Laser protective lens high damage threshold coating method based on semiconductor wafer process

Abstract

The application belongs to the field of coating technology, and relates to a laser protective lens high-damage threshold coating method based on a semiconductor wafer process, comprising the following steps: sequentially performing ultrasonic cleaning and plasma activation on an optical lens substrate to obtain a pretreated lens; alternately depositing hafnium dioxide film layers and silicon dioxide film layers on the surface of the pretreated lens by using a double-target co-sputtering process to obtain a coated lens; using trimethylaluminum and ozone as precursors, growing an aluminum oxide packaging layer on the surface of the coated lens by using an atomic layer deposition process, and then performing gradient annealing treatment to obtain a laser protective lens. The whole process is systematically optimized from interface bonding, film layer structure to surface packaging. Through the synergistic effect of optimizing each link of the coating process, the intrinsic quality of the film layer is improved while the environmental adaptability is enhanced, so that the lens can withstand long-term irradiation of high-power laser, and the damage resistance and long-term stability of the laser protective lens are significantly improved.

Description

Technical Field

[0001] This invention belongs to the field of coating technology and relates to a high damage threshold coating method for laser protective lenses based on semiconductor wafer technology. Background Technology

[0002] With the rapid development of industrial laser systems, protective lenses for high-power laser equipment face increasingly stringent performance challenges. These lenses are exposed to high-energy-density laser radiation for extended periods, and their surface optical films are prone to thermal ablation, structural collapse, and even permanent failure under continuous operation. Traditional coating techniques, such as physical vapor deposition or electron beam evaporation, often produce films with porous structures, high micropore defect density, and significant interlayer diffusion, resulting in a laser damage threshold (LIDT) that remains stagnant at 20–30 J / cm². 2 The current power levels are insufficient to meet the demands of upgrading industrial lasers. Especially under the impact of high-frequency pulsed lasers, microcracks, columnar grain boundaries, and residual impurities in the film layer become energy absorption hotspots, triggering a chain reaction of damage, significantly shortening the lifespan of the lens and increasing equipment maintenance costs.

[0003] Existing technologies improve thin film performance through composite processes, such as adding low-temperature annealing after sputtering to reduce stress, or adding a magnesium fluoride protective layer to the film surface. However, on the one hand, insufficient annealing temperature results in residual stress reaching hundreds of megapascals, while excessively high temperatures induce crystallization phase transitions; on the other hand, the surface sealing layer has difficulty penetrating deep micropores and has poor thermal compatibility with the main film layer, leading to cracking after temperature cycling. These technological limitations have resulted in a long-term reliance on imports for protective lenses in high-end laser equipment, hindering the independent development of advanced manufacturing equipment. Therefore, a novel coating method integrating semiconductor-level precision control and optical adaptation characteristics is urgently needed to solve these problems. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a high damage threshold coating method for laser protective lenses based on semiconductor wafer technology. The entire process is systematically optimized from interface bonding and film structure to surface encapsulation. By optimizing the synergistic effect of each step of the coating process, the intrinsic quality of the film is improved while enhancing environmental adaptability, enabling the lens to withstand long-term irradiation by high-power lasers, and significantly improving the damage resistance and long-term stability of the laser protective lens.

[0005] To achieve this objective, the present invention adopts the following technical solution:

[0006] In a first aspect, the present invention provides a high damage threshold coating method for laser protective lenses based on semiconductor wafer technology, the coating method comprising:

[0007] (I) The optical lens substrate is subjected to ultrasonic cleaning and plasma activation in sequence to obtain a pretreated lens;

[0008] (II) A hafnium dioxide film and a silicon dioxide film are alternately deposited on the surface of the pretreated lens obtained in step (I) using a dual-target co-sputtering process to obtain a coated lens;

[0009] (III) Using trimethylaluminum and ozone as precursors, an aluminum oxide encapsulation layer is grown on the surface of the coated lens using atomic layer deposition, followed by gradient annealing to obtain the laser protection lens.

[0010] This invention significantly improves the damage resistance, long-term stability, and interfacial bonding strength of laser protective lenses by optimizing the synergistic effect of each stage of the coating process. The substrate pretreatment stage employs ultrasonic cleaning and plasma activation to effectively remove contaminants from the optical lens substrate surface and enhance substrate activity, providing a stable bonding interface for subsequent film layers. A dual-target co-sputtering process is used to alternately deposit hafnium dioxide and silicon dioxide films on the pretreated lens surface, constructing a stacked structure that alleviates thermal stress while meeting optical anti-reflection requirements. An alumina encapsulation layer grown by atomic layer deposition, combined with water vapor repair, fills the micropores in the sputtered film and repairs lattice defects. Finally, gradient annealing removes impurities, promotes structural densification, and releases thermal stress.

[0011] During the substrate pretreatment stage, ultrasonic cleaning effectively removes micron-sized particulate contaminants and organic residues from the surface of the optical lens substrate. Plasma activation, through the dual effects of ion bombardment and oxidation, forms high-density active chemical bonding sites on the surface of the optical lens substrate. This not only enhances the bonding strength between the optical lens substrate and the first thin film but also creates a moderately rough nanoscale structure, significantly improving the interfacial bonding performance between the substrate and the film. This provides a stable and reliable interfacial foundation for subsequent film deposition and effectively prevents film peeling caused by high-energy laser irradiation.

[0012] This invention employs a dual-target co-sputtering process to alternately deposit hafnium dioxide and silicon dioxide films on the surface of a pre-treated lens. Argon gas is ionized to generate plasma, which bombards both the hafnium dioxide and silicon dioxide targets. Sputtered target atoms react with oxygen and deposit as films on the pre-treated lens surface. The hafnium dioxide film provides high refractive index and mechanical strength, while the silicon dioxide film provides stress buffering due to its low elastic modulus. During the dual-target co-sputtering process, the pre-treated lens is heated to 200-250°C and rotated at 60-80 rpm to ensure the uniformity of the sputtered films. A mixed atmosphere of 75-85 sccm of argon and 8-9 sccm of oxygen is used during hafnium dioxide deposition to effectively suppress oxygen vacancy defects. During silicon dioxide deposition, the oxygen flow rate is reduced to 3-4 sccm to avoid lattice distortion caused by over-oxidation. The alternating 3-5 layer stack structure allows thermal stress to be released at the heterogeneous interface, significantly reducing residual stress between the layers. The stacked structure prepared by this invention can not only disperse the laser thermal shock energy, but also meet the anti-reflection requirements of 1064nm wavelength by precisely controlling the thickness of the sputtered film. At the same time, the columnar crystal structure is effectively suppressed, reducing the energy absorption channels at the grain boundaries.

[0013] Atomic layer deposition (ALD) uses trimethylaluminum / ozone as a precursor. Through the alternating reaction of trimethylaluminum and ozone, a dense alumina encapsulation layer is grown on the sputtered film surface. This process utilizes a self-limiting surface chemical reaction. Trimethylaluminum vapor undergoes chemisorption on the lens surface to form a monolayer. Subsequently, ozone is introduced to oxidize the adsorbed layer into alumina, and byproducts are removed by nitrogen purging. A stepwise cyclic deposition method allows for molecular-scale thickness control and uniform coverage. Periodic water vapor repair effectively hydrolyzes residual aluminum methyl groups and fills oxygen vacancy defects, significantly reducing carbon impurities and lattice distortion within the alumina encapsulation layer. The entire deposition process is carried out at a low temperature of 180–200°C, ensuring sufficient reaction while avoiding the transformation from amorphous to crystalline phases. The resulting alumina encapsulation layer exhibits excellent continuity and density, effectively sealing the micropores of the sputtered film and providing robust surface protection for laser protective lenses.

[0014] The gradient annealing process is implemented in three stages. The first stage involves holding the temperature at 145~155℃ for 120~150 min to remove physically adsorbed impurities from the lens surface. The second stage involves holding the temperature at 190~200℃ for 70~80 min to promote atomic rearrangement and achieve surface densification of the alumina encapsulation layer. The third stage involves slow cooling to 80~100℃ at a cooling rate of 0.3~0.5℃ / min to fix the surface structure of the alumina encapsulation layer. This temperature gradient enables the alumina encapsulation layer to form a highly dense amorphous structure with surface roughness controlled at the sub-nanometer level, significantly reducing the absorption of laser energy.

[0015] As a preferred technical solution of the present invention, in step (I), the ultrasonic power of the ultrasonic cleaning is 300~400W, for example, it can be 300W, 310W, 320W, 330W, 340W, 350W, 360W, 370W, 380W, 390W or 400W, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0016] In some optional instances, the ultrasonic cleaning time is 10 to 20 minutes, for example, 10 minutes, 11 minutes, 12 minutes, 13 minutes, 14 minutes, 15 minutes, 16 minutes, 17 minutes, 18 minutes, 19 minutes or 20 minutes, but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0017] In some optional instances, the plasma activation is carried out in a mixed atmosphere of argon and oxygen.

