Bendable toughened energy-saving glass for cold chain and preparation method thereof

Abstract

The present application relates to the technical field of glass preparation, in particular to a bendable energy-saving glass for cold chain and a preparation method thereof. The glass comprises an ultrathin sodium-calcium glass substrate, and a silicon nitride barrier layer, a zinc oxide transition layer, a gallium-doped zinc oxide layer, a silver layer, a zinc oxide cover layer and a fluorine-doped tin oxide protective layer arranged on the substrate in sequence. The gallium-doped zinc oxide layer has a gallium-rich band on the side adjacent to the silver layer and contains tin-oxygen-gallium composite pinning sites. In the preparation, after forming the zinc oxide skeleton, trimethyl gallium post-pulse treatment is performed, and then anhydrous tin tetrachloride short pulse, hydrogen reduction stop, dry oxygen short pulse and water vapor sub-pulse treatment are performed in sequence, followed by deposition of the silver layer and the protective layer. The present application can improve the continuous film formation and interface stability of the silver layer, reduce the risk of silver layer migration, cracking and performance attenuation in cold bending and low-temperature high-humidity cycles, and is suitable for arc-shaped cold chain display cabinet doors.

Description

Technical Field

[0001] This invention relates to the field of glass preparation technology, specifically to a bendable tempered energy-saving glass for cold chain applications and its preparation method. Background Technology

[0002] Cold chain display cabinet doors operate in environments characterized by low temperatures, high humidity, frequent opening and closing, and cleaning and maintenance. They must simultaneously meet requirements for transparent display, heat insulation and energy saving, and anti-condensation. Existing doors often utilize a combination of insulated glass, low-emissivity coated glass, or tempered glass. However, as display cabinets become thinner, more curved, and have larger windows, traditional thicker glass presents challenges such as heavy weight, poor adaptability to bending, and difficulty in assembling irregularly shaped cabinets.

[0003] Silver-based low-emissivity films reflect far-infrared radiation and are commonly used in energy-saving glass. This system typically includes a zinc oxide layer, a silver layer, and a protective layer, with the silver layer being the key functional layer for reducing emissivity. However, if the silver layer is too thin, it is prone to discontinuous nucleation and the formation of island-like structures, while thickening the silver layer reduces visible light transmittance and increases internal stress. For ultra-thin soda-lime glass, the strain generated during cold bending assembly is more easily transmitted to the film interface, causing silver layer cracks, migration, or agglomeration.

[0004] Current processes often use zinc oxide or gallium-doped zinc oxide layers as nucleation layers for silver layers, but they focus more on the total amount of dopant and lack control over the thickness distribution, grain boundary location, and deposition sequence on the side adjacent to the silver layer. If gallium is uniformly dispersed in the zinc oxide layer, it is difficult to form stable and localized nucleation sites before silver deposition. After cold bending and thermal cycling, sheet resistance may still increase, radiation performance may be degraded, and localized fogging may occur.

[0005] Meanwhile, cold chain doors are affected by moisture, defrosting, and cleaning fluids during use, and moisture can easily enter the vicinity of the silver layer along film defects or grain boundaries. Existing methods of increasing the thickness of the silver layer, protective layer, or barrier layer can improve initial performance, but they can easily lead to decreased transmittance, increased film stress, and reduced bending adaptability, making it difficult to ensure long-term stability during low-temperature and high-humidity service. Summary of the Invention

[0006] In view of this, the purpose of this invention is to propose a bendable tempered energy-saving glass for cold chain applications and its preparation method, so as to solve the problems of film layer attenuation, silver layer migration and cracking, and insufficient anti-condensation stability of existing ultra-thin low-emissivity glass for cold chain display cabinets during cold bending assembly and low temperature and high humidity service.

[0007] To achieve the above objectives, the present invention provides a method for preparing bendable tempered energy-saving glass for cold chain applications, comprising the following steps: An ultrathin soda-lime glass sheet is chemically tempered; a silicon nitride barrier layer is deposited on the surface of the chemically tempered ultrathin soda-lime glass sheet; a zinc oxide transition layer is deposited on the surface of the silicon nitride barrier layer; a gallium-doped zinc oxide layer is deposited on the surface of the zinc oxide transition layer, the deposition of the gallium-doped zinc oxide layer includes first forming a zinc oxide framework, then performing a trimethylgallium post-pulse treatment to enrich gallium elements in the zinc oxide grain boundary region adjacent to the subsequent silver layer; anhydrous tin tetrachloride short-pulse treatment and hydrogen reduction residence treatment are sequentially performed on the surface of the gallium-doped zinc oxide layer; subsequently, dry oxygen short-pulse treatment and water vapor sub-pulse treatment are sequentially performed; a silver layer is deposited on the surface of the gallium-doped zinc oxide layer after the above treatment; finally, a zinc oxide capping layer and a fluorine-doped tin oxide protective layer are sequentially deposited on the surface of the silver layer; after post-processing and cold bending assembly, a bendable tempered energy-saving glass for cold chain is obtained.

[0008] Preferably, the thickness of the ultrathin soda-lime glass sheet is 800-1100μm, and the ultrathin soda-lime glass sheet is cut into a rectangular sheet of 300mm×500mm, with a chamfer width of 200-350μm.

[0009] Preferably, the chemical tempering treatment includes: immersing a pretreated ultrathin soda-lime glass sheet in potassium nitrate molten salt and holding it at 400-420°C for 100-140 minutes to allow sodium ions on the glass surface to exchange with potassium ions in the molten salt.

[0010] Preferably, the silicon nitride barrier layer is formed by plasma-enhanced chemical vapor deposition, during which a mixture of silane and nitrogen gas at 20-30 sccm, ammonia at 70-90 sccm, and nitrogen at 450-550 sccm are introduced, the working pressure of the cavity is 90-110 Pa, the radio frequency power is 70-90 W, and the deposition time is 8-12 min.

[0011] Preferably, the thickness of the silicon nitride barrier layer is 20-25 nm.

[0012] Preferably, the zinc oxide transition layer is formed by pulsed chemical vapor deposition, and the deposition is performed in a cyclic sequence of diethylzinc pulse, nitrogen purging, water vapor pulse, and nitrogen purging; wherein the temperature of the diethylzinc source bottle is 20-30℃, the temperature of the water source bottle is 20-30℃, the diethylzinc carrier gas flow rate is 15-25 sccm, the water vapor carrier gas flow rate is 15-25 sccm, the diethylzinc pulse time is 220-280 ms, the water vapor pulse time is 130-170 ms, the nitrogen purging flow rate is 90-110 sccm, and the cycle is repeated for 110-130 times.

[0013] Preferably, the thickness of the zinc oxide transition layer is 18-22 nm.

[0014] Preferably, the gallium-doped zinc oxide layer is deposited using a cyclic sequence of diethylzinc pulse, nitrogen purging, water vapor pulse, and nitrogen purging, at a deposition temperature of 180-190℃ and a deposition pressure of 70-90Pa. When forming the zinc oxide framework, the diethylzinc pulse duration is 220-280ms, the water vapor pulse duration is 130-170ms, the diethylzinc carrier gas flow rate is 15-25sccm, the nitrogen purging flow rate is 90-110sccm, and the water vapor carrier gas flow rate is 15-25sccm, repeated for 80-100 cycles.

[0015] Preferably, during the trimethylgallium post-pulse processing, deposition is performed in a cyclic sequence of diethylzinc short pulse, nitrogen purging, trimethylgallium post-pulse, nitrogen purging, water vapor short pulse, and nitrogen purging; wherein the diethylzinc short pulse duration is 80-120 ms, the diethylzinc carrier gas flow rate is 15-25 sccm, the nitrogen purging flow rate is 90-110 sccm, the trimethylgallium post-pulse duration is 60-100 ms, the trimethylgallium carrier gas flow rate is 8-12 sccm, the nitrogen purging flow rate is 90-110 sccm, the water vapor short pulse duration is 100-140 ms, the water vapor carrier gas flow rate is 15-25 sccm, the third nitrogen purging duration is 8-12 s, and the nitrogen purging flow rate is 90-110 sccm, and this cycle is repeated 10-14 times.

[0016] Preferably, the thickness of the gallium-doped zinc oxide layer is 24-30 nm.

[0017] Preferably, the anhydrous tin tetrachloride short-pulse treatment includes: controlling the temperature of the anhydrous tin tetrachloride source bottle to 20-30℃, controlling the temperature of the delivery pipeline to 55-65℃, using nitrogen at 8-12 sccm as the carrier gas for anhydrous tin tetrachloride, the anhydrous tin tetrachloride short-pulse time to be 40-60 ms, the nitrogen purging time to be 14-16 s, and repeating 2-4 cycles.

[0018] Preferably, the hydrogen reduction residence treatment includes: introducing a mixed gas of hydrogen and nitrogen, wherein the hydrogen component in the mixed gas is 4%, the flow rate of the mixed gas is 40-60 sccm, the pressure is 90-110 Pa, the residence time is 35-55 s, and then purging with nitrogen at 90-110 sccm for 15-25 s.

