent and difficult-to-optimize contradiction between its visible light transmittance (Tvis) and hemispherical emissivity (ε). The physical essence of this contradiction is that the thickness and continuity of the silver functional layer, which is the core of achieving low emissivity, directly determine the infrared reflection performance, i.e., hemispherical emissivity. However, the silver layer itself has strong absorption in the visible light band. Increasing the thickness of the silver layer or optimizing its continuity to pursue a lower hemispherical emissivity often exacerbates the absorption of visible light and the loss of interface reflection, resulting in a decrease in visible light transmittance. Conversely, thinning the silver layer to pursue a high visible light transmittance weakens its infrared reflection capability, resulting in an increase in hemispherical emissivity and a deterioration in heat insulation performance.

[0004] To reconcile this contradiction, existing technologies have continuously increased the total number of film layers, introduced more types of oxide and nitride media materials, and carried out extremely complex optical interference and stress buffer structure designs to balance visible light transmittance and hemispherical emissivity. However, this often leads to industrialization problems such as abnormally complex film structure, narrow production process window, high manufacturing cost, and difficulty in controlling product yield and batch stability. Other technologies use doped oxides and composite nitrides as media or protective layers to seek better optical or mechanical properties, but they do not have the high infrared reflectivity of metallic silver functional layers. The film systems prepared by these technologies do not inherently possess low-emissivity functions and cannot meet the stringent requirements for building energy conservation scenarios with thermal insulation performance, thus limiting their application scope.

[0005] Therefore, there is an urgent need for a new type of triple-silver low-emissivity coated glass and its production process, which has a simplified film structure, stable and controllable production process, and can synergistically achieve high visible light transmittance and low hemispherical emissivity, in order to promote the industrialization of high-performance energy-saving glass. Summary of the Invention

[0006] The purpose of this invention is to overcome the shortcomings of the prior art and provide a coated tempered glass with a simplified film structure, controllable process, and the ability to synergistically achieve high visible light transmittance and low hemispherical emissivity, as well as its production process.

[0007] To achieve the above objectives, the present invention adopts the following technical solution: In a first aspect, a low-emissivity, high-transmittance coated tempered glass is provided, comprising a glass substrate and a functional film system disposed on at least one surface of the glass substrate, wherein the functional film system comprises a first metallic silver functional layer, a second metallic silver functional layer, and a third metallic silver functional layer sequentially stacked. Between the first metallic silver functional layer and the third metallic silver functional layer, a silicon-aluminum-nitrogen composite dielectric layer is disposed. In the silicon-aluminum-nitrogen composite dielectric layer, from the side closer to the first metallic silver functional layer to the side closer to the third metallic silver functional layer, the ratio of nitrogen atom concentration to the sum of silicon and aluminum atom concentrations increases linearly. Furthermore, the silicon-aluminum-nitrogen composite dielectric layer is uniformly doped with 0.8-3.0 at.% zirconium. The sheet resistance of the silicon-aluminum-nitrogen composite dielectric layer formed between the first and third silver functional layers is 1.0 × 10⁻⁶. 4 -5.0×10 5 Ω / □; The outermost layer of the functional film system is a top optical protective layer, which, from the inside out, consists of a first zirconia sublayer, a silicon oxide sublayer, and a second zirconia sublayer. The optical thickness of the first zirconia sublayer is 62-68 nm, the optical thickness of the silicon oxide sublayer is 90-98 nm, and the physical thickness of the second zirconia sublayer is 15-25 nm. The coated tempered glass has a visible light transmittance ≥89.0% and a hemispherical emissivity ε ≤0.019.

[0008] Furthermore, the ratio of the nitrogen atom concentration to the sum of the silicon and aluminum atom concentrations increases linearly from 0.6-0.9 to 1.2-1.4.

[0009] Furthermore, the total number of layers in the functional membrane system is 14.