[0018] In some optional instances, the flow rate of argon in the mixed atmosphere is 50 to 80 sccm, for example, 50 sccm, 55 sccm, 60 sccm, 65 sccm, 70 sccm, 75 sccm or 80 sccm; and the flow rate of oxygen is 20 to 30 sccm, for example, 20 sccm, 21 sccm, 22 sccm, 23 sccm, 24 sccm, 25 sccm, 26 sccm, 27 sccm, 28 sccm, 29 sccm or 30 sccm, but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0019] In some optional instances, the plasma activation pressure is 0.1 to 0.3 Pa, for example, 0.1 Pa, 0.12 Pa, 0.14 Pa, 0.16 Pa, 0.18 Pa, 0.2 Pa, 0.22 Pa, 0.24 Pa, 0.26 Pa, 0.28 Pa, or 0.3 Pa, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0020] In some optional instances, the radio frequency power of the plasma activation is 300 to 500 W, for example, 300 W, 320 W, 340 W, 360 W, 380 W, 400 W, 420 W, 440 W, 460 W, 480 W or 500 W, but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0021] In some optional instances, the plasma activation time is 3 to 5 minutes, for example, 3.0 minutes, 3.2 minutes, 3.4 minutes, 3.6 minutes, 3.8 minutes, 4.0 minutes, 4.2 minutes, 4.4 minutes, 4.6 minutes, 4.8 minutes, or 5.0 minutes, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0022] As a preferred technical solution of the present invention, in step (II), the dual-target co-sputtering uses hafnium dioxide target and silicon dioxide target.

[0023] In some optional instances, during dual-target co-sputtering, the rotational speed of the pretreatment lens is 60 to 80 rpm, for example, 60 rpm, 62 rpm, 64 rpm, 66 rpm, 68 rpm, 70 rpm, 72 rpm, 74 rpm, 76 rpm, 78 rpm or 80 rpm, but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0024] In some optional instances, during the dual-target co-sputtering process, the temperature of the pre-treated lens is 200~250°C, for example, 200°C, 205°C, 210°C, 215°C, 220°C, 225°C, 230°C, 235°C, 240°C, 245°C or 250°C, but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0025] In some optional instances, the dual-target co-sputtering is performed in a mixed atmosphere of argon and oxygen.

[0026] In some alternative instances, during the deposition of the hafnium dioxide film, the argon flow rate is 75-85 sccm, for example, 75 sccm, 76 sccm, 77 sccm, 78 sccm, 79 sccm, 80 sccm, 81 sccm, 82 sccm, 83 sccm, 84 sccm, or 85 sccm; the oxygen flow rate is 8-9 sccm, for example, 8.0 sccm, 8.1 sccm, 8.2 sccm, 8.3 sccm, 8.4 sccm, 8.5 sccm, 8.6 sccm, 8.7 sccm, 8.8 sccm, 8.9 sccm, or 9.0 sccm, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0027] In some optional instances, the sputtering power of the hafnium dioxide target is 800~1000W, for example, it can be 800W, 820W, 840W, 860W, 880W, 900W, 920W, 940W, 960W, 980W or 1000W, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0028] In some optional instances, the deposition rate of the hafnium dioxide film is 0.3 to 0.5 nm / s, for example, 0.3 nm / s, 0.32 nm / s, 0.34 nm / s, 0.36 nm / s, 0.38 nm / s, 0.4 nm / s, 0.42 nm / s, 0.44 nm / s, 0.46 nm / s, 0.48 nm / s or 0.5 nm / s, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0029] In some optional instances, the thickness of the single hafnium dioxide film layer is 70-80 nm, for example, it can be 70 nm, 71 nm, 72 nm, 73 nm, 74 nm, 75 nm, 76 nm, 77 nm, 78 nm, 79 nm or 80 nm, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0030] This invention specifically limits the thickness of the single-layer hafnium dioxide film to 70-80 nm. Within this range, the high refractive index characteristics of the hafnium dioxide film are fully utilized, achieving optical thickness matching with the silicon dioxide film at a wavelength of 1064 nm, effectively reducing laser reflection loss. Simultaneously, this thickness range avoids both insufficient stress release due to an excessively thin film and stress accumulation caused by an excessively thick film, providing a stable mechanical basis for the sputtered film.

[0031] When the thickness of the hafnium dioxide film is less than 70 nm, the resulting sputtered film cannot meet the quarter-wavelength optical thickness requirement, leading to a significant increase in laser reflectivity. High reflectivity means less laser energy is transmitted or dissipated, while more energy is absorbed by the film or defects within it, resulting in localized overheating and thermal stress concentration, thus inducing film damage. This invention aims to achieve a film with low reflectivity (high transmission) and low absorption / low defects, which is key to achieving a high damage threshold. Furthermore, insufficient film thickness prevents the full release of residual stress, significantly increasing interfacial shear stress and making it prone to micro-buckling deformation under humid and hot conditions. Simultaneously, an excessively thin sputtered film has insufficient masking ability for substrate surface defects, causing micro-scratches on the substrate to be reproduced and amplified within the sputtered film, forming penetrating structural defects.

[0032] When the thickness of the hafnium dioxide film exceeds 80 nm, transgranular cracks perpendicular to the substrate are formed inside the sputtered film, and shearing and peeling easily occur at the interface. At the same time, the excessive thickness of the hafnium dioxide film leads to a longer deposition time, excessive growth of columnar grains, and an increase in grain boundary width, which becomes a preferential channel for laser energy absorption. In addition, the thermal capacity gradient of the excessively thick sputtered film is intensified, which will cause large differences in local temperature rise during laser irradiation, resulting in thermal shock cracks in the laser protective lens.

[0033] In some alternative instances, during the deposition of the silica film, the argon flow rate is 75-85 sccm, for example, 75 sccm, 76 sccm, 77 sccm, 78 sccm, 79 sccm, 80 sccm, 81 sccm, 82 sccm, 83 sccm, 84 sccm, or 85 sccm; and the oxygen flow rate is 3-4 sccm, for example, 3.0 sccm, 3.1 sccm, 3.2 sccm, 3.3 sccm, 3.4 sccm, 3.5 sccm, 3.6 sccm, 3.7 sccm, 3.8 sccm, 3.9 sccm, or 4.0 sccm, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0034] In some optional instances, the sputtering power of the silica target is 1200~1400W, for example, it can be 1200W, 1220W, 1240W, 1260W, 1280W, 1300W, 1320W, 1340W, 1360W, 1380W or 1400W, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0035] In some alternative examples, the deposition rate of the silicon dioxide film is 0.8 to 1.2 nm / s, for example, 0.8 nm / s, 0.85 nm / s, 0.9 nm / s, 0.95 nm / s, 1.0 nm / s, 1.05 nm / s, 1.1 nm / s, 1.15 nm / s or 1.2 nm / s, but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0036] In some optional instances, the thickness of the single layer of said silicon dioxide film is 45~55nm, for example, it can be 45nm, 46nm, 47nm, 48nm, 49nm, 50nm, 51nm, 52nm, 53nm, 54nm or 55nm, but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0037] This invention specifically limits the thickness of the monolayer silica film to 45-55 nm. Within this range, the low elastic modulus of the silica film is fully utilized, forming an effective stress-buffering stack structure with the adjacent hafnium dioxide film. Simultaneously, the 45-55 nm thickness meets the design requirement of one-quarter optical thickness, synergistically reducing laser reflection loss with the hafnium dioxide film. Furthermore, the deposition time corresponding to this thickness is beneficial for forming a uniform and dense amorphous structure, avoiding grain boundary weakening problems caused by abnormal columnar crystal growth.

[0038] When the single-layer silicon dioxide film is less than 45 nm, the excessively thin silicon dioxide film cannot effectively absorb the compressive stress of adjacent hafnium dioxide films, leading to interfacial shear stress concentration. This, in turn, causes interfacial microcracks to propagate along grain boundaries, making the sputtered film prone to localized delamination between layers under humid and hot conditions. Furthermore, the excessively thin silicon dioxide film cannot satisfy the destructive interference condition, resulting in a significant increase in laser reflectivity. More laser energy is absorbed by the film or defects within it, leading to localized overheating and thermal stress concentration, thus inducing film damage. Simultaneously, the excessively thin silicon dioxide film has insufficient coverage of substrate surface defects, causing substrate micro-scratches to reproduce and amplify within the sputtered film, forming penetrating structural defects.

[0039] When the monolayer silica film exceeds 55 nm, the surface of the excessively thick silica film forms periodic wrinkles and transverse delamination cracks parallel to the substrate, compromising the optical smoothness of the sputtered film. Simultaneously, the excessive thickness of the monolayer silica film prolongs the deposition time, leading to excessive columnar crystal growth, increased grain size, and weakened grain boundaries. Furthermore, the excessively thick sputtered film exacerbates the local temperature gradient during laser irradiation, inducing thermal stress cracking.

[0040] In some optional instances, 3 to 5 hafnium dioxide films and 3 to 5 silicon dioxide films are alternately deposited on the surface of the pretreated lens.

[0041] As a preferred technical solution of the present invention, in step (III), the atomic layer deposition process includes performing 20 to 30 deposition cycles;

[0042] Each of the aforementioned deposition cycles includes a trimethylaluminum pulse phase, a first nitrogen purging phase, an ozone pulse phase, and a second nitrogen purging phase performed sequentially.

[0043] Every 5 deposition cycles, a water vapor remediation stage and a third nitrogen purging stage are performed sequentially.

[0044] As a preferred technical solution of the present invention, in step (III), the atomic layer deposition process specifically includes:

[0045] The coated lens is placed in the reaction chamber of an atomic layer deposition apparatus, and the pressure in the reaction chamber is adjusted to 10~50 Pa, for example, it can be 10 Pa, 15 Pa, 20 Pa, 25 Pa, 30 Pa, 35 Pa, 40 Pa, 45 Pa or 50 Pa; the coated lens is heated to 180~200℃, for example, it can be 180℃, 182℃, 184℃, 186℃, 188℃, 190℃, 192℃, 194℃, 196℃, 198℃ or 200℃, but is not limited to the listed values, other unlisted values ​​within this range are also applicable;

[0046] Subsequently, trimethylaluminum is introduced into the reaction chamber, and after a period of continuous introduction, the introduction is stopped and the chamber is left to stand for a period of time to complete one trimethylaluminum pulse phase.