[0019] Preferably, the dry oxygen short-pulse treatment includes: introducing a mixture of oxygen and nitrogen gas, wherein the oxygen volume fraction in the mixture is 1500-2500 ppm, the flow rate of the mixture is 40-60 sccm, the introduction time is 6-10 s, and then purging with nitrogen at 90-110 sccm for 15-25 s.

[0020] Preferably, the water vapor subpulse treatment includes: controlling the temperature of the water source bottle to 20-30°C, using nitrogen as the water vapor carrier gas, the water vapor carrier gas flow rate is 8-12 sccm, the water vapor pulse time is 20-50 ms, followed by purging with nitrogen at 90-110 sccm for 15-25 s, and the water vapor subpulse treatment is repeated only once.

[0021] Preferably, the silver layer is formed by DC magnetron sputtering with a target-substrate distance of 70-90 mm, a stage temperature of 50-70 °C, an argon flow rate of 20-30 sccm, and a working pressure of 250-350 mPa. The process involves pre-sputtering at 10 W power for 20-40 s, followed by deposition at 15-25 W power for 15-25 s, and then deposition at 30-40 W power for 50-70 s.

[0022] Preferably, the thickness of the silver layer is 9-10 nm.

[0023] Preferably, the zinc oxide coating is formed by radio frequency magnetron sputtering, with argon gas introduced at 25-35 sccm, working pressure at 250-350 mPa, radio frequency power at 70-90 W, deposition time at 10-14 min, and the thickness of the zinc oxide coating is 14-18 nm.

[0024] Preferably, the fluorine-doped tin oxide protective layer is formed by radio frequency magnetron sputtering, with argon gas introduced at 25-32 sccm, oxygen at 1-3 sccm, and a mixture of carbon tetrafluoride and argon gas at 4-6 sccm. The volume fraction of carbon tetrafluoride in the mixture of carbon tetrafluoride and argon gas is 5%. The working pressure is 350-450 mPa, the radio frequency power is 90-110 W, the deposition time is 18-22 min, and the thickness of the fluorine-doped tin oxide protective layer is 30-35 nm.

[0025] Preferably, the post-processing includes: placing a glass slide with a fluorine-doped tin oxide protective layer in a nitrogen-protected oven, continuously introducing nitrogen at 150-250 sccm, maintaining the temperature at 170-190°C for 15-25 minutes, and then naturally cooling it to 25°C under nitrogen protection.

[0026] Preferably, the cold bending assembly includes: placing the post-treated glass sheet on an arc-shaped fixture with a radius of 130-180 mm with the film layer located on the concave side of the arc, slowly bonding it at a displacement speed of 1-3 mm / min, and maintaining it at 25°C for 20-40 min.

[0027] Furthermore, the present invention also provides a bendable tempered energy-saving glass for cold chain applications, wherein the visible light transmittance of the bendable tempered energy-saving glass for cold chain applications is not less than 73.0%, the emissivity before cold bending is not higher than 0.125, the emissivity after cold bending is not higher than 0.135, the sheet resistance increase rate after 100 cycles of cold and heat from -20℃ to 25℃ is not higher than 6.5%, and the bending strength is not less than 330MPa.

[0028] The beneficial effects of this invention are: This invention introduces a trimethylgallium post-pulse at the end of the gallium-doped zinc oxide seed layer deposition, which helps to form stable gallium-oxygen nucleation sites before silver layer deposition, reduces random aggregation of silver atoms, and improves the continuity and low-radiation retention capability of thinner silver layers.

[0029] This invention introduces anhydrous tin tetrachloride short pulses into the gallium-rich region and combines them with hydrogen reduction and residence, so that tin species are preferentially fixed near the gallium-oxygen sites to form a tin-oxygen-gallium composite structure. This structure is located in the interface region below the silver layer, which helps to restrict the migration of silver along the zinc oxide grain boundary and reduce the risk of silver layer agglomeration, edge darkening and increased sheet resistance after low temperature and high humidity cycling.

[0030] This invention divides the interface stabilization process into dry oxygen short pulses and water vapor sub-pulses, and specifies the processing order as dry oxygen first, followed by water vapor. Dry oxygen short pulses are used to stabilize the tin-oxygen-gallium bridging structure, while water vapor sub-pulses are used to passivate adjacent zinc-oxygen undercoordinated sites, thereby reducing nucleation at non-target locations and the propagation of local cracks after cold bending.

[0031] This invention improves the continuity and service stability of the film layer without simply increasing the thickness of the silver layer. It helps to maintain the light transmittance of the glass, reduce the internal stress of the film layer, and improve the adaptability of ultra-thin tempered glass to cold bending assembly in curved cold chain display cabinet doors.

[0032] In summary, compared with existing methods that improve stability by increasing the thickness of the silver layer or protective layer, this invention focuses more on nucleation, migration and defect control at the near-silver interface, and can balance energy saving, heat insulation, anti-fogging, appearance stability and bending assembly reliability in cold chain low temperature, high humidity and frequent door opening and closing environments. Detailed Implementation

[0033] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to specific embodiments.

[0034] Raw material source and model Ultra-thin soda-lime glass sheet: Commercially available ultra-thin float soda-lime clear glass, with a thickness of 900μm and a size of 300mm×500mm.

