Magnetron three-silver heat insulation base film and preparation method thereof
By using a 9-layer magnetron sputtering triple silver thermal insulation base film and employing magnetron sputtering and co-sputtering processes to control the copper doping of the silver alloy layer and the composition of the barrier layer, the mechanical properties and durability issues of the triple silver thermal insulation base film are solved, achieving high thermal insulation performance and long-term stability.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- JIANGSU SHUANGXING COLOR PLASTIC NEW MATERIALS
- Filing Date
- 2026-02-02
- Publication Date
- 2026-06-12
AI Technical Summary
Existing triple silver heat insulation base films have problems with poor mechanical properties and insufficient durability.
A nine-layer magnetron sputtering triple silver thermal insulation film is adopted, including a bottom dielectric layer, an AZO nucleation layer, a silver alloy layer, a barrier layer, a central dielectric layer, an AZO nucleation layer, a silver alloy layer, a barrier layer, and a top dielectric layer. It is deposited through magnetron sputtering and co-sputtering processes, and the copper doping ratio of the silver alloy layer and the composition of the barrier layer are controlled to form an Ag-Cu/NiCr/Ti interface structure. The gas pressure is dynamically controlled to adjust the stress gradient of the dielectric layer.
It significantly improves the hardness and oxidation resistance of the film, ensures the continuity and integrity of the conductive network, enhances the reflectivity of infrared light and the solar energy blocking rate, and maintains high light transmittance and mechanical stability.
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Figure CN122189579A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of heat insulation film technology, specifically relating to a magnetically controlled triple silver heat insulation base film and its preparation method. Background Technology
[0002] In the fields of modern building energy conservation and materials science, the development of thin-film materials capable of intelligently filtering solar radiation is crucial. Among them, low-emissivity heat-insulating films based on nano-silver layers are one of the most efficient spectrally selective coating technologies currently available, playing a central role, especially in the fields of high-performance energy-saving window films and curtain wall glass.
[0003] To achieve the ultimate balance between the inherent contradiction of "high light transmittance" and "high heat insulation," silver-based coating technology has evolved from single-silver to double-silver, and now to the most advanced triple-silver structure. The single-silver structure uses a basic "dielectric / silver / dielectric" structure, initially achieving spectral selectivity. The double-silver structure introduces a second silver film, and through more complex optical interference effects, it improves heat insulation by more than 30% while maintaining high light transmittance. The triple-silver structure, by constructing a precision multi-cavity resonant system containing three core silver films and a greater total number of layers, pushes spectral selectivity to new heights. It can block nearly 75% of solar infrared and ultraviolet energy while maintaining up to 70% visible light transmittance, achieving a light-to-heat ratio of over 2.2, far exceeding single-silver and double-silver products. However, current triple-silver heat-insulating films still suffer from significant durability and mechanical fragility issues due to the reactive nature of the silver layer, making it difficult to maintain performance over the long term.
[0004] To address the issues of poor mechanical properties and insufficient durability of existing triple silver heat-insulating base films, a magnetically controlled triple silver heat-insulating base film and its preparation method are proposed. Summary of the Invention
[0005] The purpose of this invention is to provide a magnetron-controlled triple silver thermal insulation film and its preparation method. The magnetron-controlled triple silver thermal insulation film prepared by this invention comprises nine layers, in the following order: a bottom dielectric layer, an AZO nucleation layer, a silver alloy layer, a barrier layer, a central dielectric layer, an AZO nucleation layer, a silver alloy layer, a barrier layer, and a top dielectric layer. The central dielectric layer is obtained by co-deposition of an Nb₂O₅ target and a silver target, and effectively becomes the third silver-containing layer.
[0006] To achieve the above objectives, the present invention provides the following technical solution:
[0007] A method for preparing a magnetron-controlled triple silver heat-insulating film includes the following steps:
[0008] After cleaning and drying the glass substrate, proceed with the deposition process as follows:
[0009] The first bottom dielectric layer is produced by magnetron sputtering with an Nb2O5 target and pulsed DC power supply. The process gas is a mixture of argon and oxygen in a volume ratio of 10:1.
[0010] At the start of deposition, the pressure was set to 2.0 mTorr, and then increased to 3.0-4.0 mTorr as deposition progressed. The target deposition thickness of the bottom medium layer was 35 nm.
[0011] The second AZO nucleation layer is produced using magnetron sputtering with an AZO target, pulsed DC power supply, and argon as the process gas.
