Strengthening, cleaning and coating production process for cerium-containing ultrathin glass cover plate

Abstract

The invention relates to the technical field of cerium-containing glass cover plate production processes, and particularly discloses a cerium-containing ultra-thin glass cover plate strengthening, cleaning and coating production process which effectively improves the surface quality and structural integrity of a cerium-containing ultra-thin glass cover plate through the design of multi-process collaborative pretreatment and strengthening pretreatment. Countercurrent rinsing of the first processing pool is combined with the ultrasonic technology, and surface floating dust and cutting chippings can be more thoroughly removed; the composite working solution in the second processing pool performs multi-level repair on microcracks and edge collapsing openings with different scales by utilizing the synergistic effect of barium sulfate microcrystals and nano silicon dioxide, and stress concentration is reduced; uniform chemical polishing is achieved through mixed acid liquor in the third processing pool under ultrasonic assistance, the surface flatness is optimized, and a good surface foundation is laid for subsequent procedures; the production flexibility and adaptability are enhanced through the multifunctional reuse design of the processing pools 4-6, and the processing pools serve as pure water cleaning standby units during normal production, so that it is guaranteed that surface impurities are thoroughly removed.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of production process of cerium-containing glass cover plate, in particular to a cerium-containing ultra-thin glass cover plate strengthening, cleaning and coating production process. BACKGROUND

[0002] The cerium-containing ultra-thin glass cover plate is widely used in the fields of electronic display and optical instrument due to excellent optical performance and chemical stability of cerium element. However, the ultra-thin characteristic makes it easy to produce edge collapse and surface micro-cracks after cutting, resulting in insufficient mechanical strength and easy breakage during processing and use. The existing pretreatment process mainly adopts single cleaning or simple polishing, which is difficult to completely remove surface dust, cutting debris and stubborn impurities, and the repair effect on micro-defects of different scales is limited, which directly affects the stability of subsequent strengthening and coating processes.

[0003] The existing strengthening and coating process has obvious shortcomings: the glass surface is not fully activated before chemical strengthening, resulting in low ion exchange efficiency and uneven depth of compressive stress layer; the coating process mainly adopts flat layout, and the edge is prone to thickness deviation during deposition of film material vapor, and the film-substrate adhesion is insufficient, which is prone to film peeling or performance degradation under the influence of environmental humidity and temperature; in addition, the production equipment has fixed functions and cannot dynamically adjust the production capacity according to the production volume, which is prone to low efficiency or insufficient production capacity when the order fluctuates, and has poor adaptability. SUMMARY

[0004] In view of the above problems, the present application provides a cerium-containing ultra-thin glass cover plate strengthening, cleaning and coating production process to overcome the defects of the prior art. The existing cerium-containing ultra-thin glass cover plate production process has the following technical defects: the surface dust, cutting debris and stubborn impurities remaining after glass cutting are difficult to completely remove, affecting the subsequent strengthening and coating effect; the micro-cracks and collapse of the glass edge are not completely repaired, resulting in insufficient glass strength and easy breakage; the glass surface flatness is poor during chemical polishing due to uneven acid reaction, affecting the optical performance; the production equipment has insufficient flexibility and cannot dynamically adjust the production capacity according to the production volume, resulting in poor adaptability; the glass surface is not fully activated before strengthening, resulting in low ion exchange efficiency and poor strengthening effect; the film thickness uniformity is poor during the coating process, the edge film thickness deviation is large, and the film-substrate adhesion is insufficient, resulting in poor weather resistance.

[0005] To achieve the above purpose, the present application realizes the following technical scheme: a cerium-containing ultra-thin glass cover plate strengthening, cleaning and coating production process, comprising the following steps:

[0006] Pure water pre-cleaning: Put the ultra-thin glass sheet containing cerium into No. 1 processing tank, inject pure water with a resistivity of > 30 MΩ·cm, and use reverse flow rinsing (pure water flows in from one end and flows out from the other end) combined with 40 kHz ultrasonic treatment for 8-10 minutes to remove surface dust, cutting debris and stubborn impurities.

[0007] Composite solution softening treatment: Transfer the glass sheet into No. 2 processing tank, use a composite working solution mixed by 40% barium sulfate solution, 0.5% nano-silica dispersion liquid (particle size 20-50 nm) and water in a volume ratio of 1:0.1:3, and treat at 50°C under 2.3 Hz ultrasonic wave for 8-10 minutes to fill micro-cracks by barium sulfate microcrystals and nano-silica and repair edge collapse.

[0008] Mixed acid polishing: Transfer the glass sheet into No. 3 processing tank, use a mixed acid liquid prepared by nitric acid, sodium bicarbonate, sodium hydrogen fluoride, and water in a mass ratio of 1:0.6:0.4:5, and treat at 30°C under 30 kHz ultrasonic wave for 8 minutes to achieve chemical polishing and improve surface flatness. Then heat the glass sheet in a high-frequency furnace at 260-300 MPa and 350-400°C for 90-120 minutes to completely immerse the glass sheet in potassium nitrate solution, fully wrap and replace sodium ions in the glass sheet, and cool to 60-100°C for subsequent cleaning steps.