[0035] Example 1: A method for preparing bendable tempered energy-saving glass for cold chain applications, the specific steps of which are as follows: Step 1, Glass substrate pretreatment: Take an ultrathin soda-lime glass sheet and cut it into rectangular sheets of 300mm × 500mm. Grind the edges sequentially with 600-mesh, 1200-mesh, and 2000-mesh diamond grinding wheels to achieve a chamfer width of 200-350μm. Weigh 2g of sodium dodecyl sulfate, 10g of sodium carbonate, and deionized water to prepare 2000g of a weak alkaline cleaning solution. Immerse the glass sheet in the solution and ultrasonically clean it at 40℃ for 8 minutes. Then rinse it twice with 2000g of deionized water for 5 minutes each time, followed by immersion in 1000g of anhydrous ethanol for 3 minutes. Finally, purge the glass surface with nitrogen gas at a flow rate of 10L / min for 2 minutes until no visible droplets remain. Step 2, Chemical Tempering Treatment: Weigh 10,000 g of potassium nitrate and place it in a stainless steel molten salt bath. Melt it at 410°C and keep the temperature constant for 60 minutes. Immerse the glass slide treated in step one completely in the molten salt and keep it at 410°C for 120 minutes to allow sodium ions on the glass surface to exchange with potassium ions in the molten salt. After removing the glass slide, immediately wash it twice with 1,000 g of deionized water at 80°C for 5 minutes each time, then wash it once with 1,000 g of deionized water at 25°C, and then dry it at 180°C for 30 minutes. Step 3, Silicon nitride barrier layer deposition: The glass slide obtained in step two is placed into the plasma-enhanced chemical vapor deposition chamber, and the chamber is evacuated to a base pressure not exceeding 1×10⁻⁶. -3 Pa, raise the substrate temperature to 230℃ and hold for 10 min; introduce a mixture of silane and nitrogen gas at 25 sccm, ammonia at 80 sccm, and nitrogen at 500 sccm, control the cavity working pressure to 100 Pa, control the RF power to 80 W, and the deposition time to 10 min; after deposition, turn off the RF power and purge with nitrogen at 500 sccm for 3 min. Step 4, Deposition of zinc oxide transition layer: Without contact with air, the glass slide obtained in step three is transferred into the pulsed chemical vapor deposition chamber, and the chamber is evacuated to a base pressure not exceeding 1 × 10⁻⁶. -3The substrate temperature was controlled at 185℃ and the chamber pressure at 80Pa. 3000mg of diethylzinc was added to the diethylzinc source bottle, and the source bottle temperature was controlled at 25℃, using nitrogen at 20sccm as the carrier gas. 2000mg of deionized water was added to the water source bottle, and the source bottle temperature was controlled at 25℃, using nitrogen at 20sccm as the water vapor carrier gas. Deposition was performed using a cycle of diethylzinc pulse, nitrogen purging, water vapor pulse, and nitrogen purging. The diethylzinc pulse duration was 250ms, the diethylzinc carrier gas flow rate was 20sccm, the first nitrogen purging duration was 8s, the nitrogen purging flow rate was 100sccm, the water vapor pulse duration was 150ms, the water vapor carrier gas flow rate was 20sccm, and the second nitrogen purging duration was 8s, the nitrogen purging flow rate was 100sccm. This cycle was repeated 120 times. Step 5: Deposit a gallium-doped zinc oxide layer: A gallium-doped zinc oxide layer is deposited on the zinc oxide transition layer formed in step four, with the reaction temperature maintained at 185℃ and the pressure maintained at 80Pa. First, a basic zinc oxide framework deposition is performed, using a cyclic sequence of diethylzinc pulse, nitrogen purging, water vapor pulse, and nitrogen purging. The diethylzinc pulse duration is 250ms, the diethylzinc carrier gas flow rate is 20sccm, the first nitrogen purging duration is 8s, the nitrogen purging flow rate is 100sccm, the water vapor pulse duration is 150ms, the water vapor carrier gas flow rate is 20sccm, and the second nitrogen purging duration is 8s, with a nitrogen purging flow rate of 100sccm. This cycle is repeated 90 times. Then, the post-gallium pulse stage begins, where 500mg of trimethylgallium is added to the trimethylgallium source bottle, and the temperature of the trimethylgallium source bottle is controlled at [temperature missing]. At 10℃, using nitrogen at 10 sccm as the trimethylgallium carrier gas, a cycle of diethylzinc short pulse, nitrogen purging, trimethylgallium post-pulse, nitrogen purging, water vapor short pulse, and nitrogen purging was employed. The diethylzinc short pulse duration was 100 ms, and the diethylzinc carrier gas flow rate was 20 sccm. The first nitrogen purging duration was 6 s, and the nitrogen purging flow rate was 100 sccm. The trimethylgallium post-pulse duration was 80 ms, and the trimethylgallium carrier gas flow rate was 10 sccm. The second nitrogen purging duration was 6 s, and the nitrogen purging flow rate was 100 sccm. The water vapor short pulse duration was 120 ms, and the water vapor carrier gas flow rate was 20 sccm. The third nitrogen purging duration was 10 s, and the nitrogen purging flow rate was 100 sccm. This cycle was repeated 12 times. Step 6: Construct tin-oxygen-gallium composite pinning sites in the gallium-rich band: After completing step five, without disrupting the vacuum environment, maintain the cavity temperature at 185℃ and the pressure at 80Pa. Add 1000mg of anhydrous tin tetrachloride to the anhydrous tin tetrachloride source bottle, maintaining the anhydrous tin tetrachloride source bottle temperature at 25℃ and the delivery pipeline temperature at 60℃. Use 10sccm of nitrogen as the carrier gas for anhydrous tin tetrachloride. Treat the surface of the gallium-doped zinc oxide layer using a short pulse of anhydrous tin tetrachloride and nitrogen purging. The short pulse duration of anhydrous tin tetrachloride is 50ms, the flow rate of anhydrous tin tetrachloride carrier gas is 10sccm, the nitrogen purging time is 15s, and the nitrogen purging flow rate is 100sccm. Repeat this cycle three times. Then, introduce a mixed gas of hydrogen and nitrogen, with hydrogen comprising 4% of the total gas volume, a flow rate of 50sccm, and a pressure of 100Pa. After a 45s residence time, purge with 100sccm of nitrogen for 20s. The exhaust gas is then absorbed by an alkaline solution and discharged. Step 7: Segmented stabilization of dry oxygen short pulses and water vapor subpulses: After the hydrogen reduction residence in step six, maintain the chamber temperature at 185°C and the pressure at 100Pa; first, introduce a mixture of oxygen and nitrogen gas, with an oxygen volume fraction of 2000ppm, a flow rate of 50sccm, and an introduction time of 8s, followed by purging with nitrogen at 100sccm for 20s; then, introduce a sub-pulse of water vapor, with the water source bottle temperature controlled at 25°C, nitrogen as the carrier gas, a flow rate of 10sccm, and a water vapor pulse time of 30ms, followed by purging with nitrogen at 100sccm for 20s, repeating only once; Step 8, Silver Deposition: After completing step seven, transfer the glass slide into a conventional DC magnetron sputtering chamber without exposing it to air; load 50g of silver target material into the sputtering chamber, control the target-substrate distance to 80mm, control the stage temperature to 60℃, and evacuate the chamber until the base pressure does not exceed 1×10⁻⁶. -3 Pa, argon gas was introduced at 25 sccm, and the working pressure was controlled at 300 mPa; first, pre-sputtering was performed at 10W power for 30s and the glass plate was shielded with a baffle to remove adsorbates on the surface of the silver target; then the baffle was opened, and deposition was performed at 15W power for 20s, and then at 35W power for 60s to form a silver layer. Step 9: Deposition of the upper zinc oxide capping layer and fluorine-doped tin oxide protective layer: Without exposing the silver layer to air, the glass slide obtained in step eight is kept in a conventional multi-target magnetron sputtering cavity, with the target-substrate distance controlled at 80 mm and the substrate stage temperature controlled at 80 °C. First, 50 g of zinc oxide target material is loaded, argon gas is introduced at 30 sccm, the working pressure is controlled at 300 mPa, and deposition is carried out at 80 W RF power for 12 min. Then, 50 g of tin oxide target material is loaded, argon gas at 28 sccm, oxygen gas at 2 sccm, and a mixture of carbon tetrafluoride and argon gas at 5 sccm, wherein the volume fraction of carbon tetrafluoride in the mixture of carbon tetrafluoride and argon gas is 5%, the working pressure is controlled at 400 mPa, and deposition is carried out at 100 W RF power for 20 min to form a fluorine-doped tin oxide protective layer. After deposition, the layer is cooled and purged with argon gas at 30 sccm for 5 min, then the gas supply is stopped and the vacuum is released. Step 10, Post-processing and Cold Bending Assembly: The coated glass sheet obtained in step nine is placed in a nitrogen-protected oven and continuously purged with 200 sccm of nitrogen. It is then kept at 180°C for 20 minutes and naturally cooled to 25°C under the protection of 200 sccm of nitrogen. Subsequently, the glass sheet is placed on an arc-shaped fixture with the coating layer located on the concave side of the arc. It is then slowly bonded at a displacement speed of 2 mm / min and kept at 25°C for 30 minutes to obtain bendable tempered energy-saving glass for cold chain applications.

[0036] The difference between Example 2 and Example 1 is as follows: In step one, 2g of sodium dodecyl sulfate, 9g of sodium carbonate and 1989g of deionized water were weighed to prepare 2000g of weak alkaline cleaning solution, which was ultrasonically cleaned at 38℃ for 7min; then rinsed twice with 2000g of deionized water for 5min each time, and then immersed in 1000g of anhydrous ethanol for 4min; finally, it was purged with nitrogen gas at a flow rate of 9L / min for 2min. In step two, 10,000 g of potassium nitrate was weighed and placed in a stainless steel molten salt tank, melted at 405°C and kept at a constant temperature for 55 min, and the glass slide was completely immersed in the molten salt and kept at 405°C for 130 min. After taking it out, it was washed twice with 1,000 g of deionized water at 78°C for 5 min each time, and then washed once with 1,000 g of deionized water at 25°C. Finally, it was dried at 175°C for 30 min. In step three, the substrate temperature is raised to 225℃ and held for 9 minutes; a mixture of silane and nitrogen gas at 22 sccm, ammonia at 75 sccm, and nitrogen at 480 sccm is introduced, the working pressure of the chamber is controlled at 95 Pa, the radio frequency power is controlled at 75 W, and the deposition time is 9 minutes; after deposition, the chamber is purged with nitrogen at 480 sccm for 3 minutes. In step four, the substrate temperature is controlled at 182℃, and the cavity pressure is controlled at 75Pa; the diethylzinc source bottle temperature is controlled at 22℃, and the diethylzinc carrier gas is nitrogen at 18 sccm; the water source bottle temperature is controlled at 22℃, and the water vapor carrier gas is nitrogen at 18 sccm; the diethylzinc pulse time is 230ms, the first nitrogen purging time is 7s, the nitrogen purging flow rate is 95 sccm, the water vapor pulse time is 140ms, the second nitrogen purging time is 7s, the nitrogen purging flow rate is 95 sccm, and this is repeated for 115 cycles; In step five, during the deposition of the gallium-doped zinc oxide layer, the reaction temperature was maintained at 182℃ and the pressure at 75Pa. During the basic zinc oxide framework deposition stage, the diethylzinc pulse duration was 230ms, the diethylzinc carrier gas flow rate was 18sccm, the first nitrogen purging time was 7s, the nitrogen purging flow rate was 95sccm, the water vapor pulse duration was 140ms, the water vapor carrier gas flow rate was 18sccm, the second nitrogen purging time was 7s, and the nitrogen purging flow rate was 95sccm, repeated for 85 cycles. In the post-gallium pulse stage, 450mg of trimethylgallium was added to the trimethylgallium source vial. The temperature of the gallium (Ga) trimethylgallium (GMG) source bottle was controlled at 8°C. The carrier gas for GMG was nitrogen at 9 sccm. The short pulse duration of diethylzinc was 90 ms, and the carrier gas flow rate of diethylzinc was 18 sccm. The first nitrogen purging time was 6 s, and the nitrogen purging flow rate was 95 sccm. The post-pulse duration of GMG was 70 ms. The second nitrogen purging time was 6 s, and the nitrogen purging flow rate was 95 sccm. The short pulse duration of water vapor was 110 ms, and the water vapor carrier gas flow rate was 18 sccm. The third nitrogen purging time was 9 s, and the nitrogen purging flow rate was 95 sccm. This process was repeated for 11 cycles. In step six, maintain the chamber temperature at 182℃ and the pressure at 75Pa; add 900mg of anhydrous tin tetrachloride to the anhydrous tin tetrachloride source bottle, maintain the anhydrous tin tetrachloride source bottle temperature at 22℃, and maintain the delivery pipeline temperature at 58℃; use nitrogen at 9sccm as the carrier gas for anhydrous tin tetrachloride, with an anhydrous tin tetrachloride short pulse duration of 45ms, a nitrogen purging time of 15s, and a nitrogen purging flow rate of 95sccm, repeating 3 cycles; then introduce a mixture of hydrogen and nitrogen gas at a flow rate of 45sccm and a pressure of 95Pa, hold for 40s, and then purge with nitrogen at 95sccm for 18s; In step seven, the cavity temperature is maintained at 182℃ and the pressure is controlled at 95Pa. First, a mixture of oxygen and nitrogen is introduced, with an oxygen volume fraction of 1800ppm, a flow rate of 45sccm, and an introduction time of 7s. Then, nitrogen is purged at 95sccm for 18s. Next, water vapor is introduced in a sub-pulse, with the water source bottle temperature controlled at 22℃, a water vapor carrier gas flow rate of 9sccm, and a water vapor pulse time of 25ms. Then, nitrogen is purged at 95sccm for 18s. This process is repeated only once. In step eight, the target-substrate distance is controlled at 75 mm, the substrate stage temperature is controlled at 55 °C, argon gas is introduced at 22 sccm, and the working pressure is controlled at 280 mPa. First, pre-sputter at 10 W power for 25 s and shield the glass sheet with a baffle. Then, open the baffle and deposit at 18 W power for 18 s, and then deposit at 32 W power for 55 s to form a silver layer. In step nine, the target-substrate distance is controlled at 75 mm, and the substrate stage temperature is controlled at 75 °C. During the deposition of the zinc oxide capping layer, argon gas is introduced at 28 sccm, the working pressure is controlled at 280 mPa, and the deposition is carried out at 75 W RF power for 11 min. During the deposition of the fluorine-doped tin oxide protective layer, argon gas at 26 sccm, oxygen gas at 2 sccm, and a mixture of carbon tetrafluoride and argon gas at 4 sccm are introduced, the working pressure is controlled at 380 mPa, and the deposition is carried out at 95 W RF power for 19 min. After deposition, the layer is cooled and purged with argon gas at 28 sccm for 5 min. In step ten, nitrogen gas is continuously introduced at 180 sccm, and the temperature is maintained at 175°C for 18 minutes. Then, the glass sheet is naturally cooled to 25°C under the protection of nitrogen gas at 180 sccm. Subsequently, the glass sheet is placed on an arc-shaped fixture with a radius of 140 mm with the film layer located on the concave side of the arc. The glass sheet is slowly bonded at a displacement speed of 2 mm / min and maintained at 25°C for 25 minutes to obtain bendable tempered energy-saving glass for cold chain. The remaining conditions are the same as in Example 1.