[0012] At the start of deposition, a working pressure of 1.5 mTorr was used to deposit a target thickness of 3 nm. Subsequently, the working pressure was increased to 2.5 mTorr to deposit a total target thickness of 12 nm, and the working pressure was increased linearly with the deposition process.
[0013] The third silver alloy layer is produced using a co-sputtering process with silver and copper targets, DC power supply, and argon as the process gas.
[0014] The deposition working pressure was 2.0 mTorr, the power ratio of the silver target to the copper target was 100:1-3, and the deposition target thickness was 12 nm.
[0015] The fourth barrier layer is constructed using a co-sputtering process with NiCr and Ti targets, and argon gas is used as the process gas, powered by DC.
[0016] At the start of deposition, only the NiCr target was used, with a target thickness of 0.8 nm; subsequently, only the Ti target was used, with a target thickness of 1.5 nm.
[0017] The fifth layer, the central dielectric layer, is co-sputtered using an Nb2O5 target and a silver target. The process gas is a mixture of argon and oxygen in a volume ratio of 10:1, powered by pulsed DC.
[0018] The working pressure was 3.0 mTorr, the power ratio of Nb2O5 target to silver target was 100:2-5, and the deposition target thickness was 70 nm.
[0019] The sixth AZO nucleation layer uses the same process as the second layer;
[0020] The seventh silver alloy layer is manufactured using the same process as the third layer.
[0021] The eighth barrier layer is manufactured using the same process as the fourth layer.
[0022] The ninth layer, the top dielectric layer, is produced using magnetron sputtering with an Nb2O5 target and pulsed DC power supply. The process gas is a mixture of argon and oxygen in a volume ratio of 10:1.
[0023] At the start of deposition, the pressure was set at 1.8 mTorr, and then increased to 2.8-3.3 mTorr as deposition progressed. The target deposition thickness of the top dielectric layer was 40 nm.
[0024] After all nine layers are deposited, a deposited film is obtained on the glass substrate, which is the magnetron-controlled silver thermal insulation base film.
[0025] A magnetron-controlled triple silver thermal insulation film comprises, in sequence: a bottom dielectric layer, an AZO nucleation layer, a silver alloy layer, a barrier layer, a middle dielectric layer, an AZO nucleation layer, a silver alloy layer, a barrier layer, and a top dielectric layer.
[0026] Compared with the prior art, the beneficial effects of the present invention are as follows:
[0027] 1. An AZO nucleation layer was deposited using a two-step magnetron sputtering process. First, a thin, dense initial layer with preferred (002) crystal orientation was deposited under low pressure. Then, the pressure was increased to grow the nucleation layer to the designed thickness. The dense AZO layer with a regular surface lattice formed by the two-stage deposition provides a low-energy, highly ordered epitaxial growth platform for the subsequent growth of the silver alloy. As a lattice template, AZO induces the formation of a microstructure in the silver alloy with larger grains, fewer grain boundaries, and stronger (111) preferred orientation. This high-quality structure can significantly reduce the thin film resistivity, thereby improving its reflectivity to infrared light and forming the physical basis for achieving high thermal insulation performance.
[0028] 2. Through a co-sputtering process, the power ratio of the silver and copper targets is controlled, allowing copper atoms to be doped into the silver film in a specific proportion, forming a silver alloy layer. Copper atoms dissolve or partially replace silver atoms in the silver lattice, forming an Ag-Cu solid solution alloy film, which effectively bonds with the AZO nucleation layer. Compared to pure silver, trace amounts of copper doping significantly improve the film's hardness and resistance to sulfidation and oxidation. The AZO nucleation layer allows the Ag-Cu alloy film to form a continuous conductive network even at thinner thicknesses, compensating for the conductivity loss caused by copper doping and ensuring that durability is improved without sacrificing the core's low-emissivity performance.
[0029] 3. After the silver alloy layer is deposited, a composite metal barrier layer is sputtered onto the surface of the silver alloy layer while maintaining vacuum conditions. The barrier layer consists of a nickel-chromium alloy layer and a titanium metal layer, forming an Ag-Cu / NiCr / Ti interface structure. The NiCr layer acts as an adhesion enhancement layer, firmly bonding the silver alloy layer to the subsequent oxide layer. The Ti layer acts as a protective layer, preferentially reacting with oxygen during the subsequent Nb2O5 deposition to form a dense TiO2 interface, constructing a robust barrier to prevent oxygen plasma from eroding the underlying Ag-Cu alloy layer. This ensures the structural integrity of the silver alloy layer throughout the entire process and improves the overall solar energy blocking efficiency.