[0010] The total number of functional film layers is 14, including: bottom layer SiAlOx, thin layer NiCr, first metallic silver functional layer, gradient doped silicon aluminum nitrogen composite dielectric layer, middle layer SiAlOx, thin layer NiCr, second metallic silver functional layer, middle layer SiAlOx, thin layer NiCr, third metallic silver functional layer, thin layer NiCr, first zirconium oxide sublayer, silicon oxide sublayer, and second zirconium oxide sublayer.

[0011] Further, the thickness of the first silver metal functional layer is 10.8 - 11.6 nm, the thickness of the second silver metal functional layer is 8.8 - 9.6 nm, and the thickness of the third silver metal functional layer is 11.0 - 11.8 nm.

[0012] In a second aspect, a production process for preparing the low - emissivity and high - light - transmittance coated tempered glass as described above is provided, including the following steps: S1. Provide a glass substrate and perform surface cleaning and plasma activation pretreatment on it; S2. In a vacuum magnetron sputtering coating equipment, sequentially deposit each layer of the thin film constituting the functional film system on the surface of the pretreated glass substrate; S3. Perform low - temperature annealing treatment on the glass deposited with the functional film system; S4. Perform tempering treatment on the annealed glass; Among them, when depositing the silicon - aluminum - nitrogen composite dielectric layer in step S2, a silicon - aluminum alloy target is used, the working gas is argon and nitrogen, and the flow rate of nitrogen is controlled by a mass flow controller, so that the flow rate linearly increases from an initial value Q1 to a final value Q2 during the deposition duration of the silicon - aluminum - nitrogen composite dielectric layer. Here, 500 sccm ≤ Q1 < Q2 ≤ 800 sccm, and (Q2 - Q1) ≥ 150 sccm. At the same time, introduce the vapor of zirconium - containing organometallic precursor into the vacuum chamber of the vacuum magnetron sputtering coating equipment to co - dope zirconium element into the silicon - aluminum - nitrogen composite dielectric layer, and control the doping amount to be 0.8 - 3.0 at.%; Among them, when depositing the top - layer optical protection laminate in step S2, a zirconia target and a silica target are used for reactive sputtering, and the deposition parameters are controlled so that the optical thickness of the formed first zirconia sub - layer is 62 - 68 nm and the optical thickness of the formed silica sub - layer is 90 - 98 nm.

[0013] Further, in step S1, the plasma activation pretreatment is carried out in an argon atmosphere, the treatment pressure is 8.0×10 -2 -1.2×10 -1 Pa, and the plasma source power is 2.5 - 3.5 kW.

[0014] Further, in step S3, the temperature of the low - temperature annealing treatment is 280 - 350 °C, the heat - preservation time is 5 - 15 minutes, and the treatment atmosphere is air or nitrogen.

[0015] Further, in step S4, the process parameters of the tempering treatment are: the temperature of the heating furnace is 660 - 690 °C, the heating time is 220 - 260 s, and the rapid cooling air pressure is 2800 - 3500 Pa.

[0016] Furthermore, the zirconium-containing organometallic precursor is trimethylzirconium, which is introduced into the vacuum chamber via a carrier gas.

[0017] Thirdly, a building curtain wall or window is provided that uses the low-emissivity, high-transmittance coated tempered glass as described in the first aspect above.

[0018] The beneficial effects of this invention are: (1) In this invention, a breakthrough in low emissivity is achieved by introducing an “interface functional layer with adjustable electrical properties.” Specifically, a silicon-aluminum-nitrogen composite dielectric layer with a continuously gradient composition and doped with zirconium is deposited between the first and third silver layers, which determine the infrared reflectance performance. This causes the electrical properties to gradually change from a metal-like conductive state near the first silver layer to a silicon nitride-like insulating state near the third silver layer. This unique gradient structure forms a tunneling resistance channel with controllable resistance between the two silver layers, adjusting the sheet resistance between the first and third silver layers to 1.0 × 10⁻⁶. 4 Ω / □ to 5.0×10 5 The optimal range of Ω / □, within which the interface resistance is within the range, allows the two main silver layers to produce the best constructive interference effect in the far-infrared band reflected electromagnetic waves, enhancing the overall infrared reflectivity of the film system, thereby reducing the hemispherical emissivity of the glass to below 0.019.