[0047] Subsequently, nitrogen gas is introduced into the reaction chamber to purge the surface of the coated lens with nitrogen gas. After purging, the lens is left to stand for a period of time to complete the first nitrogen purging stage.

[0048] Subsequently, ozone is introduced into the reaction chamber, and after a period of continuous introduction, the introduction is stopped and the chamber is left to stand for a period of time to complete one ozone pulse phase.

[0049] Subsequently, nitrogen gas is introduced into the reaction chamber to purge the surface of the coated lens with nitrogen gas. After purging, the lens is left to stand for a period of time to complete the second nitrogen purging stage.

[0050] One deposition cycle consists of one trimethylaluminum pulse phase, one first nitrogen purging phase, one ozone pulse phase, and one second nitrogen purging phase.

[0051] After 20 to 30 deposition cycles, the alumina encapsulation layer is formed on the surface of the coated lens. For example, it can be 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0052] During the trimethylaluminum pulse phase, trimethylaluminum is introduced into the reaction chamber at a flow rate of 20–30 sccm for 0.1–0.2 s to ensure monolayer adsorption saturation on the coated lens surface. A subsequent 8–10 s settling period provides sufficient time for molecular migration, allowing the precursor to penetrate into the nanopores of the coated lens surface. Unreacted precursors are then thoroughly removed by a first nitrogen purging to prevent gas-phase side reactions. During the ozone pulse phase, ozone is introduced into the reaction chamber at a flow rate of 25–35 sccm for 0.2–0.3 s to oxidize the trimethylaluminum adsorption layer to aluminum oxide. A 4–6 s settling period promotes the complete oxidation reaction. Reaction byproducts are then removed by a second nitrogen purging, followed by settling to complete lattice relaxation.

[0053] In this invention, a water vapor remediation stage is performed every 5 deposition cycles. Water vapor remediation significantly improves film quality because: firstly, water molecules can hydrolyze unreacted aluminum methyl groups, eliminating carbon residue; secondly, water molecules can react with oxygen vacancies to undergo redox reactions, filling lattice defects. After water vapor remediation, nitrogen purging effectively removes physically adsorbed water, and allowing the film to stand for 3-5 seconds allows residual molecules to naturally desorb.

[0054] As a preferred embodiment of the present invention, during the trimethylaluminum pulse phase, the flow rate of trimethylaluminum is 20~30 sccm, for example, it can be 20 sccm, 21 sccm, 22 sccm, 23 sccm, 24 sccm, 25 sccm, 26 sccm, 27 sccm, 28 sccm, 29 sccm or 30 sccm, but it is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0055] In some alternative instances, during the trimethylaluminum pulse phase, the duration of the continuous infusion of trimethylaluminum is 0.1 to 0.2 s, for example, 0.1 s, 0.11 s, 0.12 s, 0.13 s, 0.14 s, 0.15 s, 0.16 s, 0.17 s, 0.18 s, 0.19 s, or 0.2 s, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0056] In some alternative instances, during the trimethylaluminum pulse phase, the settling time after the trimethylaluminum is stopped is 8 to 10 seconds, for example, 8.0 seconds, 8.2 seconds, 8.4 seconds, 8.6 seconds, 8.8 seconds, 9.0 seconds, 9.2 seconds, 9.4 seconds, 9.6 seconds, 9.8 seconds, or 10.0 seconds, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0057] In some optional instances, during the first nitrogen purging stage, the nitrogen flow rate is 450~550 sccm, for example, it can be 450 sccm, 460 sccm, 470 sccm, 480 sccm, 490 sccm, 500 sccm, 510 sccm, 520 sccm, 530 sccm, 540 sccm or 550 sccm, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0058] In some optional instances, the nitrogen purging time during the first nitrogen purging phase is 5 to 8 seconds, for example, 5.0 seconds, 5.5 seconds, 6.0 seconds, 6.5 seconds, 7.0 seconds, 7.5 seconds, or 8.0 seconds, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0059] In some optional instances, the settling time after the nitrogen purging phase is 3 to 5 seconds, for example, 3.0 seconds, 3.2 seconds, 3.4 seconds, 3.6 seconds, 3.8 seconds, 4.0 seconds, 4.2 seconds, 4.4 seconds, 4.6 seconds, 4.8 seconds, or 5.0 seconds, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0060] As a preferred technical solution of the present invention, during the ozone pulse phase, the ozone flow rate is 25~35 sccm, for example, it can be 25 sccm, 26 sccm, 27 sccm, 28 sccm, 29 sccm, 30 sccm, 31 sccm, 32 sccm, 33 sccm, 34 sccm or 35 sccm, but it is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0061] In some alternative instances, during the ozone pulse phase, the duration of the continuous ozone introduction is 0.2 to 0.3 s, for example, 0.2 s, 0.21 s, 0.22 s, 0.23 s, 0.24 s, 0.25 s, 0.26 s, 0.27 s, 0.28 s, 0.29 s, or 0.3 s, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0062] In some optional instances, during the ozone pulse phase, the settling time after the ozone supply stops is 4 to 6 seconds, for example, 4.0 seconds, 4.2 seconds, 4.4 seconds, 4.6 seconds, 4.8 seconds, 5.0 seconds, 5.2 seconds, 5.4 seconds, 5.6 seconds, 5.8 seconds, or 6.0 seconds, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0063] In some optional instances, during the second nitrogen purging stage, the nitrogen flow rate is 350 to 450 sccm, for example, 350 sccm, 360 sccm, 370 sccm, 380 sccm, 390 sccm, 400 sccm, 410 sccm, 420 sccm, 430 sccm, 440 sccm, or 450 sccm, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0064] In some optional instances, the nitrogen purging time in the second nitrogen purging stage is 5 to 8 seconds, for example, 5.0 seconds, 5.5 seconds, 6.0 seconds, 6.5 seconds, 7.0 seconds, 7.5 seconds, or 8.0 seconds, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0065] In some optional instances, the settling time after the nitrogen purging phase is 3 to 5 seconds, for example, 3.0 seconds, 3.2 seconds, 3.4 seconds, 3.6 seconds, 3.8 seconds, 4.0 seconds, 4.2 seconds, 4.4 seconds, 4.6 seconds, 4.8 seconds, or 5.0 seconds, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0066] As a preferred embodiment of the present invention, in step (III), the atomic layer deposition process further includes performing the following operation every 5 deposition cycles:

[0067] Water vapor is introduced into the reaction chamber and introduced for a period of time. Then the introduction is stopped and the mixture is left to stand for a period of time to complete the first water vapor repair stage. Subsequently, nitrogen gas is introduced into the reaction chamber to purge the surface of the coated lens. After purging, the mixture is left to stand for a period of time to complete the third nitrogen purging stage.

[0068] The water vapor repair stage significantly improves the intrinsic quality and structural stability of the alumina encapsulation layer, primarily addressing the unavoidable residue and lattice defect issues encountered during atomic layer deposition. On one hand, water vapor molecules dissociate on the film surface to form active hydroxyl groups. These groups hydrolyze unreacted trimethylaluminum precursors, converting organoaluminum compounds into aluminum hydroxide structures, while simultaneously generating volatile methane products that exit the reaction chamber. This process effectively removes organic residues within the alumina encapsulation layer, preventing the formation of carbide absorption centers. On the other hand, water molecule penetration has a reconstructive effect on the alumina lattice. After diffusing into the interior of the alumina encapsulation layer, water molecules react with oxygen vacancy defects, filling lattice gaps. This process promotes the thermodynamically stable coordination state of aluminum atoms, enhancing the connectivity of the amorphous network. Particularly for the interface region between the sputtered film and the alumina encapsulation layer, water molecule repair can adjust the structural mismatch between the sputtered film and the alumina encapsulation layer, significantly improving the density and continuity of the alumina encapsulation layer and reducing stress concentration problems caused by local lattice distortion.

[0069] As a preferred technical solution of the present invention, in the water vapor repair stage, the water vapor flow rate is 12~15 sccm, for example, it can be 12 sccm, 12.5 sccm, 13 sccm, 13.5 sccm, 14 sccm, 14.5 sccm or 15 sccm, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0070] The present invention specifically limits the flow rate of water vapor to 12~15 sccm. Within this range, it can ensure that water molecules fully cover the surface of the alumina encapsulation layer within 0.3~0.5s, thereby achieving the removal of residual aluminum methyl groups and the repair of oxygen vacancies, while avoiding deep penetration that could cause structural changes in the alumina encapsulation layer.

[0071] When the steam flow rate is below 12 sccm, the reaction on the surface of the alumina encapsulation layer is incomplete. The number of water molecules is insufficient to cover the reaction sites on the surface of the alumina encapsulation layer, and some aluminum methyl groups fail to participate in the hydrolysis reaction. The residual organic groups form carbide particles during subsequent high-temperature processing. In addition, the low steam flow rate leads to insufficient repair of oxygen vacancies, leaving unrepaired lattice defects in the subsurface region of the alumina encapsulation layer.

[0072] When the water vapor flow rate exceeds 15 sccm, the excess water molecules exacerbate gas-phase side reactions, generating reactive substances such as hydroxyl radicals that attack the alumina network. Water molecules penetrating deep into the alumina encapsulation layer also alter the coordination state of aluminum atoms, leading to an increase in local lattice expansion rate. Furthermore, high-velocity water vapor disrupts the flow field stability of the reaction chamber, causing eddies to form at the lens edge and resulting in uneven distribution of the repair effect.