[0030] 4. During the deposition of the central dielectric layer, both a silver target and an Nb₂O₅ target are used simultaneously. A specific amount of silver is introduced into the Nb₂O₅ layer, causing the silver to no longer form a continuous conductive film, but rather to be randomly but uniformly dispersed as isolated, nano-sized particles within the amorphous Nb₂O₅ dielectric matrix, forming a metal-ceramic composite material. The silver nanoparticles in the central dielectric layer exhibit strong absorption and scattering of incident sunlight at specific wavelengths, achieving a localized surface plasmon resonance effect. The Nb₂O₅ dielectric matrix provides a transparent carrier for the silver nanoparticles and protects them from oxidation, forming a de facto third silver-containing coating. Simultaneously, its high refractive index environment modulates the wavelength position at which the silver nanoparticles exhibit the localized surface plasmon resonance effect, enabling the central dielectric layer to produce stronger absorption and scattering in the near-infrared band of 750-1200 nm, further improving the solar energy blocking efficiency of the triple-silver thermal insulation film product.
[0031] 5. During the deposition of the bottom and top dielectric layers, the deposition pressure is dynamically controlled, resulting in a small density gradient in the microstructure of the single-layer Nb2O5 from bottom to top. The internal stress also smoothly transitions from compressive stress to tensile stress. The stress accumulation of the bottom and top dielectric layers located at the bottom and top layers respectively can cancel each other out, eventually approaching zero, thus ensuring the durability and good mechanical properties of the triple silver heat insulation base film product during long-term use. Attached Figure Description
[0032] Figure 1 This is a schematic diagram of the structure of the magnetically controlled triple silver heat-insulating base film in this invention.
[0033] The layers are: 1. First bottom dielectric layer; 2. Second AZO nucleation layer; 3. Third silver alloy layer; 4. Fourth barrier layer; 5. Fifth central dielectric layer; 6. Sixth AZO nucleation layer; 7. Seventh silver alloy layer; 8. Eighth barrier layer; 9. Ninth top dielectric layer; 10. Glass substrate. Detailed Implementation
[0034] The technical solution of the present invention will be clearly and completely described below through some embodiments and experimental examples. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.
[0035] Reference Figure 1 The schematic diagram shown illustrates that this invention provides a magnetically controlled triple silver heat-insulating film and its preparation method. The technical solution is as follows:
[0036] Example 1
[0037] After cleaning and drying the glass substrate, proceed with the deposition process as follows:
[0038] First layer: Bottom dielectric layer, using magnetron sputtering process, Nb2O5 target, pulsed DC power supply, process gas is a mixture of argon and oxygen in a volume ratio of 10:1.
[0039] At the start of deposition, the pressure was set to 2.0 mTorr, and then increased to 3.0 mTorr as deposition progressed. The target deposition thickness of the bottom medium layer was 35 nm.
[0040] The second layer, the AZO nucleation layer, is produced using magnetron sputtering with an AZO target, pulsed DC power supply, and argon as the process gas.
[0041] At the start of deposition, a working pressure of 1.5 mTorr was used to deposit a target thickness of 3 nm. Subsequently, the working pressure was increased to 2.5 mTorr to deposit a total target thickness of 12 nm.
[0042] The third layer is a silver alloy layer, which is produced using a co-sputtering process with silver and copper targets, DC power supply, and argon as the process gas.
[0043] The deposition working pressure was 2.0 mTorr, the power ratio of the silver target to the copper target was 100:1, and the deposition target thickness was 12 nm.
[0044] The fourth layer is a barrier layer, which is produced using a co-sputtering process with NiCr and Ti targets. Argon is used as the process gas, and DC power is supplied.
[0045] At the start of deposition, only the NiCr target was used, with a target thickness of 0.8 nm; subsequently, only the Ti target was used, with a target thickness of 1.5 nm.
[0046] Fifth layer: Central dielectric layer, using co-sputtering process, Nb2O5 target and silver target, process gas is a mixture of argon and oxygen in volume ratio of 10:1, pulsed DC power supply.
[0047] The working pressure was 3.0 mTorr, the power ratio of Nb2O5 target to silver target was 100:2, and the deposition target thickness was 70 nm.