[0019] (2) In this invention, a high visible light transmittance is achieved by designing an "optical stack with targeted compensation function". Specifically, for the characteristic reflection peak generated by the gradient layer near the wavelength of 550 nm, a zirconium oxide / silicon oxide phase compensation stack with a fixed optical thickness is constructed on the outermost layer. The optical thickness of zirconium oxide and the optical thickness of silicon oxide are both fixed values ​​optimized around λ=550 nm. This structure can induce interference light with the opposite phase to the internal reflection peak near 550 nm, thereby achieving active cancellation and light energy recovery of the characteristic reflection peak, effectively improving the transmittance of the entire visible light band, and finally increasing the visible light transmittance to more than 89.0%, overcoming the traditional technical contradiction that it is difficult to synergistically improve high transmittance and low emissivity.

[0020] (3) In this invention, while breaking through the performance indicators of visible light transmittance and emissivity, the structure and production process of the film system are simplified and optimized. The total number of functional film system layers is only 14, which reduces material consumption and process complexity, improves production efficiency and product yield. Moreover, the core process parameters of this invention are clear and easy to programmatically control. For example, the composition gradient is achieved by linearly increasing the nitrogen flow rate, zirconium doping is achieved by co-doping precursor vapor, and the top layer with fixed optical thickness is obtained by controlling the sputtering parameters. In addition, the proprietary low-temperature annealing process is used to stabilize the film system, ensuring the excellent thermal stability and off-site tempering of the product. The entire process path is clear and repeatable, and has excellent potential for large-scale production. Detailed Implementation

[0021] To further illustrate the technical means and effects of the present invention in achieving its intended purpose, the following detailed description of the specific implementation methods, structures, features, and effects of the present invention, in conjunction with embodiments, is provided below.

[0022] Example 1

[0023] S1, Glass substrate pretreatment

[0024] The glass substrate undergoes surface cleaning and plasma activation pretreatment. After cleaning, the surface of the glass substrate should be free of visible watermarks and oil stains. The plasma activation pretreatment is carried out in an argon atmosphere at a pressure of 1.0 × 10⁻⁶. -1 Pa, plasma source power is 3.0 kW.

[0025] S2, Functional film system deposited by vacuum magnetron sputtering

[0026] The following films are deposited sequentially on the pretreated glass substrate.

[0027] Deposition of the main film system: Bottom layer SiAlO x ; Thin-layer NiCr; The first metallic silver functional layer uses a high-purity silver (purity ≥99.99%) target and is sputtered in a pure argon atmosphere under the drive of a DC power supply of 5.2 kW. The glass substrate moving speed is controlled at 0.8 m / min, so that silver atoms grow at a deposition rate of about 0.14 nm / s under these conditions, and a silver film with a physical thickness of 11.2 nm is deposited. This layer serves as the first main reflective layer for reflecting far-infrared radiation. To achieve precise control of the interfacial resistance between the first and third silver layers, a gradient-doped silicon-aluminum-nitrogen composite dielectric layer was deposited. A silicon-aluminum alloy rotating target was used, and the nitrogen flow rate was linearly controlled via a mass flow controller under a constant argon flow rate of 400 sccm. Within a total deposition time of 300 seconds, the nitrogen flow rate was linearly increased from an initial value of 550 sccm to a final value of 750 sccm. This linear increase in nitrogen flow rate resulted in a continuous increase in nitrogen doping during film deposition. To stabilize the gradient structure and improve the thermal stability of the film, trimethylzirconium vapor was simultaneously introduced into the vacuum chamber during sputtering, with argon as the carrier gas at a flow rate of 18 sccm, achieving uniform co-doping of zirconium. Using a 12.0 kW DC power supply to drive the target, a glass substrate temperature of 160℃, and a moving speed of 0.8 m / min, a SiAlN:Zr film with a physical thickness of approximately 42 nm was finally obtained. X-ray photoelectron spectroscopy (XPS) analysis confirmed that the ratio of nitrogen atom concentration to the sum of silicon and aluminum atom concentrations in the film linearly increases from approximately 0.7 near the first silver layer to approximately 1.3 further away, achieving a continuous gradient from a "metal-like" weakly conductive state to a "silicon nitride-like" highly insulating state. The average zirconium content is approximately 2.0 at.%, with uniform distribution. This unique gradient structure forms a barrier-controlled tunneling resistance channel between the first and third silver layers, laying the electrical foundation for subsequent infrared coordinated reflection. Intermediate layer SiAlOx; Thin-layer NiCr; The second metallic silver functional layer is deposited using the same process as the first silver layer, with a physical thickness of 9.0 nm. This layer is mainly used for fine adjustment of the visible and near-infrared spectra. Intermediate layer SiAlO x ; Thin-layer NiCr; The third metallic silver functional layer: using the same process as the first silver layer, a silver film with a physical thickness of 11.5 nm is deposited. This layer serves as the second main reflective layer and needs to work in conjunction with the first silver layer. Thin-layer NiCr; Deposition and fixation of outer layer stacks: To counteract the characteristic reflection peak introduced by the internal gradient layer near 550 nm wavelength and maximize visible light transmittance, the following stacked structure was designed and deposited as the top protective layer. The innermost first zirconia sublayer and silicon oxide sublayer form an interference pair with a fixed optical thickness, specifically designed to counteract the characteristic reflection peak at 550 nm to maximize visible light transmittance. The outermost second zirconia sublayer primarily provides supplementary mechanical protection and fine-tuning of appearance and color.