[0073] In some optional instances, during the water vapor remediation phase, the continuous introduction of water vapor lasts for 0.3 to 0.5 seconds, for example, 0.3 seconds, 0.32 seconds, 0.34 seconds, 0.36 seconds, 0.38 seconds, 0.4 seconds, 0.42 seconds, 0.44 seconds, 0.46 seconds, 0.48 seconds, or 0.5 seconds, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0074] The present invention specifically limits the continuous introduction time of water vapor to 0.3~0.5s. Within this range, it can ensure that water molecules can fully diffuse to the subsurface region of the alumina encapsulation layer to complete the hydrolysis and removal of residual aluminum methyl groups; and it can also react with oxygen vacancy defects to fill lattice vacancies.

[0075] When the steam introduction time is less than 0.3 s, the surface reaction of the alumina encapsulation layer is incomplete, and water molecules cannot fully contact the unreacted aluminum methyl groups in the deeper layers. The residual organic groups then pyrolyze during subsequent annealing to form carbide impurities. Furthermore, the degree of oxygen vacancy repair is significantly reduced, leaving unrepaired structural defects in the subsurface region of the alumina encapsulation layer. Simultaneously, some hydrolysis products, aluminum hydroxyl groups, fail to complete dehydration condensation, increasing the number of residual hydroxyl groups. These defects become absorption points for laser energy during laser irradiation, causing damage to the film.

[0076] When the water vapor is introduced for more than 0.5 seconds, excessive water molecules penetrate into the deep region of the alumina encapsulation layer, causing changes in the coordination state of aluminum atoms and resulting in local lattice expansion. At the same time, deep hydration also attacks the underlying silicon-oxygen bonds, forming migratable silanol groups, which leads to a decrease in the structural stability of the alumina encapsulation layer and makes it prone to microcracks during subsequent gradient annealing.

[0077] In some optional instances, during the water vapor repair phase, the settling time after the water vapor supply is stopped is 3 to 5 seconds, for example, 3.0 seconds, 3.2 seconds, 3.4 seconds, 3.6 seconds, 3.8 seconds, 4.0 seconds, 4.2 seconds, 4.4 seconds, 4.6 seconds, 4.8 seconds, or 5.0 seconds, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0078] In some optional instances, during the third nitrogen purging stage, the nitrogen flow rate is 200-300 sccm, for example, 200 sccm, 210 sccm, 220 sccm, 230 sccm, 240 sccm, 250 sccm, 260 sccm, 270 sccm, 280 sccm, 290 sccm or 300 sccm, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0079] In some optional instances, the nitrogen purging time in the third nitrogen purging stage is 5 to 8 seconds, for example, it can be 3.0 seconds, 3.2 seconds, 3.4 seconds, 3.6 seconds, 3.8 seconds, 4.0 seconds, 4.2 seconds, 4.4 seconds, 4.6 seconds, 4.8 seconds or 5.0 seconds, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0080] In some optional instances, the settling time after the nitrogen purging in the third nitrogen purging stage is 3 to 5 seconds, for example, 3.0 seconds, 3.2 seconds, 3.4 seconds, 3.6 seconds, 3.8 seconds, 4.0 seconds, 4.2 seconds, 4.4 seconds, 4.6 seconds, 4.8 seconds, or 5.0 seconds, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0081] As a preferred technical solution of the present invention, in step (III), the gradient annealing process includes the following steps:

[0082] First, heat to the first annealing temperature at the first heating rate and hold at that temperature. Then, continue heating to the second annealing temperature at the second heating rate and hold at that temperature. Next, cool to the third annealing temperature at the first cooling rate. Finally, stop the furnace and allow it to cool to room temperature.

[0083] The initial heating stage involves raising the temperature to 145-155℃ at a rate of 1.5-2.5℃ / min, followed by a holding period of 120-150 min. This stage primarily removes physically adsorbed impurities and releases initial stress. The annealing temperature of 145-155℃ is lower than the decomposition temperature of organic impurities to avoid carbonization residues, while being higher than the glass transition temperature to ensure appropriate atomic mobility. The holding time of 120-150 min ensures sufficient desorption of water molecules and residual gases adsorbed on the surface and deep layers of the alumina encapsulation layer.

[0084] In the core annealing stage, the temperature is increased to 190-200℃ at a rate of 0.8-1.2℃ / min and held for 70-80 min. This annealing temperature of 190-200℃ provides sufficient thermal energy to drive aluminum atom migration and recombination while remaining below the amorphous-to-crystalline phase transition temperature. During the 70-80 min holding period, aluminum atoms rearrange their positions, promoting a denser packing structure of the amorphous network. This stage achieves deep densification of the alumina encapsulation layer, significantly improving its mechanical strength and thermal stability.

[0085] The cooling phase involves a slow cooling rate of 0.3–0.5 °C / min to 80–100 °C. This process primarily addresses the interfacial stress caused by differences in the thermal expansion coefficients of the materials. The slow cooling rate provides ample time for atomic positions to gradually adjust, releasing thermal stress through viscoelastic creep. When the temperature drops below 100 °C, atomic mobility significantly decreases, allowing the optimized film structure to be stabilized. Finally, the furnace is shut down for further cooling to avoid residual stress caused by rapid cooling, ensuring the morphological stability of the alumina encapsulation layer.

[0086] In some optional instances, the entire gradient annealing process is carried out in a nitrogen atmosphere and at a pressure of 100 to 150 Pa, for example, 100 Pa, 105 Pa, 110 Pa, 115 Pa, 120 Pa, 125 Pa, 130 Pa, 135 Pa, 140 Pa, 145 Pa or 150 Pa, but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0087] In some alternative instances, the first heating rate is 1.5 to 2.5 °C / min, for example, it can be 1.5 °C / min, 1.6 °C / min, 1.7 °C / min, 1.8 °C / min, 1.9 °C / min, 2.0 °C / min, 2.1 °C / min, 2.2 °C / min, 2.3 °C / min, 2.4 °C / min or 2.5 °C / min, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0088] In some optional instances, the first annealing temperature is 145~155°C, for example, it can be 145°C, 146°C, 147°C, 148°C, 149°C, 150°C, 151°C, 152°C, 153°C, 154°C or 155°C, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0089] In some optional instances, the holding time at the first annealing temperature is 120 to 150 minutes, for example, 120 minutes, 125 minutes, 130 minutes, 135 minutes, 140 minutes, 145 minutes or 150 minutes, but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0090] In some alternative instances, the second heating rate is 0.8 to 1.2 °C / min, for example, it can be 0.8 °C / min, 0.85 °C / min, 0.9 °C / min, 0.95 °C / min, 1.0 °C / min, 1.05 °C / min, 1.1 °C / min, 1.15 °C / min or 1.2 °C / min, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0091] In some optional instances, the second annealing temperature is 190~200℃, for example, it can be 190℃, 191℃, 192℃, 193℃, 194℃, 195℃, 196℃, 197℃, 198℃, 199℃ or 200℃, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0092] The present invention specifically limits the second annealing temperature to 190~200℃. Within this range, aluminum atoms obtain sufficient migration energy to rearrange their positions, causing the amorphous network structure to become dense and stable. This temperature range achieves film densification while avoiding the starting point of the amorphous-to-crystalline phase transition, thus avoiding optical scattering problems caused by grain boundary formation.

[0093] When the second annealing temperature is below 190℃, the migration ability of aluminum atoms is insufficient to overcome the diffusion barrier. The positions of aluminum atoms in the alumina encapsulation layer are not adequately adjusted, the repair rate of oxygen vacancy defects decreases significantly, and structural defects such as micropores cannot be effectively eliminated. Furthermore, the heat required for the decomposition of organic impurities in the alumina encapsulation layer cannot be fully met, making it difficult to completely remove residual hydrocarbons and failing to achieve the expected densification effect.

[0094] When the second annealing temperature exceeds 200℃, the transformation from amorphous to crystalline phase begins. Grain formation is accompanied by volume shrinkage, generating significant tensile stress within the confined film structure. Newly formed grain boundaries become stress concentration points, easily triggering microcrack propagation. Furthermore, increased temperature exacerbates the difference in thermal expansion between the alumina encapsulation layer and the substrate, leading to edge warping of the alumina encapsulation layer. Simultaneously, high temperatures accelerate the removal rate of residual hydroxyl groups in the alumina encapsulation layer, forming nanoscale porous structures within it, ultimately resulting in a significant reduction in the protective performance of the alumina encapsulation layer.