[0037] The difference between Example 3 and Example 1 is as follows: In step one, 2g of sodium dodecyl sulfate, 11g of sodium carbonate and 1987g of deionized water were weighed to prepare 2000g of weak alkaline cleaning solution, which was ultrasonically cleaned at 42℃ for 9min; then rinsed twice with 2000g of deionized water for 6min each time, and then immersed in 1000g of anhydrous ethanol for 5min; finally, it was purged with nitrogen gas at a flow rate of 11L / min for 3min. In step two, 10,000g of potassium nitrate was weighed and placed in a stainless steel molten salt bath. It was melted at 415℃ and kept at a constant temperature for 65 minutes. The glass slide was completely immersed in the molten salt and kept at 415℃ for 110 minutes. After being removed, it was washed twice with 1,000g of deionized water at 82℃ for 6 minutes each time, and then washed once with 1,000g of deionized water at 28℃. Finally, it was dried at 185℃ for 35 minutes. In step three, the substrate temperature is raised to 235℃ and held for 11 minutes; a mixture of silane and nitrogen gas at 28 sccm, ammonia at 85 sccm, and nitrogen at 520 sccm is introduced, the working pressure of the chamber is controlled at 105 Pa, the radio frequency power is controlled at 85 W, and the deposition time is 11 minutes; after deposition, the chamber is purged with nitrogen at 520 sccm for 4 minutes. In step four, the substrate temperature is controlled at 188℃, and the cavity pressure is controlled at 85Pa; the diethylzinc source bottle temperature is controlled at 28℃, and the diethylzinc carrier gas is nitrogen at 22 sccm; the water source bottle temperature is controlled at 28℃, and the water vapor carrier gas is nitrogen at 22 sccm; the diethylzinc pulse time is 270ms, the first nitrogen purging time is 9s, the nitrogen purging flow rate is 105 sccm, the water vapor pulse time is 160ms, the second nitrogen purging time is 9s, and the nitrogen purging flow rate is 105 sccm, and this is repeated for 125 cycles; In step five, during the deposition of the gallium-doped zinc oxide layer, the reaction temperature was maintained at 188℃ and the pressure at 85Pa. During the basic zinc oxide framework deposition stage, the diethylzinc pulse time was 270ms, the diethylzinc carrier gas flow rate was 22sccm, the first nitrogen purging time was 9s, and the nitrogen purging flow rate was 105sccm. The water vapor pulse time was 160ms, the water vapor carrier gas flow rate was 22sccm, and the second nitrogen purging time was 9s, with a nitrogen purging flow rate of 105sccm. This process was repeated 95 times. In the post-gallium pulse stage, 550mg of trimethylgallium was added to the trimethylgallium source vial. The temperature of the methylgallium source bottle was controlled at 12℃. The carrier gas for trimethylgallium was nitrogen at 11 sccm. The short pulse duration of diethylzinc was 110 ms, and the carrier gas flow rate of diethylzinc was 22 sccm. The first nitrogen purging time was 7 s, and the nitrogen purging flow rate was 105 sccm. The post-pulse duration of trimethylgallium was 90 ms. The second nitrogen purging time was 7 s, and the nitrogen purging flow rate was 105 sccm. The short pulse duration of water vapor was 130 ms, and the water vapor carrier gas flow rate was 22 sccm. The third nitrogen purging time was 11 s, and the nitrogen purging flow rate was 105 sccm. This cycle was repeated 13 times. In step six, maintain the chamber temperature at 188℃ and the pressure at 85Pa; add 1100mg of anhydrous tin tetrachloride to the anhydrous tin tetrachloride source bottle, maintain the anhydrous tin tetrachloride source bottle temperature at 28℃, maintain the delivery pipeline temperature at 62℃, use nitrogen at 11sccm as the anhydrous tin tetrachloride carrier gas, the anhydrous tin tetrachloride short pulse time is 55ms, the nitrogen purging time is 16s, and the nitrogen purging flow rate is 105sccm, repeat 3 cycles; then introduce a mixture of hydrogen and nitrogen gas, the mixed gas flow rate is 55sccm, the pressure is controlled at 105Pa, hold for 50s, and then purge with nitrogen at 105sccm for 22s; In step seven, the cavity temperature is maintained at 188℃ and the pressure is controlled at 105Pa. First, a mixture of oxygen and nitrogen is introduced, with an oxygen volume fraction of 2200ppm, a flow rate of 55sccm, and an introduction time of 9s. Then, it is purged with nitrogen at 105sccm for 22s. Next, a sub-pulse of water vapor is introduced, with the water source bottle temperature controlled at 28℃, a water vapor carrier gas flow rate of 11sccm, and a water vapor pulse time of 40ms. Then, it is purged with nitrogen at 105sccm for 22s. This process is repeated only once. In step eight, the target-substrate distance is controlled at 85 mm, the substrate stage temperature is controlled at 65 °C, argon gas is introduced at 28 sccm, and the working pressure is controlled at 320 mPa. First, pre-sputter at 10 W power for 35 s and shield the glass sheet with a baffle. Then, open the baffle and deposit at 22 W power for 22 s, and then deposit at 38 W power for 65 s to form a silver layer. In step nine, the target-substrate distance is controlled at 85 mm, and the substrate stage temperature is controlled at 85 °C. During the deposition of the zinc oxide capping layer, argon gas is introduced at 32 sccm, the working pressure is controlled at 320 mPa, and the deposition is carried out at 85 W RF power for 13 min. During the deposition of the fluorine-doped tin oxide protective layer, argon gas at 30 sccm, oxygen gas at 3 sccm, and a mixture of carbon tetrafluoride and argon gas at 6 sccm are introduced, the working pressure is controlled at 420 mPa, and the deposition is carried out at 105 W RF power for 21 min. After deposition, argon gas is used for cooling and purging at 32 sccm for 6 min. In step ten, nitrogen gas at 220 sccm is continuously introduced and the temperature is maintained at 185°C for 22 min. Then, the glass sheet is naturally cooled to 25°C under the protection of nitrogen gas at 220 sccm. Subsequently, the glass sheet is placed on an arc-shaped fixture with a radius of 170 mm with the film layer located on the concave side of the arc. The glass sheet is slowly bonded at a displacement speed of 3 mm / min and maintained at 25°C for 35 min to obtain bendable tempered energy-saving glass for cold chain. The remaining conditions are the same as in Example 1.