[0028] The first zirconia sublayer was obtained by reactive sputtering in an argon-oxygen mixed atmosphere using a zirconia target at a power frequency of 40 kHz and a power of 90 kW. The sputtering time was controlled to be 60 seconds at a deposition rate of approximately 31 nm / min, resulting in a film with an optical thickness of approximately 65 nm. The silicon oxide sublayer was obtained by reactive sputtering in an argon-oxygen mixed atmosphere using a silicon oxide target at a power frequency of 40 kHz and a power of 75 kW. The sputtering time was controlled to be 60 seconds at a deposition rate of approximately 64 nm / min, resulting in a film with an optical thickness of approximately 94 nm. The second zirconia sublayer is fabricated using the same process as the first zirconia sublayer, with a sputtering time controlled at 40 seconds, resulting in a film with a physical thickness of approximately 20 nm. This sublayer primarily serves to supplement protection and fine-tune the appearance.

[0029] At this point, the deposition of a functional film system with a total of 14 layers (excluding the glass substrate) is complete.

[0030] S3, Low-temperature annealing treatment

[0031] The coated glass is then placed in a continuous annealing furnace and held at 320°C in air for 10 minutes.

[0032] S4, Tempered finish

[0033] The annealed glass is sent into a horizontal tempering furnace and heated at 675°C for 240 seconds to soften it uniformly. Then it is immediately sent into an air grid and rapidly quenched with uniform high-pressure cold air at 3200 Pa. A uniform compressive stress layer is formed on the glass surface, resulting in coated tempered glass that meets safety standards.

[0034] Example 2

[0035] S1, Glass substrate pretreatment

[0036] The glass substrate undergoes surface cleaning and plasma activation pretreatment. After cleaning, the surface of the glass substrate should be free of visible watermarks and oil stains. The plasma activation pretreatment is carried out in an argon atmosphere at a pressure of 8.0 × 10⁻⁶. -2 Pa, plasma source power is 2.5 kW.

[0037] S2, Functional film system deposited by vacuum magnetron sputtering

[0038] The following films are deposited sequentially on the pretreated glass substrate.