[0095] In some optional instances, the second annealing temperature is held for 70 to 80 minutes, for example, 70 minutes, 71 minutes, 72 minutes, 73 minutes, 74 minutes, 75 minutes, 76 minutes, 77 minutes, 78 minutes, 79 minutes, or 80 minutes, but not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0096] In some alternative instances, the first cooling rate is 0.3~0.5℃ / min, for example, it can be 0.3℃ / min, 0.32℃ / min, 0.34℃ / min, 0.36℃ / min, 0.38℃ / min, 0.4℃ / min, 0.42℃ / min, 0.44℃ / min, 0.46℃ / min, 0.48℃ / min or 0.5℃ / min, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0097] In some optional instances, the third annealing temperature is 80~100℃, for example, it can be 80℃, 82℃, 84℃, 86℃, 88℃, 90℃, 92℃, 94℃, 96℃, 98℃ or 100℃, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0098] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0099] This invention significantly improves the damage resistance, long-term stability, and interfacial bonding strength of laser protective lenses by optimizing the synergistic effect of each stage of the coating process. The substrate pretreatment stage employs ultrasonic cleaning and plasma activation to effectively remove contaminants from the optical lens substrate surface and enhance substrate activity, providing a stable bonding interface for subsequent film layers. A dual-target co-sputtering process is used to alternately deposit hafnium dioxide and silicon dioxide films on the pretreated lens surface, constructing a stacked structure that alleviates thermal stress while meeting optical anti-reflection requirements. An alumina encapsulation layer grown by atomic layer deposition, combined with water vapor repair, fills the micropores in the sputtered film and repairs lattice defects. Finally, gradient annealing removes impurities, promotes structural densification, and releases thermal stress. Attached Figure Description

[0100] Figure 1 The above is a process flow diagram of the method for preparing laser protective lenses provided in Embodiments 1-15 of the present invention. Detailed Implementation

[0101] The technical solutions of the present invention will be described in detail below with reference to specific embodiments and accompanying drawings. The embodiments described herein are specific implementations of the present invention, used to illustrate the concept of the present invention; these descriptions are explanatory and exemplary, and should not be construed as limiting the implementation methods or the scope of protection of the present invention. In addition to the embodiments described herein, those skilled in the art can employ other obvious technical solutions based on the content disclosed in the claims and specification of this application. These technical solutions include those that make any obvious substitutions and modifications to the embodiments described herein.

[0102] Example 1

[0103] This embodiment provides a high damage threshold coating method for laser protective lenses based on semiconductor wafer technology, such as... Figure 1 As shown, the coating method specifically includes the following steps:

[0104] (1) The optical lens substrate (made of fused silica) was ultrasonically cleaned with an ultrasonic power of 300W and an ultrasonic time of 20min.

[0105] Subsequently, the ultrasonically cleaned optical lens substrate was plasma activated in a mixed atmosphere of argon and oxygen. The flow rate of argon in the mixed atmosphere was 50 sccm, the flow rate of oxygen was 20 sccm, the plasma activation pressure was 0.1 Pa, the radio frequency power was 300 W, and the plasma activation time was 5 min. The pre-treated lens was obtained after plasma activation.

[0106] (2) Using a dual-target co-sputtering process, hafnium dioxide film and silicon dioxide film are alternately deposited on the surface of the pretreated lens obtained in step (1) in a mixed atmosphere of argon and oxygen. The rotation speed of the pretreated lens is 60 rpm and the temperature of the pretreated lens is 200℃.

[0107] During the deposition of hafnium dioxide film, the argon flow rate was 75 sccm, the oxygen flow rate was 8 sccm, the sputtering power of the hafnium dioxide target was 800 W, the deposition rate of the hafnium dioxide film was 0.3 nm / s, and the thickness of a single hafnium dioxide film was 70 nm. During the deposition of silicon dioxide film, the argon flow rate was 75 sccm, the oxygen flow rate was 3 sccm, the sputtering power of the silicon dioxide target was 1200 W, the deposition rate of the silicon dioxide film was 0.8 nm / s, and the thickness of a single silicon dioxide film was 45 nm. After alternating deposition of 5 hafnium dioxide films and 5 silicon dioxide films, a coated lens was obtained.

[0108] (3) Place the coated lens in the reaction chamber of the atomic layer deposition equipment, adjust the pressure in the reaction chamber to 10 Pa, and heat the coated lens to 180 °C; introduce trimethylaluminum into the reaction chamber at a flow rate of 20 sccm, continue to introduce for 0.2 s, stop and let stand for 10 s to complete one trimethylaluminum pulse stage; then, introduce nitrogen into the reaction chamber at a flow rate of 450 sccm to purge the surface of the coated lens with nitrogen, purge for 8 s and let stand for 5 s to complete one nitrogen purging stage; then, introduce ozone into the reaction chamber at a flow rate of 25 sccm, continue to introduce for 0.3 s, stop and let stand for 6 s to complete one ozone pulse stage; finally, introduce nitrogen into the reaction chamber at a flow rate of 350 sccm to purge the surface of the coated lens with nitrogen, purge for 8 s and let stand for 5 s to complete one nitrogen purging stage;

[0109] One deposition cycle consists of a trimethylaluminum pulse stage, a first nitrogen purging stage, an ozone pulse stage, and a second nitrogen purging stage. Every 5 deposition cycles, a water vapor repair stage and a third nitrogen purging stage are performed. The water vapor repair stage involves introducing water vapor into the reaction chamber at a flow rate of 12 sccm for 0.5 seconds, then stopping and allowing it to stand for 5 seconds. The third nitrogen purging stage involves introducing nitrogen into the reaction chamber at a flow rate of 200 sccm to purge the surface of the coated lens for 8 seconds, followed by a 5-second stand. After 20 deposition cycles, an aluminum oxide encapsulation layer is formed on the surface of the coated lens.

[0110] (4) The encapsulated lens obtained in step (3) is subjected to gradient annealing under a nitrogen atmosphere and a pressure of 100 Pa. It is heated to 145°C at a heating rate of 1.5°C / min and held for 150 min. Then it is heated to 190°C at a heating rate of 0.8°C / min and held for 80 min. Then it is cooled to 80°C at a cooling rate of 0.3°C / min. Finally, the furnace is stopped and cooled to room temperature to obtain the laser protection lens.

[0111] Example 2

[0112] This embodiment provides a high damage threshold coating method for laser protective lenses based on semiconductor wafer technology, such as... Figure 1 As shown, the coating method specifically includes the following steps:

[0113] (1) The optical lens substrate was ultrasonically cleaned with an ultrasonic power of 320W and an ultrasonic time of 18min.

[0114] Subsequently, the ultrasonically cleaned optical lens substrate was plasma activated in a mixed atmosphere of argon and oxygen. The flow rate of argon in the mixed atmosphere was 60 sccm, the flow rate of oxygen was 22 sccm, the plasma activation pressure was 0.15 Pa, the radio frequency power was 350 W, and the plasma activation time was 4.5 min. The pre-treated lens was obtained after plasma activation.

[0115] (2) Using a dual-target co-sputtering process, hafnium dioxide film and silicon dioxide film are alternately deposited on the surface of the pretreated lens obtained in step (1) in a mixed atmosphere of argon and oxygen. The rotation speed of the pretreated lens is 65 rpm and the temperature of the pretreated lens is 210℃.

[0116] During the deposition of hafnium dioxide film, the argon flow rate was 78 sccm, the oxygen flow rate was 8.2 sccm, the sputtering power of the hafnium dioxide target was 850 W, the deposition rate of the hafnium dioxide film was 0.35 nm / s, and the thickness of a single hafnium dioxide film was 72 nm. During the deposition of silicon dioxide film, the argon flow rate was 78 sccm, the oxygen flow rate was 3.2 sccm, the sputtering power of the silicon dioxide target was 1250 W, the deposition rate of the silicon dioxide film was 0.9 nm / s, and the thickness of a single silicon dioxide film was 48 nm. After alternating deposition of 5 hafnium dioxide films and 5 silicon dioxide films, a coated lens was obtained.

[0117] (3) Place the coated lens in the reaction chamber of the atomic layer deposition equipment, adjust the pressure in the reaction chamber to 20 Pa, and heat the coated lens to 185 °C; introduce trimethylaluminum into the reaction chamber at a flow rate of 22 sccm, continue to introduce for 0.18 s, stop and let stand for 9.5 s to complete one trimethylaluminum pulse stage; then, introduce nitrogen into the reaction chamber at a flow rate of 480 sccm to purge the surface of the coated lens with nitrogen, purge for 7 s and let stand for 4.5 s to complete one nitrogen purging stage; then, introduce ozone into the reaction chamber at a flow rate of 28 sccm, continue to introduce for 0.28 s, stop and let stand for 5.5 s to complete one ozone pulse stage; finally, introduce nitrogen into the reaction chamber at a flow rate of 380 sccm to purge the surface of the coated lens with nitrogen, purge for 7 s and let stand for 4.5 s to complete one nitrogen purging stage;

[0118] One deposition cycle consists of a trimethylaluminum pulse stage, a first nitrogen purging stage, an ozone pulse stage, and a second nitrogen purging stage. Every 5 deposition cycles, a water vapor repair stage and a third nitrogen purging stage are performed. The water vapor repair stage involves introducing water vapor into the reaction chamber at a flow rate of 13 sccm for 0.45 s, then stopping and allowing it to stand for 4.5 s. The third nitrogen purging stage involves introducing nitrogen into the reaction chamber at a flow rate of 220 sccm to purge the surface of the coated lens for 7 s, followed by a 4.5 s stand. After 22 deposition cycles, an aluminum oxide encapsulation layer is formed on the surface of the coated lens.

[0119] (4) The encapsulated lens obtained in step (3) is subjected to gradient annealing under a nitrogen atmosphere and a pressure of 110 Pa. It is heated to 148°C at a heating rate of 1.8°C / min and held for 140 min. Then it is heated to 192°C at a heating rate of 0.9°C / min and held for 78 min. Then it is cooled to 85°C at a cooling rate of 0.35°C / min. Finally, the furnace is stopped and cooled to room temperature to obtain the laser protection lens.

[0120] Example 3

[0121] This embodiment provides a high damage threshold coating method for laser protective lenses based on semiconductor wafer technology, such as... Figure 1 As shown, the coating method specifically includes the following steps:

[0122] (1) The optical lens substrate was ultrasonically cleaned with an ultrasonic power of 350W and an ultrasonic time of 15min.