[0038] Example 4: A method for preparing bendable tempered energy-saving glass for cold chain applications, the specific steps of which are as follows: Step 1: Weigh 1g sodium dodecyl sulfate, 8g sodium carbonate, and 1991g deionized water to prepare 2000g of weak alkaline cleaning solution. Immerse the glass slide in the weak alkaline cleaning solution and ultrasonically clean it at 35°C for 6 minutes. Then rinse it twice with 2000g deionized water for 4 minutes each time, and then soak it in 1000g anhydrous ethanol for 3 minutes. Finally, purge it with nitrogen gas at a flow rate of 8L / min for 2 minutes until there are no visible droplets on the glass surface. Step 2, Chemical Tempering: Weigh 10,000g of potassium nitrate and place it in a stainless steel molten salt bath. Melt it at 400℃ and keep it at that temperature for 50 minutes. Completely immerse the glass slide treated in Step 1 in the molten salt and keep it at 400℃ for 100 minutes to allow sodium ions on the glass surface to exchange with potassium ions in the molten salt. After removing the glass slide, immediately rinse it twice with 1,000g of deionized water at 75℃ for 4 minutes each time, then rinse it once with 1,000g of deionized water at 20℃, and finally dry it at 170℃ for 25 minutes. Step 3, Silicon nitride barrier layer deposition: Place the glass slide obtained in Step 2 into the plasma-enhanced chemical vapor deposition chamber, and evacuate the chamber to a base pressure not exceeding 1×10⁻⁶. -3 Pa, raise the substrate temperature to 220℃ and hold for 8 min; introduce a mixture of silane and nitrogen gas at 20 sccm, ammonia at 70 sccm, and nitrogen at 450 sccm, control the cavity working pressure to 90 Pa, control the RF power to 70 W, and the deposition time to 8 min; after deposition, turn off the RF power and purge with nitrogen at 450 sccm for 2 min. Step 4, Zinc oxide transition layer deposition: Under conditions of no contact with air, the glass slide obtained in Step 3 is transferred into the pulsed chemical vapor deposition chamber, and the chamber is evacuated to a base pressure not exceeding 1×10⁻⁶. -3 The substrate temperature was controlled at 180℃ and the chamber pressure at 70Pa. 3000mg of diethylzinc was added to the diethylzinc source bottle, and the temperature of the diethylzinc source bottle was controlled at 20℃. Nitrogen gas at 15sccm was used as the carrier gas for diethylzinc. 2000mg of deionized water was added to the water source bottle, and the temperature of the water source bottle was controlled at 20℃. Nitrogen gas at 15sccm was used as the carrier gas for water vapor. Deposition was performed using a cycle of diethylzinc pulse, nitrogen purging, water vapor pulse, and nitrogen purging. The diethylzinc pulse duration was 220ms, the first nitrogen purging duration was 7s, the nitrogen purging flow rate was 90sccm, the water vapor pulse duration was 130ms, the second nitrogen purging duration was 7s, and the nitrogen purging flow rate was 90sccm. This cycle was repeated 110 times. Step 5, Deposition of Gallium-Doped Zinc Oxide Layer: A gallium-doped zinc oxide layer is deposited on the zinc oxide transition layer formed in Step 4, maintaining the reaction temperature at 180℃ and the pressure at 70Pa. First, a basic zinc oxide framework deposition is performed, using a cyclic sequence of diethylzinc pulse, nitrogen purging, water vapor pulse, and nitrogen purging. The diethylzinc pulse duration is 220ms, the diethylzinc carrier gas flow rate is 15sccm, the first nitrogen purging duration is 7s, the nitrogen purging flow rate is 90sccm, the water vapor pulse duration is 130ms, the water vapor carrier gas flow rate is 15sccm, and the second nitrogen purging duration is 7s, the nitrogen purging flow rate is 90sccm. This cycle is repeated 80 times. Then, the post-gallium pulse stage begins, adding 400mg of trimethylgallium to the trimethylgallium source bottle. The temperature of the gallium source bottle was controlled at 5℃. Nitrogen gas at 8 sccm was used as the trimethylgallium (TMG) carrier gas. The cycle sequence was: diethylzinc short pulse, nitrogen purging, TMG post-pulse, nitrogen purging, water vapor short pulse, and nitrogen purging. The diethylzinc short pulse duration was 80 ms and the diethylzinc carrier gas flow rate was 15 sccm. The first nitrogen purging duration was 5 s and the nitrogen purging flow rate was 90 sccm. The TMG post-pulse duration was 60 ms and the TMG carrier gas flow rate was 8 sccm. The second nitrogen purging duration was 5 s and the nitrogen purging flow rate was 90 sccm. The water vapor short pulse duration was 100 ms and the water vapor carrier gas flow rate was 15 sccm. The third nitrogen purging duration was 8 s and the nitrogen purging flow rate was 90 sccm. This cycle was repeated 10 times. Step Six: Constructing Tin-Oxide-Galan Composite Pinning Sites in the Gallium-Enriched Zone: After completing Step Five, without disrupting the vacuum environment, maintain the cavity temperature at 180℃ and the pressure at 70Pa; add 800mg of anhydrous tin tetrachloride to the anhydrous tin tetrachloride source bottle, maintaining the anhydrous tin tetrachloride source bottle temperature at 20℃ and the delivery pipeline temperature at 55℃; use 8sccm of nitrogen as the carrier gas for anhydrous tin tetrachloride; treat the surface of the gallium-doped zinc oxide layer using a short pulse of anhydrous tin tetrachloride and nitrogen purging, wherein the short pulse duration of anhydrous tin tetrachloride is 40ms, the nitrogen purging time is 14s, and the nitrogen purging flow rate is 90sccm, repeating 2 cycles; then introduce a mixed gas of hydrogen and nitrogen, wherein the hydrogen component in the mixed gas is 4%, the mixed gas flow rate is 40sccm, and the pressure is controlled at 90Pa, hold for 35s, then purge with nitrogen at 90sccm for 15s, and the exhaust gas is discharged after being absorbed by alkaline solution.

[0039] Step 7, segmented stabilization of dry oxygen short pulse and water vapor subpulse: After the hydrogen reduction residence in Step 6, maintain the chamber temperature at 180℃ and the pressure at 90Pa; first, introduce a mixture of oxygen and nitrogen gas, with an oxygen volume fraction of 1500ppm, a flow rate of 40sccm, and an introduction time of 6s, followed by purging with nitrogen at 90sccm for 15s; then, introduce a water vapor subpulse, with the water source bottle temperature controlled at 20℃, nitrogen as the water vapor carrier gas, a water vapor carrier gas flow rate of 8sccm, and a water vapor pulse time of 20ms, followed by purging with nitrogen at 90sccm for 15s, repeating only once.

[0040] Step 8, Silver Deposition: After completing Step 7, transfer the glass slide into a conventional DC magnetron sputtering chamber without exposing it to air; load 50g of silver target material into the sputtering chamber, control the target-substrate distance to 70mm, control the stage temperature to 50℃, and evacuate the chamber until the base pressure does not exceed 1×10⁻⁶. -3 Pa, argon gas was introduced at 20 sccm, and the working pressure was controlled at 250 mPa; first, pre-sputtering was performed at 10 W power for 20 s and the glass slide was shielded with a baffle to remove adsorbates on the surface of the silver target; then the baffle was opened and deposition was performed at 15 W power for 15 s, and then at 30 W power for 50 s to form a silver layer. Step 9, deposition of the upper zinc oxide capping layer and fluorine-doped tin oxide protective layer: Under the condition that the silver layer is not exposed to air, the glass slide obtained in Step 8 is kept in the conventional multi-target magnetron sputtering cavity, the target-substrate distance is controlled at 70 mm, and the substrate stage temperature is controlled at 70 °C; first, 50 g of zinc oxide target material is loaded, argon gas is introduced at 25 sccm, the working pressure is controlled at 250 mPa, and deposition is carried out at 70 W RF power for 10 min; then, 50 g of tin oxide target material is loaded, argon gas is introduced at 25 sccm, oxygen at 1 sccm, and a mixture of carbon tetrafluoride and argon gas at 4 sccm, wherein the volume fraction of carbon tetrafluoride in the mixture of carbon tetrafluoride and argon gas is 5%, the working pressure is controlled at 350 mPa, and deposition is carried out at 90 W RF power for 18 min; after deposition, argon gas is used for cooling and purging at 25 sccm for 4 min, then the gas intake is stopped and the vacuum is released; Step 10, Post-processing and Cold Bending Assembly: Place the coated glass sheet obtained in Step 9 in a nitrogen-protected oven, continuously introduce nitrogen at 150 sccm, and keep it at 170℃ for 15 min. Then, naturally cool it to 25℃ under the protection of nitrogen at 150 sccm. Subsequently, place the glass sheet on an arc-shaped fixture with the coating layer located on the concave side of the arc, and slowly adhere it at a displacement speed of 1 mm / min. Keep it at 25℃ for 20 min to obtain bendable tempered energy-saving glass for cold chain applications.