[0039] Deposition of the main film system: Bottom layer SiAlO x ; Thin-layer NiCr; The first metallic silver functional layer uses a high-purity silver (purity ≥99.99%) target and is sputtered in a pure argon atmosphere under the drive of a DC power supply of 4.8 kW. The glass substrate moving speed is controlled at 0.6 m / min, so that silver atoms grow at a deposition rate of about 0.10 nm / s under these conditions, and a silver film with a physical thickness of 10.8 nm is deposited. A gradient-doped silicon-aluminum-nitrogen composite dielectric layer was constructed using a silicon-aluminum alloy rotating target. Under a constant argon flow rate of 350 sccm, the nitrogen flow rate was linearly controlled via a mass flow controller: within a total deposition time of 350 seconds, the nitrogen flow rate was linearly increased from an initial value of 500 sccm to a final value of 650 sccm. This linear increase in nitrogen flow rate resulted in a continuous increase in nitrogen doping during film deposition. To stabilize the gradient structure and improve the thermal stability of the film, trimethylzirconium vapor was simultaneously introduced into the vacuum chamber during sputtering, using argon as the carrier gas at a flow rate of 12 sccm to achieve uniform co-doping of zirconium. Using a 10.0 kW DC power supply to drive the target, a glass substrate temperature of 150℃, and a moving speed of 1.0 m / min, a SiAlN:Zr film with a physical thickness of approximately 38 nm was finally obtained. X-ray photoelectron spectroscopy (in-depth analysis) confirmed that the ratio of nitrogen atom concentration to the sum of silicon and aluminum atom concentrations in the film increases linearly from about 0.6 near the first silver layer to about 1.2 away from the first silver layer, achieving a continuous gradual transition from a "metal-like" weakly conductive state to a "silicon nitride-like" highly insulating state. The average zirconium content is about 0.8 at.%, and the distribution is uniform. Intermediate layer SiAlOx; Thin-layer NiCr; The second functional silver layer is deposited using the same process as the first silver layer, with a physical thickness of 8.8 nm. Intermediate layer SiAlOx; Thin-layer NiCr; The third functional layer of metallic silver: A silver film with a physical thickness of 11.0 nm is deposited using the same process as the first silver layer; Thin-layer NiCr; Deposition and fixation of the top layer stack: The first zirconia sublayer was obtained by reactive sputtering in an argon-oxygen mixed atmosphere under the drive of a zirconia target at a medium frequency of 45 kHz and a power of 93 kW. The sputtering time was controlled at a deposition rate of about 35 nm / min and the film thickness was about 62 nm. The silicon oxide sublayer was obtained by reactive sputtering in an argon-oxygen mixed atmosphere using a silicon oxide target at a power frequency of 42 kHz and a power of 73 kW. The sputtering time was controlled at 57 seconds under the condition that the deposition rate was about 67 nm / min, resulting in a film with an optical thickness of about 90 nm. The second zirconia sublayer was fabricated using the same process as the first zirconia sublayer, with a sputtering time controlled at 43 seconds, resulting in a film with a physical thickness of approximately 15 nm.

[0040] At this point, the deposition of a functional film system with a total of 14 layers (excluding the glass substrate) is complete.

[0041] S3, Low-temperature annealing treatment

[0042] The coated glass is then placed in a continuous annealing furnace and held at 280°C in air for 15 minutes.

[0043] S4, Tempered finish

[0044] The annealed glass is sent into a horizontal tempering furnace and heated at 660°C for 260 seconds to soften the glass uniformly. Then it is immediately sent into an air grid and rapidly quenched with uniform high-pressure cold air at 2800 Pa. A uniform compressive stress layer is formed on the glass surface to obtain coated tempered glass.

[0045] Example 3

[0046] S1, Glass substrate pretreatment

[0047] The glass substrate undergoes surface cleaning and plasma activation pretreatment. After cleaning, the glass substrate surface should be free of visible watermarks and oil stains. The plasma activation pretreatment is carried out in an argon atmosphere at a pressure of 1.2 × 10⁻⁶. -1 Pa, plasma source power is 3.5 kW.

[0048] S2, Functional film system deposited by vacuum magnetron sputtering

[0049] The following films are deposited sequentially on the pretreated glass substrate.