[0123] Subsequently, the ultrasonically cleaned optical lens substrate was plasma activated in a mixed atmosphere of argon and oxygen. The flow rate of argon in the mixed atmosphere was 70 sccm, the flow rate of oxygen was 25 sccm, the plasma activation pressure was 0.2 Pa, the radio frequency power was 400 W, and the plasma activation time was 4 min. The pre-treated lens was obtained after plasma activation.

[0124] (2) Using a dual-target co-sputtering process, hafnium dioxide film and silicon dioxide film are alternately deposited on the surface of the pretreated lens obtained in step (1) in a mixed atmosphere of argon and oxygen. The rotation speed of the pretreated lens is 70 rpm and the temperature of the pretreated lens is 220℃.

[0125] During the deposition of hafnium dioxide film, the argon flow rate was 80 sccm, the oxygen flow rate was 8.5 sccm, the sputtering power of the hafnium dioxide target was 900 W, the deposition rate of the hafnium dioxide film was 0.4 nm / s, and the thickness of a single hafnium dioxide film was 75 nm. During the deposition of silicon dioxide film, the argon flow rate was 80 sccm, the oxygen flow rate was 3.5 sccm, the sputtering power of the silicon dioxide target was 1300 W, the deposition rate of the silicon dioxide film was 1 nm / s, and the thickness of a single silicon dioxide film was 50 nm. After alternating deposition of 4 hafnium dioxide films and 4 silicon dioxide films, a coated lens was obtained.

[0126] (3) Place the coated lens in the reaction chamber of the atomic layer deposition equipment, adjust the pressure in the reaction chamber to 30 Pa, and heat the coated lens to 190 °C; introduce trimethylaluminum into the reaction chamber at a flow rate of 25 sccm, continue to introduce for 0.15 s, stop and let stand for 9 s to complete one trimethylaluminum pulse stage; then, introduce nitrogen into the reaction chamber at a flow rate of 500 sccm to purge the surface of the coated lens with nitrogen, purge for 6 s and let stand for 4 s to complete one nitrogen purging stage; then, introduce ozone into the reaction chamber at a flow rate of 30 sccm, continue to introduce for 0.25 s, stop and let stand for 5 s to complete one ozone pulse stage; finally, introduce nitrogen into the reaction chamber at a flow rate of 400 sccm to purge the surface of the coated lens with nitrogen, purge for 6 s and let stand for 4 s to complete one nitrogen purging stage;

[0127] One deposition cycle consists of a trimethylaluminum pulse stage, a first nitrogen purging stage, an ozone pulse stage, and a second nitrogen purging stage. Every 5 deposition cycles, a water vapor repair stage and a third nitrogen purging stage are performed. The water vapor repair stage is as follows: water vapor is introduced into the reaction chamber at a flow rate of 13 sccm for 0.4 s, then stopped and left to stand for 4 s. The third nitrogen purging stage is as follows: nitrogen is introduced into the reaction chamber at a flow rate of 250 sccm to purge the surface of the coated lens for 6 s, then left to stand for 4 s. After 25 deposition cycles, an aluminum oxide encapsulation layer is formed on the surface of the coated lens.

[0128] (4) The encapsulated lens obtained in step (3) is subjected to gradient annealing under a nitrogen atmosphere and a pressure of 120 Pa. It is heated to 150°C at a heating rate of 2°C / min and held for 130 min. Then it is heated to 195°C at a heating rate of 1°C / min and held for 75 min. Then it is cooled to 90°C at a cooling rate of 0.4°C / min. Finally, the furnace is stopped and cooled to room temperature to obtain the laser protection lens.

[0129] Example 4

[0130] This embodiment provides a high damage threshold coating method for laser protective lenses based on semiconductor wafer technology, such as... Figure 1 As shown, the coating method specifically includes the following steps:

[0131] (1) The optical lens substrate was ultrasonically cleaned with an ultrasonic power of 380W and an ultrasonic time of 12min.

[0132] Subsequently, the ultrasonically cleaned optical lens substrate was plasma activated in a mixed atmosphere of argon and oxygen. The flow rate of argon in the mixed atmosphere was 70 sccm, the flow rate of oxygen was 28 sccm, the plasma activation pressure was 0.25 Pa, the radio frequency power was 450 W, and the plasma activation time was 3.5 min. The pre-treated lens was obtained after plasma activation.

[0133] (2) Using a dual-target co-sputtering process, hafnium dioxide film and silicon dioxide film are alternately deposited on the surface of the pretreated lens obtained in step (1) in a mixed atmosphere of argon and oxygen. The rotation speed of the pretreated lens is 75 rpm and the temperature of the pretreated lens is 230℃.

[0134] During the deposition of hafnium dioxide film, the argon flow rate was 82 sccm, the oxygen flow rate was 8.8 sccm, the sputtering power of the hafnium dioxide target was 950 W, the deposition rate of the hafnium dioxide film was 0.45 nm / s, and the thickness of a single hafnium dioxide film was 78 nm. During the deposition of silicon dioxide film, the argon flow rate was 82 sccm, the oxygen flow rate was 3.8 sccm, the sputtering power of the silicon dioxide target was 1350 W, the deposition rate of the silicon dioxide film was 1.1 nm / s, and the thickness of a single silicon dioxide film was 52 nm. After alternating deposition of 4 hafnium dioxide films and 4 silicon dioxide films, a coated lens was obtained.

[0135] (3) Place the coated lens in the reaction chamber of the atomic layer deposition equipment, adjust the pressure in the reaction chamber to 40 Pa, and heat the coated lens to 195 °C; introduce trimethylaluminum into the reaction chamber at a flow rate of 28 sccm, continue to introduce for 0.12 s, stop the introduction and let it stand for 8.5 s to complete one trimethylaluminum pulse stage; then, introduce nitrogen into the reaction chamber at a flow rate of 520 sccm to purge the surface of the coated lens with nitrogen, purge for 6 s and let it stand for 3.5 s to complete one first nitrogen purging stage; then, introduce ozone into the reaction chamber at a flow rate of 32 sccm, continue to introduce for 0.22 s, stop the introduction and let it stand for 4.5 s to complete one ozone pulse stage; finally, introduce nitrogen into the reaction chamber at a flow rate of 420 sccm to purge the surface of the coated lens with nitrogen, purge for 6 s and let it stand for 3.5 s to complete one second nitrogen purging stage;

[0136] One deposition cycle consists of a trimethylaluminum pulse stage, a first nitrogen purging stage, an ozone pulse stage, and a second nitrogen purging stage. Every 5 deposition cycles, a water vapor repair stage and a third nitrogen purging stage are performed. The water vapor repair stage involves introducing water vapor into the reaction chamber at a flow rate of 14 sccm for 0.35 s, then stopping and allowing it to stand for 3.5 s. The third nitrogen purging stage involves introducing nitrogen into the reaction chamber at a flow rate of 280 sccm to purge the surface of the coated lens for 6 s, followed by a 3.5 s stand. After 28 deposition cycles, an aluminum oxide encapsulation layer is formed on the surface of the coated lens.

[0137] (4) The encapsulated lens obtained in step (3) is subjected to gradient annealing under a nitrogen atmosphere and a pressure of 130 Pa. It is heated to 152°C at a heating rate of 2.2°C / min and held for 130 min. Then it is heated to 198°C at a heating rate of 1.1°C / min and held for 72 min. Then it is cooled to 95°C at a cooling rate of 0.45°C / min. Finally, the furnace is stopped and cooled to room temperature to obtain the laser protection lens.

[0138] Example 5

[0139] This embodiment provides a high damage threshold coating method for laser protective lenses based on semiconductor wafer technology, such as... Figure 1 As shown, the coating method specifically includes the following steps:

[0140] (1) The optical lens substrate was ultrasonically cleaned with an ultrasonic power of 400W and an ultrasonic time of 10min.

[0141] Subsequently, the ultrasonically cleaned optical lens substrate was plasma activated in a mixed atmosphere of argon and oxygen. The flow rate of argon in the mixed atmosphere was 80 sccm, the flow rate of oxygen was 30 sccm, the plasma activation pressure was 0.3 Pa, the radio frequency power was 500 W, and the plasma activation time was 3 min. The pre-treated lens was obtained after plasma activation.

[0142] (2) Using a dual-target co-sputtering process, hafnium dioxide film and silicon dioxide film are alternately deposited on the surface of the pretreated lens obtained in step (1) in a mixed atmosphere of argon and oxygen. The rotation speed of the pretreated lens is 80 rpm and the temperature of the pretreated lens is 250℃.

[0143] During the deposition of hafnium dioxide film, the argon flow rate was 85 sccm, the oxygen flow rate was 9 sccm, the sputtering power of the hafnium dioxide target was 1000 W, the deposition rate of the hafnium dioxide film was 0.5 nm / s, and the thickness of a single hafnium dioxide film was 80 nm. During the deposition of silicon dioxide film, the argon flow rate was 85 sccm, the oxygen flow rate was 4 sccm, the sputtering power of the silicon dioxide target was 1400 W, the deposition rate of the silicon dioxide film was 1.2 nm / s, and the thickness of a single silicon dioxide film was 55 nm. After alternating deposition of 3 hafnium dioxide films and 3 silicon dioxide films, a coated lens was obtained.