[0048] Sixth layer: AZO nucleation layer, with the same process as the second layer;
[0049] Seventh layer: Silver alloy layer, with the same process as the third layer;
[0050] Eighth layer: Barrier layer, with the same process as the fourth layer;
[0051] Ninth layer: Top dielectric layer, using magnetron sputtering process, Nb2O5 target, pulsed DC power supply, process gas is a mixture of argon and oxygen in a volume ratio of 10:1.
[0052] At the start of deposition, the pressure was set to 1.8 mTorr, and then increased to 2.8 mTorr as deposition progressed. The target deposition thickness of the top dielectric layer was 40 nm.
[0053] After all nine layers have been deposited, a film is obtained on the glass substrate, which is the magnetron-controlled triple silver thermal insulation base film.
[0054] Examples 2-18 differ from Example 1 in operating parameters, but the other process steps and the range of raw material selection are the same.
[0055] The specific changes in operating parameters are summarized in Table 1.
[0056]
[0057] Comparative Example 1
[0058] Unlike Example 1, the deposition of the second and sixth AZO nucleation layers was carried out using a constant working pressure of 2.5 mTorr, while all other process parameters remained the same.
[0059] Comparative Example 2
[0060] Unlike Example 1, the second layer was removed, and a silver alloy layer was deposited directly on the bottom dielectric layer of the first layer, while all other process parameters remained the same.
[0061] Comparative Example 3
[0062] Unlike Example 5, in the deposition of the third and seventh layers, the power ratio of the silver target to the copper target was adjusted to 100:10, while other process parameters remained the same.
[0063] Comparative Example 4
[0064] Unlike Example 5, only a silver target was used in the deposition of the third and seventh layers, while all other process parameters remained the same.
[0065] Comparative Example 5
[0066] Unlike Example 5, the seventh layer is removed, i.e., a barrier layer is deposited directly on the surface of the sixth AZO nucleation layer, while all other process parameters remain the same.
[0067] Comparative Example 6
[0068] Unlike Example 9, only Ti targets were used in the deposition of the fourth and eighth layers, with the target thickness set to 2.3 nm, while other process parameters remained the same.
[0069] Comparative Example 7
[0070] Unlike Example 9, the target thicknesses of the NiCr and Ti layers were changed to 1.5 nm and 0.8 nm, respectively, during the deposition of the fourth and eighth layers, while other process parameters remained the same.
[0071] Comparative Example 8
[0072] Unlike Example 9, no barrier layer was set, and the deposition processes of the fourth and eighth layers were not performed, while all other process parameters remained the same.
[0073] Comparative Example 9
[0074] Unlike Example 13, the power ratio of the Nb2O5 target to the silver target was adjusted to 100:15 during the deposition of the central dielectric layer, while other process parameters remained the same.
[0075] Comparative Example 10
[0076] Unlike Example 13, no silver target was used during the deposition of the central dielectric layer, but all other process parameters were the same.
[0077] Comparative Example 11
[0078] Unlike Example 17, no pressure adjustment was performed during the deposition of the first and ninth layers. Constant operating pressures of 3.0 mTorr and 2.8 mTorr were maintained, respectively, while other process parameters remained the same.
[0079] Comparative Example 12
[0080] Unlike Example 17, no pressure adjustment was performed on the ninth layer, maintaining a constant operating pressure of 2.8 mTorr, while all other process parameters remained the same.
[0081] Experimental Example 1
[0082] The sheet resistance and surface emissivity of the heat-insulating base film products prepared in Examples 1-4 and Comparative Examples 1-2 were tested, and the relevant results are summarized in Table 2.
[0083] The sheet resistance test method is as follows: referring to the relevant test methods of ASTM F390 standard, the sheet resistance (Ω / sq) of the heat insulation base film sample on the surface of the glass substrate is tested and recorded using the four-probe method.
[0084] The surface emissivity test method is as follows: referring to the ASTM C1371 standard, the total surface emissivity of the heat insulation base film sample on the glass substrate surface of the specimen is tested. This value represents the ratio of the material surface's ability to radiate heat energy to the ability of an ideal blackbody to radiate heat energy at the same temperature. The lower the ratio, the better the thermal insulation performance.
[0085]
[0086] As shown in Table 2, the sheet resistance and surface emissivity of the heat insulation base films prepared in Examples 1-4 are significantly lower than those in Comparative Examples 1 and 2, indicating that the heat insulation base films prepared in Examples 1-4 have better conductivity and thermal insulation performance.