[0050] Deposition of the main film system: The bottom layer is SiAlOx; Thin-layer NiCr; The first metallic silver functional layer uses a high-purity silver (purity ≥99.99%) target and is sputtered in a pure argon atmosphere under the drive of a DC power supply of 5.2 kW. The glass substrate moving speed is controlled at 1.0 m / min, so that silver atoms grow at a deposition rate of about 0.20 nm / s under these conditions, and a silver film with a physical thickness of 11.6 nm is deposited. To achieve precise control of the interfacial resistance between the first and third silver layers, a gradient-doped silicon-aluminum-nitrogen composite dielectric layer was deposited. A silicon-aluminum alloy rotating target was used, and the nitrogen flow rate was linearly controlled via a mass flow controller under a constant argon flow rate of 450 sccm. Within a total deposition time of 320 seconds, the nitrogen flow rate was linearly increased from an initial value of 650 sccm to a final value of 800 sccm. This linear increase in nitrogen flow rate resulted in a continuous increase in nitrogen doping during film deposition. To stabilize the gradient structure and improve the thermal stability of the film, trimethylzirconium vapor was simultaneously introduced into the vacuum chamber during sputtering, with argon as the carrier gas at a flow rate of 24 sccm, achieving uniform co-doping of zirconium. Using a 13.0 kW DC power supply to drive the target, a glass substrate temperature of 170℃, and a moving speed of 0.7 m / min, a SiAlN:Zr film with a physical thickness of approximately 45 nm was finally obtained. X-ray photoelectron spectroscopy depth analysis confirmed that the ratio of nitrogen atom concentration to the sum of silicon and aluminum atom concentration in the film layer increases linearly from about 0.9 near the first silver layer to about 1.4 away from the first silver layer, realizing a continuous gradual transition from a "metal-like" weakly conductive state to a "silicon nitride-like" highly insulating state. The average zirconium content is about 3.0 at.%, and the distribution is uniform. Intermediate layer SiAlO x ; Thin-layer NiCr; The second functional silver layer is deposited using the same process as the first silver layer, with a physical thickness of 9.6 nm. Intermediate layer SiAlO x ; Thin-layer NiCr; The third functional layer of metallic silver: A silver film with a physical thickness of 11.8 nm is deposited using the same process as the first silver layer; Thin-layer NiCr; Deposition and fixation of the top layer stack: The first zirconia sublayer was obtained by reactive sputtering in an argon-oxygen mixed atmosphere using a zirconia target at a power frequency of 42 kHz and a power of 90 kW. The sputtering time was controlled to be 63 seconds at a deposition rate of approximately 35 nm / min, resulting in a film with an optical thickness of approximately 68 nm. The silicon oxide sublayer was obtained by reactive sputtering in an argon-oxygen mixed atmosphere using a silicon oxide target at a power frequency of 40 kHz and a power of 75 kW. The sputtering time was controlled to be 61 seconds at a deposition rate of approximately 62 nm / min, resulting in a film with an optical thickness of approximately 98 nm. The second zirconia sublayer is fabricated using the same process as the first zirconia sublayer, with a sputtering time controlled at 40 seconds, resulting in a film with a physical thickness of approximately 25 nm.

[0051] At this point, the deposition of a functional film system with a total of 14 layers (excluding the glass substrate) is complete.

[0052] S3, Low-temperature annealing treatment

[0053] The coated glass is then placed in a continuous annealing furnace and held at 350°C in air for 5 minutes.

[0054] S4, Tempered finish

[0055] The annealed glass is sent into a horizontal tempering furnace and heated at 690°C for 220 seconds to soften the glass uniformly. Then it is immediately sent into an air grid and rapidly quenched with uniform high-pressure cold air at 3500 Pa. A uniform compressive stress layer is formed on the glass surface to obtain coated tempered glass.

[0056] Comparative Example 1

[0057] Based on Example 1, when depositing the SiAlN layer: the linear control program for nitrogen flow rate was turned off and replaced with a constant flow rate of 650 sccm, while other conditions remained the same as in Example 1.

[0058] Comparative Example 2

[0059] Based on Example 1, the top layer with a fixed optical thickness was replaced with a conventional thickness: ZrO2 (30 nm) / SiO2 (20 nm) / ZrO2 (30 nm), while other conditions remained the same as in Example 1.