[0144] (3) Place the coated lens in the reaction chamber of the atomic layer deposition equipment, adjust the pressure in the reaction chamber to 50 Pa, and heat the coated lens to 200 °C; introduce trimethylaluminum into the reaction chamber at a flow rate of 30 sccm, continue to introduce for 0.1 s, stop and let stand for 8 s to complete one trimethylaluminum pulse stage; then, introduce nitrogen into the reaction chamber at a flow rate of 550 sccm to purge the surface of the coated lens with nitrogen, purge for 5 s and let stand for 3 s to complete one first nitrogen purging stage; then, introduce ozone into the reaction chamber at a flow rate of 35 sccm, continue to introduce for 0.2 s, stop and let stand for 4 s to complete one ozone pulse stage; finally, introduce nitrogen into the reaction chamber at a flow rate of 450 sccm to purge the surface of the coated lens with nitrogen, purge for 5 s and let stand for 3 s to complete one second nitrogen purging stage;

[0145] One deposition cycle consists of a trimethylaluminum pulse phase, a first nitrogen purging phase, an ozone pulse phase, and a second nitrogen purging phase.

[0146] One deposition cycle consists of a trimethylaluminum pulse stage, a first nitrogen purging stage, an ozone pulse stage, and a second nitrogen purging stage. Every 5 deposition cycles, a water vapor repair stage and a third nitrogen purging stage are performed. The water vapor repair stage is as follows: water vapor is introduced into the reaction chamber at a flow rate of 15 sccm for 0.3 s, then stopped and left to stand for 3 s. The third nitrogen purging stage is as follows: nitrogen is introduced into the reaction chamber at a flow rate of 300 sccm to purge the surface of the coated lens for 5 s, then left to stand for 3 s. After 30 deposition cycles, an aluminum oxide encapsulation layer is formed on the surface of the coated lens.

[0147] (4) The encapsulated lens obtained in step (3) is subjected to gradient annealing under a nitrogen atmosphere and a pressure of 150 Pa. It is heated to 155°C at a heating rate of 2.5°C / min and held for 120 min. Then it is heated to 200°C at a heating rate of 1.2°C / min and held for 70 min. Then it is cooled to 100°C at a cooling rate of 0.5°C / min. Finally, the furnace is stopped and cooled to room temperature to obtain the laser protection lens.

[0148] Example 6

[0149] This embodiment provides a high damage threshold coating method for laser protective lenses based on semiconductor wafer technology. The difference from Embodiment 1 is that in step (2), the thickness of the single-layer hafnium dioxide film is adjusted to 50nm, while other process parameters and operation steps are exactly the same as in Embodiment 1.

[0150] Example 7

[0151] This embodiment provides a high damage threshold coating method for laser protective lenses based on semiconductor wafer technology. The difference from Embodiment 1 is that in step (2), the thickness of the single-layer hafnium dioxide film is adjusted to 100nm, while other process parameters and operation steps are exactly the same as in Embodiment 1.

[0152] Example 8

[0153] This embodiment provides a high damage threshold coating method for laser protective lenses based on semiconductor wafer technology. The difference from Embodiment 1 is that in step (2), the thickness of the single-layer silicon dioxide film is adjusted to 30nm, while other process parameters and operation steps are exactly the same as in Embodiment 1.

[0154] Example 9

[0155] This embodiment provides a high damage threshold coating method for laser protective lenses based on semiconductor wafer technology. The difference from Embodiment 1 is that in step (2), the thickness of the single-layer silicon dioxide film is adjusted to 60nm, while other process parameters and operation steps are exactly the same as in Embodiment 1.

[0156] Example 10

[0157] This embodiment provides a high damage threshold coating method for laser protective lenses based on semiconductor wafer technology. The difference from Embodiment 1 is that in step (3), during the water vapor repair stage, the water vapor flow rate is adjusted to 10 sccm. Other process parameters and operation steps are exactly the same as in Embodiment 1.

[0158] Example 11

[0159] This embodiment provides a high damage threshold coating method for laser protective lenses based on semiconductor wafer technology. The difference from Embodiment 1 is that in step (3), during the water vapor repair stage, the water vapor flow rate is adjusted to 20 sccm. Other process parameters and operation steps are exactly the same as in Embodiment 1.

[0160] Example 12

[0161] This embodiment provides a high damage threshold coating method for laser protective lenses based on semiconductor wafer technology. The difference from Embodiment 1 is that in step (3), the continuous water vapor introduction time is adjusted to 0.1s during the water vapor repair stage. Other process parameters and operation steps are exactly the same as in Embodiment 1.

[0162] Example 13

[0163] This embodiment provides a high damage threshold coating method for laser protective lenses based on semiconductor wafer technology. The difference from Embodiment 1 is that in step (3), the continuous water vapor introduction time is adjusted to 0.7s during the water vapor repair stage. Other process parameters and operation steps are exactly the same as in Embodiment 1.

[0164] Example 14

[0165] This embodiment provides a high damage threshold coating method for laser protective lenses based on semiconductor wafer technology. The difference from Embodiment 1 is that in step (4), the second annealing temperature is adjusted to 150°C, while other process parameters and operation steps are exactly the same as in Embodiment 1.

[0166] Example 15

[0167] This embodiment provides a high damage threshold coating method for laser protective lenses based on semiconductor wafer technology. The difference from Embodiment 1 is that in step (4), the second annealing temperature is adjusted to 250°C, while other process parameters and operation steps are exactly the same as in Embodiment 1.

[0168] Comparative Example

[0169] This comparative example provides a high damage threshold coating method for laser protective lenses based on semiconductor wafer technology, which differs from Example 1 in that:

[0170] (1) In step (2), the alternating multilayer stacked structure is adjusted to a single-layer film structure. Only a silicon dioxide film is deposited on the surface of the pretreated lens, and no hafnium dioxide film is deposited. The thickness of the deposited silicon dioxide film is the same as the total thickness of the alternating stacked structure of hafnium dioxide film / silicon dioxide film in Example 1.

[0171] (2) In step (3), the water vapor repair stage and the third nitrogen purging stage are omitted;

[0172] (3) In step (4), the gradient annealing process is adjusted to linear annealing process. The encapsulated lens obtained in step (3) is heated to 190°C at a heating rate of 0.8°C / min and held for 200 min. Then the furnace is stopped directly and cooled to room temperature with the furnace.

[0173] Other process parameters and operating procedures are exactly the same as in Example 1.

[0174] The laser-induced damage threshold, laser-induced damage threshold retention rate after damp heat aging, and film adhesion of the laser protective lenses prepared in Examples 1-15 and the comparative examples were tested. The specific test steps are as follows:

[0175] 1. Laser-induced damage threshold

[0176] The surface of the laser-induced protective lenses prepared in Examples 1-15 was irradiated at multiple points using a nanosecond pulsed laser with a wavelength of 1064 nm (spot diameter of 0.8~1.0 mm). The laser energy density was gradually increased until damage was observed (determined by online microscopy). The damage threshold was defined as the highest energy density (tested at 15 points) where the damage probability was 0%, which is the laser-induced damage threshold (J / cm²). 2 ).

[0177] 2. Retention rate of laser-induced damage threshold after damp heat aging

[0178] The laser-induced damage threshold (LIDT0) of the laser protective lens before the damp heat aging test was tested using the above method. Then, it was placed in a constant temperature and humidity chamber (temperature 85±2°C, relative humidity 85%±5%) for 500 hours, and then placed at room temperature for 24 hours to recover. The laser-induced damage threshold (LIDT1) of the laser protective lens after the damp heat aging test was then tested. Based on the laser-induced damage thresholds of the laser protective lens before and after damp heat aging, the damage threshold retention rate was calculated using the following formula:

[0179] Damage threshold retention rate (%) = (LIDT1 / LIDT0) × 100%.

[0180] 3. Film adhesion

[0181] Using a scratch tester, a diamond indenter (tip radius 100μm) is used to scratch the film layer at a uniform speed of 10N / min. The critical load at which the film layer peels off is determined by an optical microscope, which is the film adhesion force (N).

[0182] The test results are shown in Table 1.

[0183] Table 1. Performance test results of the laser protective lenses prepared in Examples 1-15 and the comparative examples.

[0184]

[0185] The test data from Examples 1, 6, and 7 show that in Example 6, the hafnium dioxide film was too thin, resulting in uneven laser energy absorption, increased defect density, and a decreased laser-induced damage threshold. Simultaneously, the film's poor density reduced the damage threshold retention rate and film adhesion. In Example 7, the hafnium dioxide film was too thick, increasing heat capacity but lengthening the heat conduction path. Heat could not be dissipated promptly during laser irradiation, leading to heat accumulation deep within the film and a significant decrease in film adhesion.

[0186] The test data from Examples 1, 8, and 9 show that in Example 8, the silica film layer was too thin, losing its ability to block water and oxygen. Environmental erosion led to a significant decrease in the damage threshold retention rate. Furthermore, the thin silica film layer could not effectively transfer stress, resulting in decreased film adhesion. In Example 9, the silica film layer was too thick, and the difference in thermal expansion coefficients between it and the adjacent hafnium dioxide film layer was too large, creating significant shear stress at the interface. This caused microcracks at the film interface, ultimately resulting in a significant decrease in film adhesion. Additionally, the excessively thick silica film layer also caused a shift in light transmittance, lowering the damage threshold of the laser protective lens.

[0187] The test data from Examples 1, 10, and 11 show that in Example 10, the water vapor flow rate was too low, preventing water molecules from fully diffusing into the film layer to participate in amorphous structure repair and oxygen vacancy passivation. This resulted in numerous metastable defects and oxygen vacancies within the film layer, making it highly susceptible to damage during laser irradiation and ultimately lowering the damage threshold. In Example 11, the water vapor flow rate was too high, introducing excessive water vapor. Some of this water vapor was deposited as a loose hydroxyl structure, reducing the film layer's density and significantly lowering the damage threshold. Simultaneously, water molecules condensed at the hafnium dioxide grain boundaries, forming nanoscale liquid-phase corrosion pits after annealing, weakening the interfacial bonding strength between film layers and reducing film adhesion.