[0087] Comparative Example 1 uses a constant working pressure to deposit an AZO nucleation layer, lacking the step of depositing a dense initial layer under low pressure. This results in a decrease in the ability of the AZO nucleation layer to induce the formation of a regular microstructure in the silver alloy layer. The sheet resistance and surface emissivity of the final product are significantly worse than those of the Example. Comparative Example 2 does not have an AZO nucleation layer and directly deposits a silver alloy layer on the bottom dielectric layer. The silver alloy layer cannot form a continuous and dense conductive network, and its sheet resistance and surface emissivity are the worst. This also proves the necessity of an AZO nucleation layer for achieving excellent performance.
[0088] In summary, this invention achieves significant technical advantages through a two-step magnetron sputtering process for depositing an AZO nucleation layer: firstly, the dense initial layer deposited under low pressure provides a low-energy and highly ordered epitaxial growth platform for the subsequent growth of the silver alloy layer; subsequently, increasing the pressure allows the nucleation layer to grow to the designed thickness. This AZO layer, acting as a lattice template, synergistically induces the formation of a microstructure with larger grains and fewer grain boundaries in the silver alloy layer. This high-quality structure significantly reduces the resistivity of the thin film and thus improves the reflectivity of infrared light, laying the physical foundation for the excellent thermal insulation performance of the final product.
[0089] Experiment Example 2
[0090] The visible light transmittance and haze of the heat-insulating base film products prepared in Examples 5-8 and Comparative Examples 3-5 were tested, and the relevant results are summarized in Table 3.
[0091] The test method for visible light transmittance is as follows: referring to the relevant test methods of GB / T 2680 standard, the visible light wavelength range of 400nm-750nm is used for testing and the transmittance at each wavelength is recorded. The visible light transmittance (%) of each sample in the test wavelength range is calculated using the spectral distribution data of CIE standard D65 light source. The sample is then exposed in a desiccator containing thioacetamide solution (15wt%) and treated at 60℃ for 24 hours before the visible light transmittance (%) is retested.
[0092] The haze test method is as follows: refer to the relevant test methods of ASTM D1003 standard, use a haze meter to test the sample and record the haze (%).
[0093]
[0094] As shown in Table 3, Examples 5-8 maintained high initial visible light transmittance and low haze, while their visible light transmittance changed only slightly after the sulfurization treatment, which was significantly better than Comparative Example 4.
[0095] Comparative Example 4 used only a silver target during the deposition process, and its initial visible light transmittance was close to that of the example. However, after sulfidation treatment, the visible light transmittance decreased significantly, indicating that the pure silver functional layer was insufficient in terms of chemical stability. In Comparative Example 3, the power ratio of the silver target and the copper target was adjusted too high, resulting in a significant decrease in its initial visible light transmittance and higher haze. Although the performance did not change much after sulfidation treatment, its initial optical performance could no longer meet the requirements, which proved the importance of a specific power ratio. Although Comparative Example 5 had a different structure, its silver alloy layer also showed good resistance to sulfidation.
[0096] In summary, this invention, through a co-sputtering process and precise control of the power ratio of the silver and copper targets, enables copper atoms to be doped into the silver film in a specific proportion to form a silver alloy layer. This structural design produces a significant synergistic effect: compared to pure silver, trace amounts of copper doping significantly improve the film's resistance to sulfidation and oxidation, effectively preventing performance degradation caused by environmental factors. Simultaneously, the synergistic effect with the high-quality AZO nucleation layer ensures that durability is improved without sacrificing the core's low-emissivity performance and excellent initial optical properties, achieving a balance between high transmittance, high clarity, and long-term stability.
[0097] Experimental Example 3
[0098] The sheet resistance and surface emissivity of the heat-insulating base film products prepared in Examples 9-12 and Comparative Examples 6-8 were tested. The relevant results are summarized in Table 4.
[0099] For the testing methods of sheet resistance and surface emissivity, refer to Experimental Example 1.
[0100]
[0101] As shown in Table 4, the sheet resistance and surface emissivity of the heat-insulating base films prepared in Examples 9-12 are significantly lower than those in Comparative Examples 6, 7 and 8, indicating that the heat-insulating base films of Examples 9-12 maintain a more complete conductive network and excellent low-emissivity after manufacturing.