[0041] Example 5: A method for preparing bendable tempered energy-saving glass for cold chain applications, the specific steps of which are as follows: Step 1: Weigh 3g sodium dodecyl sulfate, 12g sodium carbonate, and 1985g deionized water to prepare 2000g of weak alkaline cleaning solution. Immerse the glass slide in the weak alkaline cleaning solution and ultrasonically clean it at 45°C for 10 minutes. Then rinse it twice with 2000g deionized water for 6 minutes each time, and then soak it in 1000g anhydrous ethanol for 5 minutes. Finally, purge it with nitrogen gas at a flow rate of 12L / min for 3 minutes until there are no visible droplets on the glass surface. Step 2, Chemical Tempering: Weigh 10,000g of potassium nitrate and place it in a stainless steel molten salt bath. Melt it at 420℃ and keep the temperature constant for 70 minutes. Completely immerse the glass slide treated in Step 1 in the molten salt and keep it at 420℃ for 140 minutes to allow sodium ions on the glass surface to exchange with potassium ions in the molten salt. After removing it, immediately wash it twice with 1,000g of deionized water at 85℃ for 6 minutes each time, then wash it once with 1,000g of deionized water at 30℃, and then dry it at 190℃ for 35 minutes. Step 3, Silicon nitride barrier layer deposition: Place the glass slide obtained in Step 2 into the plasma-enhanced chemical vapor deposition chamber, and evacuate the chamber to a base pressure not exceeding 1×10⁻⁶. -3 Pa, raise the substrate temperature to 240℃ and hold for 12 min; introduce a mixture of silane and nitrogen gas at 30 sccm, ammonia at 90 sccm, and nitrogen at 550 sccm, control the cavity working pressure to 110 Pa, control the RF power to 90 W, and the deposition time to 12 min; after deposition, turn off the RF power and purge with nitrogen at 550 sccm for 4 min.

[0042] Step 4, Zinc oxide transition layer deposition: Under conditions of no contact with air, the glass slide obtained in Step 3 is transferred into the pulsed chemical vapor deposition chamber, and the chamber is evacuated to a base pressure not exceeding 1×10⁻⁶. -3 The substrate temperature was controlled at 190℃ and the chamber pressure at 90Pa. 3000mg of diethylzinc was added to the diethylzinc source bottle, and the temperature of the diethylzinc source bottle was controlled at 30℃. Nitrogen gas at 25sccm was used as the carrier gas for diethylzinc. 2000mg of deionized water was added to the water source bottle, and the temperature of the water source bottle was controlled at 30℃. Nitrogen gas at 25sccm was used as the water vapor carrier gas. Deposition was performed using a cycle of diethylzinc pulse, nitrogen purging, water vapor pulse, and nitrogen purging. The diethylzinc pulse duration was 280ms, the first nitrogen purging duration was 9s, the nitrogen purging flow rate was 110sccm, the water vapor pulse duration was 170ms, and the second nitrogen purging duration was 9s. The nitrogen purging flow rate was 110sccm. This cycle was repeated 130 times. Step 5, Deposition of Gallium-Doped Zinc Oxide Layer: A gallium-doped zinc oxide layer is deposited on the zinc oxide transition layer formed in Step 4, maintaining the reaction temperature at 190℃ and the pressure at 90Pa. First, a basic zinc oxide framework deposition is performed, using a cyclic sequence of diethylzinc pulse, nitrogen purging, water vapor pulse, and nitrogen purging. The diethylzinc pulse duration is 280ms, the diethylzinc carrier gas flow rate is 25sccm, the first nitrogen purging duration is 9s, the nitrogen purging flow rate is 110sccm, the water vapor pulse duration is 170ms, the water vapor carrier gas flow rate is 25sccm, and the second nitrogen purging duration is 9s, the nitrogen purging flow rate is 110sccm. This cycle is repeated 100 times. Then, the post-gallium pulse stage begins, adding 600mg of trimethylgallium to the trimethylgallium source vial. The bottle temperature was controlled at 15℃. Nitrogen gas at 12 sccm was used as the trimethylgallium (TMG) carrier gas. The cycle sequence was: diethylzinc short pulse, nitrogen purging, TMG post-pulse, nitrogen purging, water vapor short pulse, and nitrogen purging. The diethylzinc short pulse duration was 120 ms and the diethylzinc carrier gas flow rate was 25 sccm. The first nitrogen purging duration was 7 s and the nitrogen purging flow rate was 110 sccm. The TMG post-pulse duration was 100 ms and the TMG carrier gas flow rate was 12 sccm. The second nitrogen purging duration was 7 s and the nitrogen purging flow rate was 110 sccm. The water vapor short pulse duration was 140 ms and the water vapor carrier gas flow rate was 25 sccm. The third nitrogen purging duration was 12 s and the nitrogen purging flow rate was 110 sccm. This cycle was repeated 14 times. Step Six: Constructing Tin-Oxygen-Galan Composite Pinning Sites in the Gallium-Enriched Zone: After completing Step Five, without disrupting the vacuum environment, maintain the cavity temperature at 190℃ and the pressure at 90Pa; add 1200mg of anhydrous tin tetrachloride to the anhydrous tin tetrachloride source bottle, maintaining the anhydrous tin tetrachloride source bottle temperature at 30℃ and the delivery pipeline temperature at 65℃; use 12sccm of nitrogen as the anhydrous tin tetrachloride carrier gas; treat the surface of the gallium-doped zinc oxide layer using a short pulse of anhydrous tin tetrachloride and nitrogen purging, wherein the short pulse duration of anhydrous tin tetrachloride is 60ms, the nitrogen purging time is 16s, and the nitrogen purging flow rate is 110sccm, repeating 4 cycles; then introduce a mixed gas of hydrogen and nitrogen, wherein the hydrogen component in the mixed gas is 4%, the mixed gas flow rate is 60sccm, and the pressure is controlled at 110Pa; after a 55s residence time, purge with 110sccm of nitrogen for 25s; the exhaust gas is absorbed by alkaline solution and then discharged; Step 7, segmented stabilization of dry oxygen short pulse and water vapor subpulse: After the hydrogen reduction residence in Step 6, maintain the chamber temperature at 190℃ and the pressure at 110Pa; first, introduce a mixture of oxygen and nitrogen gas, with an oxygen volume fraction of 2500ppm, a flow rate of 60sccm, and an introduction time of 10s, followed by purging with nitrogen at 110sccm for 25s; then, introduce a water vapor subpulse, with the water source bottle temperature controlled at 30℃, nitrogen as the water vapor carrier gas, a water vapor carrier gas flow rate of 12sccm, and a water vapor pulse time of 50ms, followed by purging with nitrogen at 110sccm for 25s, repeating only once; Step 8, Silver Deposition: After completing Step 7, transfer the glass slide into a conventional DC magnetron sputtering chamber without exposing it to air; load 50g of silver target material into the sputtering chamber, control the target-substrate distance to 90mm, control the stage temperature to 70℃, and evacuate the chamber until the base pressure does not exceed 1×10⁻⁶. -3 Pa, argon gas was introduced at 30 sccm, and the working pressure was controlled at 350 mPa; first, pre-sputtering was performed at 10 W power for 40 s and the glass slide was shielded with a baffle to remove adsorbates on the surface of the silver target; then the baffle was opened and deposition was performed at 25 W power for 25 s, and then at 40 W power for 70 s to form a silver layer. Step 9, deposition of the upper zinc oxide capping layer and fluorine-doped tin oxide protective layer: Under the condition that the silver layer is not exposed to air, the glass slide obtained in Step 8 is kept in the conventional multi-target magnetron sputtering cavity, the target-substrate distance is controlled at 90 mm, and the substrate stage temperature is controlled at 90 °C; first, 50 g of zinc oxide target material is loaded, argon gas is introduced at 35 sccm, the working pressure is controlled at 350 mPa, and deposition is carried out at 90 W RF power for 14 min; then, 50 g of tin oxide target material is loaded, argon gas is introduced at 32 sccm, oxygen at 3 sccm, and a mixture of carbon tetrafluoride and argon gas at 6 sccm, wherein the volume fraction of carbon tetrafluoride in the mixture of carbon tetrafluoride and argon gas is 5%, the working pressure is controlled at 450 mPa, and deposition is carried out at 110 W RF power for 22 min; after deposition, argon gas is used for cooling and purging at 35 sccm for 6 min, then the gas intake is stopped and the vacuum is released; Step 10, Post-processing and Cold Bending Assembly: Place the coated glass sheet obtained in Step 9 in a nitrogen-protected oven, continuously introduce nitrogen at 250 sccm, and keep it at 190℃ for 25 min. Then, naturally cool it to 25℃ under the protection of nitrogen at 250 sccm. Subsequently, place the glass sheet on an arc-shaped fixture with the coating layer located on the concave side of the arc, and slowly bond it at a displacement speed of 3 mm / min. Keep it at 25℃ for 40 min to obtain bendable tempered energy-saving glass for cold chain applications.