[0060] Comparative Example 3

[0061] Based on Example 1, the gradient layer process was changed: the starting flow rate of N2 was set to 700 sccm, the ending flow rate to 750 sccm, and other conditions remained the same as in Example 1.

[0062] Comparative Example 4

[0063] Based on Example 1, the gradient layer process was changed: the starting flow rate of N2 was set to 450 sccm, the ending flow rate to 550 sccm, and other conditions remained the same as in Example 1.

[0064] Effect test

[0065] The samples prepared in Examples 1-3 and Comparative Examples 1-4 were tested. The test items included the sheet resistance of the first / third silver layer, visible light transmittance, and hemispherical emissivity. The test methods for each performance index are as follows: Visible light transmittance is referenced to the national standard GB / T 2680-2021 "Determination of visible light transmittance, direct solar transmittance, total solar transmittance, ultraviolet transmittance and related window glass parameters of architectural glass".

[0066] The hemispherical emissivity is referenced to the national standard GB / T 18915.2-2013 "Coated Glass Part 2: Low Emissivity Coated Glass".

[0067] Sheet resistance between the first and third silver layers: After the third silver layer is deposited and before the top protective layer is deposited, the sheet resistance between the first and third silver layers is directly measured at the four corners of the sample glass slide using a four-probe tester (Jandel RM3000). During measurement, ensure good ohmic contact between the probe and the film surface and read stable values.

[0068] The test results are shown in Table 1: Table 1 Performance test results of each sample

[0069] The results show that Examples 1-3 exhibit better overall performance, with Example 1 showing the best overall performance. Compared to the examples, Comparative Examples 3 and 4 show significantly worse hemispherical emissivity, indicating that controlling the interface sheet resistance between the first and third silver layers within the specific range disclosed in this invention is an important electrical condition for achieving low hemispherical emissivity. Comparative Example 1 shows high interface resistance and poor performance, demonstrating that the gradient-doped SiAlN structure is the foundation for achieving suitable interface resistance and excellent performance. Comparative Example 2 shows a decrease in visible light transmittance, but with similar interface resistance, indicating that the synergy between the internal gradient layer and the external compensation layer is an important condition for achieving high visible light transmittance and low hemispherical emissivity.

[0070] In summary, this invention achieves a fixed optical thickness for a zirconium oxide / silicon oxide top layer by linearly controlling nitrogen flow rate and co-doping zirconium precursor to form a gradient SiAlN layer, and by controlling sputtering time based on a calibrated deposition rate. The final product, after testing, exhibits a visible light transmittance of 89.8%, a hemispherical emissivity of 0.017, and a sheet resistance of 3.3 × 10⁻⁶ between the first and third silver layers. 4 The Ω / □ synergistic solution addresses the challenge of balancing light transmittance and emissivity in triple-silver low-emissivity glass with a simplified structure, providing a high-performance, low-cost, and easy-to-produce energy-saving glass product and manufacturing process.

[0071] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A low-emissivity, high-transmittance coated tempered glass, characterized in that, It includes a glass substrate and a functional film system provided on at least one surface of the glass substrate. The functional film system includes a first silver metal functional layer, a second silver metal functional layer, and a third silver metal functional layer that are sequentially stacked. A silicon-aluminum-nitrogen composite dielectric layer is provided between the first silver metal functional layer and the third silver metal functional layer. In the silicon-aluminum-nitrogen composite dielectric layer, the ratio of the nitrogen atom concentration to the sum of the silicon and aluminum atom concentrations increases linearly from the side close to the first silver metal functional layer to the side close to the third silver metal functional layer, and the silicon-aluminum-nitrogen composite dielectric layer is uniformly doped with 0.8 - 3.0 at.% of zirconium element. The sheet resistance of the silicon-aluminum-nitrogen composite dielectric layer formed between the first and third silver functional layers is 1.0 × 10⁻⁶. 4 -5.0×10 5 Ω / □; The outermost layer of the functional film system is a top-layer optical protection laminate, which sequentially includes a first zirconia sub-layer, a silica sub-layer, and a second zirconia sub-layer from the inside to the outside. The optical thickness of the first zirconia sub-layer is 62 - 68 nm, the optical thickness of the silica sub-layer is 90 - 98 nm, and the physical thickness of the second zirconia sub-layer is 15 - 25 nm. The visible light transmittance of the coated and tempered glass is ≥89.0%, and the hemispherical emissivity ε ≤ 0.