[0102] Comparative Example 8 lacked a barrier layer, resulting in severe oxidation of the silver alloy layer during subsequent processes, leading to the worst sheet resistance and surface emissivity. In Comparative Example 7, the target thickness of the Ti layer was insufficient, failing to provide complete protection, causing damage to the silver alloy layer as well, resulting in severe deterioration of electrical and low-emissivity properties. Comparative Example 6 used only a Ti target, which provided the main protection, but its final performance still lagged behind the examples, demonstrating the superiority of the combined effect of the NiCr and Ti layers.
[0103] In summary, this invention deposits a composite metal layer on the surface of the silver alloy layer, forming an Ag-Cu / NiCr / Ti interface structure. This design produces a significant synergistic effect. The NiCr layer acts as an adhesion enhancement layer, firmly bonding the silver alloy layer to the subsequent oxide layer, while the Ti layer, as a protective layer, preferentially reacts with oxygen during subsequent deposition to form a dense interface barrier, preventing oxygen plasma from eroding the underlying Ag-Cu alloy layer. This structure ensures the structural integrity of the silver alloy layer throughout the entire process, effectively maintaining the product's excellent conductivity and low emissivity, thus providing a foundation for achieving high solar energy rejection rates.
[0104] Experiment Example 4
[0105] The visible light transmittance and solar energy transmittance of the heat-insulating base film products prepared in Examples 13-16 and Comparative Examples 9-10 were tested, and the relevant results are summarized in Table 5. Comparative Example 5 was also included in the comparative test to measure the impact of reducing one layer of silver alloy.
[0106] For the test method of visible light transmittance, please refer to Experimental Example 2.
[0107] The test method for solar transmittance is as follows: referring to the relevant test methods of GB / T 2680 standard, the experiment is conducted in the near-infrared wavelength range of 750-1200nm, and the total transmittance of solar energy in this band is calculated using a spectrophotometer. The lower the transmittance in the near-infrared band, the better the heat insulation effect of the sample.
[0108] Experiments were conducted using the ultraviolet wavelength range of 300-400 nm, and the total transmittance of solar energy in this band was calculated using a spectrophotometer. The lower the transmittance in the ultraviolet band, the better the UV resistance of the sample.
[0109]
[0110] As shown in Table 5, Examples 13-16 maintained high visible light transmittance while keeping their near-infrared and ultraviolet transmittance at extremely low levels, significantly better than Comparative Examples 10 and 5.
[0111] Comparative Example 10 did not use a silver target during the deposition of the central dielectric layer, resulting in a significant increase in its near-infrared transmittance compared to the example, and a significant decrease in its heat insulation effect. This indicates that the introduction of silver elements into the central dielectric layer is crucial for blocking near-infrared heat. In Comparative Example 9, the power ratio of the silver target was set too high. Although a lower near-infrared transmittance was obtained, its visible light transmittance was also significantly reduced, failing to meet the requirements for high light transmission. This demonstrates the necessity of precisely controlling the silver content. Comparative Example 5, as a structure with one less silver alloy layer, had the worst near-infrared transmittance, which also proves the rationality of the multi-layer structure design of this scheme.
[0112] In summary, this invention utilizes both a silver target and a Nb₂O₅ target during the deposition of the central dielectric layer, introducing a specific amount of silver into the Nb₂O₅ layer to form a metal-ceramic composite material. This design produces a significant synergistic effect: silver nanoparticles are dispersed in an isolated form within the Nb₂O₅ dielectric matrix, exhibiting strong absorption and scattering of incident sunlight through localized surface plasmon resonance; while the Nb₂O₅ dielectric matrix not only provides a transparent carrier for the silver nanoparticles, but its high refractive index environment also tunes the wavelength of the resonance effect to the near-infrared band of 750-1200 nm. This specific combination of materials and process design forms a de facto third silver-containing coating, synergistically improving the product's solar energy blocking efficiency and achieving a balance between high light transmittance and high thermal insulation performance.
[0113] Experimental Example 5
[0114] The film stress and thermal cycling stability of the heat-insulating base film products prepared in Examples 17-18 and Comparative Examples 11-12 were tested, and the relevant results are summarized in Table 6.
[0115] The thin film stress was tested using the substrate curvature measurement method. A laser interferometer was used to measure the change in the radius of curvature of the glass substrate before and after coating. The sample size was 100mm×100mm. The average internal stress (MPa) of the thin film was calculated using the Stoney formula.