[0043] The difference between Comparative Example 1 and Example 1 is that in step five, trimethylgallium pulses are synchronously introduced in all cycles of the basic zinc oxide framework deposition and the post-stage. The amount of trimethylgallium source bottle, the cumulative amount of trimethylgallium introduced, the diethylzinc pulse time, the water vapor pulse time, the nitrogen purging time, and the total thickness of the gallium-doped zinc oxide layer are all the same as in Example 1, and the other conditions are the same as in Example 1.

[0044] The difference between Comparative Example 2 and Example 1 is that in step six, instead of anhydrous tin tetrachloride short pulses, nitrogen blank pulses are used instead of anhydrous tin tetrachloride short pulses. The nitrogen blank pulse time is 50ms, the nitrogen purging time is 15s, and this is repeated for 3 cycles. The flow rate, residence time, and pressure of the hydrogen and nitrogen mixed gas in step six, as well as the subsequent steps seven to ten, are the same as in Example 1. All other conditions are the same as in Example 1.

[0045] The difference between Comparative Example 3 and Example 1 is that in step six, the order of the short pulse of anhydrous tin tetrachloride and the hydrogen reduction residence is reversed. That is, a mixture of hydrogen and nitrogen gas is first introduced, wherein the hydrogen gas fraction in the mixture is 4%, the flow rate of the mixture is 50 sccm, the pressure is controlled at 100 Pa, and after residence for 45 s, it is purged with nitrogen at 100 sccm for 20 s; then the short pulse treatment of anhydrous tin tetrachloride is performed again, wherein the short pulse time of anhydrous tin tetrachloride is 50 ms, the nitrogen purging time is 15 s, and the cycle is repeated for 3 times; the other conditions are the same as in Example 1.

[0046] The difference between Comparative Example 4 and Example 1 is that in step seven, the order of the dry oxygen short pulse and the water vapor sub-pulse is reversed. That is, the water vapor sub-pulse is introduced first, the temperature of the water source bottle is controlled at 25°C, the water vapor carrier gas is nitrogen, the water vapor carrier gas flow rate is 10 sccm, and the water vapor pulse time is 30 ms, followed by purging with nitrogen at 100 sccm for 20 s; then a mixture of oxygen and nitrogen is introduced, the oxygen volume fraction in the mixture is 2000 ppm, the mixed gas flow rate is 50 sccm, the introduction time is 8 s, followed by purging with nitrogen at 100 sccm for 20 s; the remaining conditions are the same as in Example 1.

[0047] The difference between Comparative Example 5 and Example 1 is that in step seven, the dry oxygen short pulse is cancelled and the oxygen and nitrogen mixture is replaced with a nitrogen blank pulse. The nitrogen blank pulse flow rate is 50 sccm and the introduction time is 8s, followed by purging with nitrogen at 100 sccm for 20s. The water vapor subpulse, silver low-emissivity layer deposition, upper zinc oxide capping layer and fluorine-doped tin oxide protective layer deposition are the same as in Example 1. The remaining conditions are the same as in Example 1.

[0048] The difference between Comparative Example 6 and Example 1 is that in step seven, the water vapor subpulse is cancelled and replaced with a nitrogen blank pulse. The nitrogen blank pulse flow rate is 10 sccm and the pulse time is 30 ms. Then, the nitrogen is purged for 20 s at 100 sccm. The dry oxygen short pulse, silver low-emissivity layer deposition, upper zinc oxide capping layer and fluorine-doped tin oxide protective layer deposition are the same as in Example 1. The other conditions are the same as in Example 1.

[0049] The difference between Comparative Example 7 and Example 1 is that in step eight, the deposition time of the silver main functional layer is extended from 60s to 90s, while the deposition power of the silver main functional layer remains at 35W; the near-silver interface modification sequence in steps five to seven, the protective layer deposition in step nine, and the cold bending assembly in step ten are the same as in Example 1; the remaining conditions are the same as in Example 1.

[0050] Performance testing Film thickness: The film thickness was tested using the X-ray reflection method specified in GB / T 36053-2018. The test sample was a 100mm×100mm coated glass slide. The test angle range was 0.2° to 5° with a step size of 0.005°. A copper target Kα ray was used, with a working voltage of 40kV and a working current of 40mA. For each sample, five points were measured: the center point and the four corners recessed by 30mm. The average value was then taken.

[0051] Visible light transmittance and emissivity testing: Visible light transmittance was tested according to GB / T 2680-2021. The sample size was 100mm×100mm. Before the test, the non-film surface was wiped with anhydrous ethanol and placed in an environment of 25℃ and 50% relative humidity for 2 hours. The spectral transmittance was tested in the 380nm to 780nm band using an integrating sphere spectrophotometer. The visible light transmittance was calculated according to the standard light source D65 and standard observer conditions. Emissivity was tested according to the relevant testing requirements for low-emissivity coated glass in GB / T 18915.2-2013. The test surface was a low-emissivity functional surface. The reflectivity in the 8μm to 14μm band was measured using the infrared reflectance method and then converted to emissivity. Five locations were tested for each sample, and the average value was taken as the result.

[0052] Sheet resistance and thermal cycling stability test: Sheet resistance was tested using the straight-line four-probe method. The test sample was a 100mm×100mm coated glass sheet with a probe spacing of 1mm and a test current of 10mA. Nine test points were selected for each sample in a nine-square grid, and the area within 10mm of the edge was removed. The average sheet resistance was recorded. The thermal cycling was conducted according to the temperature change test procedure specified in GB / T 2423.22-2012, using a two-chamber method. The low-temperature chamber was set at -20℃, and the high-temperature chamber at 25℃. Each temperature zone was maintained for 30 minutes, with a transition time of less than 3 minutes, and the cycle was repeated 100 times. After the cycle, the sample was equilibrated in an environment of 25℃ and 50% relative humidity for 2 hours, and then the sheet resistance was tested using the same four-probe method to calculate the sheet resistance rise rate.

[0053] Cold bending compatibility and bending strength test: The cold bending compatibility test uses a 300mm×500mm coated glass sheet. The film layer is placed on the concave side of the arc. At 25°C, it is cold bent and assembled according to the bending radius and bonding speed specified in each embodiment or comparative example. After holding for 30 minutes, it is taken out and the emissivity and sheet resistance are tested again after cold bending. The bending strength test was conducted according to the four-point bending loading principle of GB / T 37781-2019 for internal relative evaluation. The sample was a 100mm×25mm strip coated glass sheet with an outer span of 80mm and an inner span of 40mm. The loading rate was 1mm / min, and the film layer was located on the tension side. Five sheets were tested in each group. The fracture load was recorded and the bending strength was calculated according to the four-point bending formula for rectangular cross-section.

[0054] Film adhesion and abrasion resistance test: The cross-cut adhesion performance of the film was tested according to GB / T 9286-2021. The sample was a 100mm×100mm coated glass sheet. A cross-cut knife with a 1mm spacing was used to form 100 scratches on the film surface. The scratches penetrated the film to the glass surface. Standard tape was applied and peeled off at a uniform speed at an angle of about 60° within 90s. The number of film peels off was observed and the grade was rated. The abrasion resistance test was conducted according to the abrasion resistance test method of medium and low emissivity coated glass in GB / T 18915.2-2013. The sample was placed on a horizontal rotary abrasion tester with a rotation speed of 60 r / min and an abrasion time of 1000 revolutions. After abrasion, the visible light transmittance of 4 points in the abrasion area was tested and the average value was taken. The difference in visible light transmittance before and after abrasion was calculated.

[0055] Table 1 Performance Test Results

[0056] As shown in Table 1, Comparative Example 1, which uses uniform gallium doping to form a gallium-doped zinc oxide seed layer, still exhibits some low-emissivity performance, but its emissivity, sheet resistance, and silver island size after cold bending are significantly inferior to those of the Example 1. This indicates that the total amount of gallium is not the key factor; the spatial distribution of gallium near the silver interface and the timing of the post-pulse are crucial for inducing continuous nucleation of the silver layer. Compared to Comparative Example 1, Examples 1-5, through trimethylgallium post-pulse, anhydrous tin tetrachloride short pulse with hydrogen reduction and residence, and segmented stabilization using dry oxygen followed by water vapor, maintain a continuous thin-layer state of the silver layer at a relatively thin thickness, while also achieving low emissivity, low sheet resistance increase rate, and cold bending stability. Example 2 shows that after removing the anhydrous tin tetrachloride short pulse, the stability of the thermal cycling decreased, indicating that the tin-oxygen-gallium composite sites play a key role in suppressing silver migration along grain boundaries. Comparative Examples 3 and 4 showed a decrease in overall performance after changing the tin source / hydrogen timing and the dry oxygen / water vapor timing, respectively, proving that the timing control of this invention cannot be achieved by simple sequential replacement. Comparative Examples 5 and 6 showed that removing the dry oxygen short pulse or the water vapor subpulse did not achieve the overall effect of Example 1, indicating that the two respectively play the roles of bridging stability and defect passivation. Comparative Example 7 showed that simply increasing the silver layer thickness improved the initial low-emissivity performance, but sacrificed transmittance and cold bending stability. This invention is applicable to curved cold chain display cabinet doors, which can reduce the risk of bending cracking, silver layer migration, and low-temperature fogging while maintaining energy-saving and heat-insulating effects, and has good long-term service stability.