019.

2. The low-emissivity, high-transmittance coated tempered glass according to claim 1, characterized in that, The ratio of the nitrogen atom concentration to the sum of the silicon and aluminum atom concentrations increases linearly from 0.6 - 0.9 to 1.2 - 1.

4.

3. The low-emissivity, high-transmittance coated tempered glass according to claim 1, characterized in that, The total number of layers of the functional film system is 14 layers.

4. The low-emissivity, high-transmittance coated tempered glass according to claim 1, characterized in that, The physical thickness of the first silver metal functional layer is 10.8 - 11.6 nm, the physical thickness of the second silver metal functional layer is 8.8 - 9.6 nm, and the physical thickness of the third silver metal functional layer is 11.0 - 11.8 nm.

5. A manufacturing process for preparing low-emissivity, high-transmittance coated tempered glass as described in any one of claims 1-4, characterized in that, It includes the following steps: S1. Provide a glass substrate, and perform surface cleaning and plasma activation pretreatment on it. S2. In a vacuum magnetron sputtering coating equipment, sequentially deposit each layer of the thin film constituting the functional film system on the surface of the pretreated glass substrate. S3. Perform low-temperature annealing treatment on the glass deposited with the functional film system. S4. Perform tempering treatment on the annealed glass. Among them, when depositing the silicon-aluminum-nitrogen composite dielectric layer in step S2, a silicon-aluminum alloy target is used, and the working gases are argon and nitrogen. The flow rate of the nitrogen is controlled by a mass flow controller, so that the flow rate linearly increases from the starting value Q₁ to the ending value Q₂ during the deposition duration of the silicon-aluminum-nitrogen composite dielectric layer, where 500 sccm ≤ Q₁ < Q₂ ≤ 800 sccm, and (Q₂ - Q₁) ≥ 150 sccm. At the same time, a zirconium-containing organometallic precursor vapor is introduced into the vacuum chamber of the vacuum magnetron sputtering coating equipment to co-dope the zirconium element into the silicon-aluminum-nitrogen composite dielectric layer, and the doping amount is controlled to be 0.8 - 3.0 at.%. Among them, when depositing the top-layer optical protection laminate in step S2, a zirconia target and a silica target are used for sputtering, and the deposition parameters are controlled to make the optical thickness of the formed first zirconia sub-layer be 62 - 68 nm and the optical thickness of the formed silica sub-layer be 90 - 98 nm.

6. The low-emissivity, high-transmittance coated tempered glass production process according to claim 5, characterized in that, In step S1, the plasma activation pretreatment is performed in an argon atmosphere at a pressure of 8.0 × 10⁻⁶. -2 -1.2×10 -1 Pa, with a plasma source power of 2.5-3.5 kW.

7. The low-emissivity, high-transmittance coated tempered glass production process according to claim 5, characterized in that, In step S3, the temperature of the low-temperature annealing treatment is 280-350℃, the holding time is 5-15 minutes, and the treatment atmosphere is air or nitrogen.

8. The low-emissivity, high-transmittance coated tempered glass production process according to claim 5, characterized in that, In step S4, the process parameters for the tempering treatment are: furnace temperature 660-690℃, heating time 220-260 s, and quenching air pressure 2800-3500 Pa.

9. The low-emissivity, high-transmittance coated tempered glass production process according to claim 5, characterized in that, The zirconium-containing organometallic precursor is trimethylzirconium, which is introduced into the vacuum chamber via a carrier gas.

10. A building curtain wall or door / window, characterized in that, It uses the low-emissivity, high-transmittance coated tempered glass as described in any one of claims 1-4.

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