[0188] The test data from Examples 1, 12, and 13 show that in Example 12, the water vapor introduction time was too short, resulting in insufficient repair. Defects, pores, and dangling bonds in the film layer were not effectively repaired, severely affecting the film layer's density and chemical stability. The laser-induced damage threshold, damage threshold retention rate, and film adhesion all decreased. In Example 13, the water vapor introduction time was too long, leading to overhydration and reduced film adhesion.

[0189] The test data from Examples 1, 14, and 15 show that the second annealing temperature in Example 14 was too low, failing to effectively drive atomic rearrangement and stress release within the film layer, resulting in high residual stress and reduced film adhesion. In Example 15, the second annealing temperature was too high, leading to excessive densification of the silica film layer, generating a microcrack network, accelerating environmental erosion, and ultimately reducing the damage threshold retention rate. Simultaneously, it also promotes interdiffusion between the hafnium dioxide and silica film layers, forming a brittle hafnium silicate transition layer, ultimately resulting in a significant reduction in film adhesion.

[0190] As can be seen from the test data of Example 1 and the comparative example, the performance of the comparative example is significantly degraded. The main reason is the intrinsic defects of the film and the decrease in environmental adaptability caused by the simplification of the process. Since the single-layer silica film lacks the stress buffer of the alternating stacked structure, it cannot disperse the thermal shock energy during high-power laser irradiation, thus forming microcracks and grain boundary weakening points inside the film, increasing the laser energy absorption hotspots and causing deep thermal accumulation damage. At the same time, the omission of the water vapor repair stage and gradient annealing treatment results in the film's micropore defects not being filled, residual impurities not being removed, and insufficient thermal stress release, which greatly reduces the film's density and bonding strength. In a humid and hot aging environment, water and oxygen penetration exacerbates interface peeling and structural degradation, ultimately resulting in a decrease in damage threshold retention rate and adhesion.

[0191] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A method for high-damage-threshold coating of laser protective lenses based on semiconductor wafer technology, characterized in that, The coating method includes: (I) The optical lens substrate is subjected to ultrasonic cleaning and plasma activation in sequence to obtain a pretreated lens; (II) A hafnium dioxide film and a silicon dioxide film are alternately deposited on the surface of the pretreated lens obtained in step (I) using a dual-target co-sputtering process to obtain a coated lens; the thickness of a single hafnium dioxide film is 70~80nm, and the thickness of a single silicon dioxide film is 45~55nm; (III) Using trimethylaluminum and ozone as precursors, an alumina encapsulation layer is grown on the surface of the coated lens using atomic layer deposition. Every 5 alumina deposition cycles, a water vapor repair stage and a third nitrogen purging stage are performed sequentially. Gradient annealing is then performed to obtain the laser protection lens. The atomic layer deposition process also includes performing the following operations every 5 alumina deposition cycles: Water vapor is introduced into the reaction chamber and introduced for a period of time. Then the introduction is stopped and the mixture is left to stand for a period of time to complete the first water vapor repair stage. Subsequently, nitrogen gas is introduced into the reaction chamber to purge the surface of the coated lens. After purging, the mixture is left to stand for a period of time to complete the third nitrogen purging stage. During the water vapor repair stage, the water vapor flow rate is 12~15 sccm, and the continuous water vapor introduction time is 0.3~0.5s; The gradient annealing process includes the following steps: First, heat to the first annealing temperature at the first heating rate and hold at that temperature. Then, continue heating to the second annealing temperature at the second heating rate and hold at that temperature. Next, heat to the third annealing temperature at the first cooling rate. Finally, stop the furnace and let it cool to room temperature. The first annealing temperature is 145~155℃; The second annealing temperature is 190~200℃.

2. The high damage threshold coating method for laser protective lenses based on semiconductor wafer technology according to claim 1, characterized in that, In step (I), the ultrasonic power of the ultrasonic cleaning is 300~400W; The ultrasonic cleaning time is 10-20 minutes; The plasma activation was carried out in a mixed atmosphere of argon and oxygen. In the mixed atmosphere, the flow rate of argon is 50-80 sccm, and the flow rate of oxygen is 20-30 sccm. The plasma activation pressure is 0.1~0.3 Pa; The radio frequency power of the plasma activation is 300~500W; The plasma activation time is 3-5 minutes.

3. The high damage threshold coating method for laser protective lenses based on semiconductor wafer technology according to claim 1, characterized in that, In step (II), the dual-target co-sputtering uses hafnium dioxide and silicon dioxide targets; During the dual-target co-sputtering process, the rotation speed of the pre-processed lens is 60~80 rpm; During the dual-target co-sputtering process, the temperature of the pre-treated lens is 200~250℃; The dual-target co-sputtering was performed in a mixed atmosphere of argon and oxygen. During the deposition of the hafnium dioxide film, the flow rate of argon gas is 75-85 sccm, and the flow rate of oxygen gas is 8-9 sccm. The sputtering power of the hafnium dioxide target is 800~1000W; The deposition rate of the hafnium dioxide film is 0.3~0.5 nm / s; During the deposition of the silica film, the flow rate of argon is 75-85 sccm and the flow rate of oxygen is 3-4 sccm. The sputtering power of the silica target is 1200~1400W; The deposition rate of the silicon dioxide film is 0.8~1.2 nm / s; Three to five hafnium dioxide films and three to five silicon dioxide films are alternately deposited on the surface of the pretreated lens.

4. The high damage threshold coating method for laser protective lenses based on semiconductor wafer technology according to claim 1, characterized in that, In step (III), the atomic layer deposition process includes performing 20 to 30 deposition cycles; Each of the aforementioned deposition cycles includes a trimethylaluminum pulse phase, a first nitrogen purging phase, an ozone pulse phase, and a second nitrogen purging phase performed sequentially.

5. The high damage threshold coating method for laser protective lenses based on semiconductor wafer technology according to claim 4, characterized in that, In step (III), the atomic layer deposition process specifically includes: The coated lens is placed in the reaction chamber of the atomic layer deposition equipment, the pressure in the reaction chamber is adjusted to 10~50Pa, and the coated lens is heated to 180~200℃. Subsequently, trimethylaluminum is introduced into the reaction chamber, and after a period of continuous introduction, the introduction is stopped and the chamber is left to stand for a period of time to complete one trimethylaluminum pulse phase. Subsequently, nitrogen gas is introduced into the reaction chamber to purge the surface of the coated lens with nitrogen gas. After purging, the lens is left to stand for a period of time to complete the first nitrogen purging stage. Subsequently, ozone is introduced into the reaction chamber, and after a period of continuous introduction, the introduction is stopped and the chamber is left to stand for a period of time to complete one ozone pulse phase. Subsequently, nitrogen gas is introduced into the reaction chamber to purge the surface of the coated lens with nitrogen gas. After purging, the lens is left to stand for a period of time to complete the second nitrogen purging stage. One deposition cycle consists of one trimethylaluminum pulse phase, one first nitrogen purging phase, one ozone pulse phase, and one second nitrogen purging phase. After 20 to 30 deposition cycles, the aluminum oxide encapsulation layer is formed on the surface of the coated lens.

6. The high damage threshold coating method for laser protective lenses based on semiconductor wafer technology according to claim 5, characterized in that, During the trimethylaluminum pulse phase, the flow rate of trimethylaluminum is 20~30 sccm; During the trimethylaluminum pulse phase, the continuous introduction time of the trimethylaluminum is 0.1~0.2s; During the trimethylaluminum pulse phase, the settling time after the trimethylaluminum is stopped is 8-10 seconds; During the first nitrogen purging stage, the nitrogen flow rate is 450~550 sccm; In the first nitrogen purging stage, the nitrogen purging time is 5~8s; During the first nitrogen purging stage, the settling time after the nitrogen purging is completed is 3-5 seconds.

7. The high damage threshold coating method for laser protective lenses based on semiconductor wafer technology according to claim 5, characterized in that, During the ozone pulse phase, the ozone flow rate is 25~35 sccm; During the ozone pulse phase, the ozone is continuously introduced for 0.2 to 0.3 seconds. During the ozone pulse phase, the settling time after the ozone supply stops is 4-6 seconds; During the second nitrogen purging stage, the nitrogen flow rate is 350~450 sccm; In the second nitrogen purging stage, the nitrogen purging time is 5~8s; In the second nitrogen purging stage, the settling time after the nitrogen purging is completed is 3-5 seconds.

8. The high damage threshold coating method for laser protective lenses based on semiconductor wafer technology according to claim 1, characterized in that, During the water vapor repair stage, the settling time after the water vapor supply is stopped is 3-5 seconds; During the third nitrogen purging stage, the nitrogen flow rate is 200~300 sccm; In the third nitrogen purging stage, the nitrogen purging time is 5~8s; In the third nitrogen purging stage, the settling time after the nitrogen purging is completed is 3-5 seconds.

9. The high damage threshold coating method for laser protective lenses based on semiconductor wafer technology according to claim 1, characterized in that, In step (III), the entire gradient annealing process is carried out under a nitrogen atmosphere and a pressure of 100~150 Pa; The first heating rate is 1.5~2.5℃ / min; Hold at the first annealing temperature for 120-150 minutes; The second heating rate is 0.8~1.2℃ / min; Hold at the second annealing temperature for 70-80 minutes; The first cooling rate is 0.3~0.5℃ / min; The third annealing temperature is 80~100℃.

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