[0057] Those skilled in the art should understand that the discussion of any of the above embodiments is merely exemplary and is not intended to imply that the scope of the invention is limited to these examples; within the framework of the invention, the technical features of the above embodiments or different embodiments can also be combined, the steps can be implemented in any order, and there are many other variations of the different aspects of the invention as described above, which are not provided in detail for the sake of brevity.

Claims

1. A method for preparing bendable tempered energy-saving glass for cold chain applications, characterized in that, Includes the following steps: The ultrathin soda-lime glass sheet is chemically tempered; a silicon nitride barrier layer is deposited on the surface of the chemically tempered ultrathin soda-lime glass sheet; a zinc oxide transition layer is deposited on the surface of the silicon nitride barrier layer. A gallium-doped zinc oxide layer is deposited on the surface of the zinc oxide transition layer. The deposition of the gallium-doped zinc oxide layer includes first forming a zinc oxide framework and then performing a trimethylgallium post-pulse treatment to enrich gallium in the zinc oxide grain boundary region adjacent to the subsequent silver layer. The surface of the gallium-doped zinc oxide layer was subjected to anhydrous tin tetrachloride short-pulse treatment and hydrogen reduction residence treatment in sequence. Subsequently, dry oxygen short-pulse treatment and water vapor sub-pulse treatment are performed in sequence; a silver layer is deposited on the surface of the gallium-doped zinc oxide layer after the above treatment; finally, a zinc oxide capping layer and a fluorine-doped tin oxide protective layer are deposited on the surface of the silver layer in sequence; after post-treatment and cold bending assembly, a bendable tempered energy-saving glass for cold chain is obtained. The gallium-doped zinc oxide layer was deposited using a cyclic sequence of diethylzinc pulse, nitrogen purging, water vapor pulse, and nitrogen purging. When performing trimethylgallium post-pulse processing, the deposition is carried out in a cyclic sequence of diethylzinc short pulse, nitrogen purging, trimethylgallium post-pulse, nitrogen purging, water vapor short pulse, and nitrogen purging. The dry oxygen short pulse treatment includes: introducing a mixture of oxygen and nitrogen gas, wherein the oxygen volume fraction in the mixture is 1500-2500 ppm, the flow rate of the mixture is 40-60 sccm, the introduction time is 6-10 s, and then purging with nitrogen. The water vapor sub-pulse treatment includes: controlling the temperature of the water source bottle to 20-30℃, using nitrogen as the water vapor carrier gas, the water vapor carrier gas flow rate is 8-12 sccm, the water vapor pulse time is 20-50 ms, followed by purging with nitrogen, and the water vapor sub-pulse treatment is repeated only once. The anhydrous tin tetrachloride short-pulse treatment includes: controlling the temperature of the anhydrous tin tetrachloride source bottle to 20-30℃, controlling the temperature of the delivery pipeline to 55-65℃, using nitrogen at 8-12 sccm as the carrier gas for anhydrous tin tetrachloride, the anhydrous tin tetrachloride short-pulse time to be 40-60 ms, the nitrogen purging time to be 14-16 s, and repeating 2-4 cycles; the hydrogen reduction residence treatment includes: introducing a mixed gas of hydrogen and nitrogen, wherein the hydrogen component in the mixed gas is 4%, the mixed gas flow rate is 40-60 sccm, the pressure is 90-110 Pa, the residence time is 35-55 s, and then purging with nitrogen at 90-110 sccm for 15-25 s.

2. The preparation method according to claim 1, characterized in that, The ultrathin soda-lime glass sheet has a thickness of 800-1100μm. After being cut, the ultrathin soda-lime glass sheet is formed into a rectangular sheet of 300mm×500mm, and the chamfer width of the edge is 200-350μm.

3. The preparation method according to claim 1, characterized in that, The chemical tempering process includes immersing a pretreated ultrathin soda-lime glass sheet in potassium nitrate molten salt and holding it at 400-420℃ for 100-140 minutes to allow sodium ions on the glass surface to exchange with potassium ions in the molten salt.

4. The preparation method according to claim 1, characterized in that, The silicon nitride barrier layer is formed by plasma-enhanced chemical vapor deposition. During deposition, a mixture of silane and nitrogen gas at 20-30 sccm, ammonia at 70-90 sccm, and nitrogen at 450-550 sccm are introduced. The working pressure of the chamber is 90-110 Pa, the radio frequency power is 70-90 W, and the deposition time is 8-12 min.

5. The preparation method according to claim 1, characterized in that, The zinc oxide transition layer is formed by pulsed chemical vapor deposition, and the deposition is performed in a cyclic sequence of diethylzinc pulse, nitrogen purging, water vapor pulse, and nitrogen purging. The temperature of the diethylzinc source bottle is 20-30℃, the temperature of the water source bottle is 20-30℃, the diethylzinc carrier gas flow rate is 15-25 sccm, the water vapor carrier gas flow rate is 15-25 sccm, the diethylzinc pulse time is 220-280 ms, the water vapor pulse time is 130-170 ms, the nitrogen purging flow rate is 90-110 sccm, and the cycle is repeated 110-130 times.

6. The preparation method according to claim 1, characterized in that, The gallium-doped zinc oxide layer is deposited using a cyclic sequence of diethylzinc pulse, nitrogen purging, water vapor pulse, and nitrogen purging, at a deposition temperature of 180-190℃ and a deposition pressure of 70-90 Pa. When forming the zinc oxide framework, the diethylzinc pulse duration is 220-280 ms, the water vapor pulse duration is 130-170 ms, the diethylzinc carrier gas flow rate is 15-25 sccm, the nitrogen purging flow rate is 90-110 sccm, and the water vapor carrier gas flow rate is 15-25 sccm, repeated for 80-100 cycles. The trimethylgallium post-pulse processing uses a sequence of short diethylzinc pulse, nitrogen purging, and trimethylgallium post-pulse. Deposition was performed in a cycle of nitrogen purging, water vapor short pulse, and nitrogen purging. The diethylzinc short pulse duration was 80-120 ms, the diethylzinc carrier gas flow rate was 15-25 sccm, the nitrogen purging flow rate was 90-110 sccm, the trimethylgallium post-pulse duration was 60-100 ms, the trimethylgallium carrier gas flow rate was 8-12 sccm, the nitrogen purging flow rate was 90-110 sccm, the water vapor short pulse duration was 100-140 ms, the water vapor carrier gas flow rate was 15-25 sccm, and the third nitrogen purging duration was 8-12 s, with a nitrogen purging flow rate of 90-110 sccm. This cycle was repeated 10-14 times.

7. The preparation method according to claim 1, characterized in that, The silver layer is formed by DC magnetron sputtering with a target-substrate distance of 70-90 mm, a stage temperature of 50-70 °C, an argon flow rate of 20-30 sccm, and a working pressure of 250-350 mPa. Pre-sputtering is performed at 10 W power for 20-40 s, followed by deposition at 15-25 W power for 15-25 s, and then deposition at 30-40 W power for 50-70 s. The zinc oxide capping layer is formed by radio frequency magnetron sputtering with argon gas introduced at 25-35 sccm, a working pressure of 250-350 mPa, a radio frequency power of 70-90 W, and a deposition time of 10-14 min. The thickness of the zinc oxide capping layer is 14-18 nm.

8. The preparation method according to claim 1, characterized in that, The fluorine-doped tin oxide protective layer is formed by radio frequency magnetron sputtering, with argon gas introduced at 25-32 sccm, oxygen at 1-3 sccm, and a mixture of carbon tetrafluoride and argon gas at 4-6 sccm. The volume fraction of carbon tetrafluoride in the mixture of carbon tetrafluoride and argon gas is 5%. The working pressure is 350-450 mPa, the radio frequency power is 90-110 W, and the deposition time is 18-22 min. The thickness of the fluorine-doped tin oxide protective layer is 30-35 nm. The post-processing includes: placing the glass slide with the fluorine-doped tin oxide protective layer in a nitrogen-protected oven, continuously introducing nitrogen gas at 150-250 sccm, holding it at 170-190℃ for 15-25 min, and then naturally cooling it to 25℃ under nitrogen protection.

9. A type of bendable tempered energy-saving glass for cold chain applications, characterized in that, The bendable tempered energy-saving glass for cold chain prepared according to any one of claims 1-8 has a visible light transmittance of not less than 73.0%, an emissivity of not more than 0.125 before cold bending, an emissivity of not more than 0.135 after cold bending, a sheet resistance increase rate of not more than 6.5% after 100 cycles of hot and cold cycling from -20°C to 25°C, and a bending strength of not less than 330 MPa.

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