[0116] The test method for thermal cycling stability is as follows: The sample is placed in a constant temperature chamber at -40℃ and 85℃ for 2 hours each, which is recorded as one cycle. After 300 cycles, the microcracks on the sample surface are examined using an optical microscope, and the crack density (cracks / mm²) within the field of view is recorded. 2 (This is the standard.)
[0117]
[0118] As shown in Table 6, the film stress of the heat-insulating base film prepared in Examples 17-18 is much lower than that in Comparative Examples 11 and 12, and no cracks appeared after the thermal cycling stability test, demonstrating excellent mechanical properties.
[0119] Comparative Example 11 did not adjust the pressure during the deposition of the first and ninth layers, using a constant operating pressure. The lack of stress balance design led to the accumulation of huge internal stress in the entire film system, resulting in severe cracking during thermal cycling tests. Comparative Example 12 did not adjust the pressure only in the ninth layer, which disrupted the symmetrical stress cancellation mechanism between the bottom and top dielectric layers, resulting in a significant increase in the total stress of the film system. Similarly, microcracks appeared after thermal cycling tests, further demonstrating the importance of symmetrical stress control.
[0120] In summary, this invention dynamically controls the deposition pressure during the deposition of the bottom and top dielectric layers, allowing the internal stress of the single-layer Nb₂O₅ to smoothly transition from compressive stress to tensile stress. The stresses generated in the bottom and top dielectric layers, after accumulation, cause the total cumulative stress of the entire membrane system to cancel each other out and eventually approach zero. This process design produces a significant synergistic effect, ensuring the durability and excellent mechanical properties of the triple-silver thermal insulation base film product during long-term use.
[0121] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.
Claims
1. A method for preparing a magnetron-controlled triple silver thermal insulation film, characterized in that: The preparation method is as follows: S1 uses Nb2O5 target sputtering to deposit the first bottom dielectric layer; S2 uses AZO target sputtering to deposit a second AZO nucleation layer; S3 uses silver and copper targets to sputter and deposit a third silver alloy layer; S4 uses NiCr and Ti targets to sputter and deposit the fourth barrier layer; S5 uses Nb2O5 and silver targets for sputtering to deposit the fifth central dielectric layer; S6. A sixth AZO nucleation layer is sputtered and deposited on the surface of the central dielectric layer using the same process as S2; a seventh silver alloy layer is sputtered and deposited using the same process as S3; an eighth barrier layer is sputtered and deposited using the same process as S4; and a ninth top dielectric layer is sputtered and deposited using an Nb2O5 target. The first to ninth layers together constitute the magnetron-controlled triple silver thermal insulation base film.
2. The method for preparing a magnetron-controlled triple silver heat-insulating film according to claim 1, characterized in that: During the deposition of the first bottom medium layer, the highest pressure during the deposition process is 3.0-4.0 mTorr, and the process gas is a mixture of argon and oxygen.
3. The method for preparing a magnetron-controlled triple silver heat-insulating film according to claim 1, characterized in that: During the deposition of the third silver alloy layer, the power ratio of the silver target to the copper target is 100:1-3.
4. The method for preparing a magnetron-controlled triple silver heat-insulating base film according to claim 1, characterized in that: During the deposition of the second AZO nucleation layer, the working pressure was 1.5-2.5 mTorr, and the working pressure increased linearly with the deposition process.
5. The method for preparing a magnetron-controlled triple silver heat-insulating film according to claim 1, characterized in that: During the deposition of the fifth central dielectric layer, the power ratio of the Nb2O5 target to the silver target is 100:2-5.
6. The method for preparing a magnetron-controlled triple silver heat-insulating base film according to claim 1, characterized in that: During the deposition of the fourth barrier layer, only the NiCr target is used at the beginning of the deposition; subsequently, only the Ti target is used.
7. The method for preparing a magnetron-controlled triple silver heat-insulating film according to claim 1, characterized in that: During the deposition of the ninth top dielectric layer, the highest working pressure is 2.8-3.3 mTorr.
8. A magnetron-controlled triple silver heat-insulating base film, comprising, in sequence: The film comprises a bottom dielectric layer, an AZO nucleation layer, a silver alloy layer, a barrier layer, a middle dielectric layer, an AZO nucleation layer, a silver alloy layer, a barrier layer, and a top dielectric layer; further characterized in that the magnetron-controlled triple silver thermal insulation base film is prepared by the preparation method described in any one of claims 1-7.