[0009] Multi-stage cleaning and capacity adjustment: The glass sheet is sequentially treated in No. 4-6 processing tanks. No. 4 tank is used to neutralize residual acid liquid with 0.3% ammonia water, and No. 5-6 tanks are used for overflow rinsing (3-6 minutes each) with pure water with a resistivity of > 30 MΩ·cm. When production capacity increases, No. 4-6 tanks can be added with the same mixed acid liquid as No. 3 tank as additional polishing tanks to improve production capacity.

[0010] Pulse cleaning: Put the glass sheet into No. 7 processing tank, inject pure water with a resistivity of > 30 MΩ·cm, and use 1 Hz pulse bubbling combined with 45 kHz ultrasonic treatment for 5-8 minutes to deeply remove residual impurities.

[0011] Alkaline activation: Transfer the glass sheet into No. 8 processing tank, use an alkaline cleaning liquid (pH 9.5-10.5) mainly composed of 3% potassium hydroxide, compounded with 0.5% fatty alcohol polyoxyethylene ether sodium sulfate and 0.3% ethylenediaminetetraacetic acid disodium salt as a special cleaning liquid, and treat at 50°C under 2.5 kHz and 35 kHz dual-frequency ultrasonic wave for 8-12 minutes to activate the surface and remove organic matter and metal impurities.

[0012] Multi-stage ultrasonic strengthening: the glass sheet is sequentially treated in No. 9-10 processing pools (2.3 Hz ultrasonic wave, arc-shaped reflection vibration plate, glass sheet inclined at 15°) for 8 minutes, and then treated in No. 11-13 processing pools (3.5 Hz→4 Hz→5 Hz gradient frequency ultrasonic wave, flexible suspension tool) for 5-8 minutes each, to pre-activate cerium ion active sites and optimize the surface microstructure.

[0013] Precise dehydration: in No. 14 processing pool, a servo motor driven lifting mechanism (with laser displacement sensor) is used to vertically lift the glass sheet away from pure water with resistivity > 30 MΩ·cm at a speed of 0.4 mm / s ± 0.02 mm / s, to avoid water mark residues.

[0014] Segmented drying: the glass sheet is first heated in No. 15 processing pool by 100℃±2℃ hot air (air speed 1.5 m / s) and 2.5-5μm infrared radiation for 8 minutes, and then vacuum assisted drying in No. 16 processing pool (vacuum degree 500 Pa, 80℃±2℃) for 10 minutes, to ensure that the surface moisture is ≤50 ppm.

[0015] Vacuum coating: the glass sheet is fixed to the inner wall of the dome top of the vacuum chamber by bolted clamping plate, with a fitting gap ≤20μm, a dome curvature radius of 500mm, and a glass sheet spacing ≥20mm. After plasma activation (13.56 MHz radio frequency power source, 150W power, Ar gas environment), a magnesium fluoride film layer (purity 99.99%, deposition temperature 150℃±5℃, rate 0.5 nm / s, thickness 100-150 nm) is deposited by electron beam evaporation. After deposition, annealing at 200℃ for 30 minutes (with a small amount of O2) and natural cooling to below 60℃ before taking out.

[0016] The beneficial effects achieved by the present application with the above structure are as follows:

[0017] 1. Through the pretreatment and strengthening pretreatment design of multiple processes, the surface quality and structural integrity of the cerium-containing ultra-thin glass cover sheet are effectively improved. The reverse flow rinsing in No. 1 processing pool combined with ultrasonic technology can more thoroughly remove surface dust and cutting debris. The composite working solution in No. 2 processing pool utilizes the synergistic effect of barium sulfate microcrystals and nanosilica to repair microcracks and edge collapses of different scales in multiple levels, reducing stress concentration. The mixed acid solution in No. 3 processing pool realizes uniform chemical polishing under ultrasonic assistance, optimizing the surface flatness and laying a good surface foundation for subsequent processes.

[0018] 2. The multi-functional reuse design of the No. 4-6 processing pool enhances the flexibility and adaptability of production. In normal production, it is used as a pure water cleaning standby unit to ensure that surface impurities are completely removed. When production capacity increases, it can be converted into a mixed acid liquid polishing pool to increase parallel processing capacity and improve processing capacity per unit time. It can ensure the stability of regular production and meet large-scale production needs, improving equipment utilization and production efficiency.

[0019] 3. The dome top fitting method and magnesium fluoride vacuum coating process used in the coating stage significantly improve the film quality. The geometric constraints of the dome surface make the vapor molecules uniformly deposit, solving the problem of film thickness deviation at the edge of traditional flat coating. Plasma activation and in-situ annealing treatment enhance the film-substrate adhesion. The magnesium fluoride film effectively reduces the reflectivity of the glass surface and improves the weather resistance and wear resistance, making the product improve in both optical and mechanical properties. BRIEF DESCRIPTION OF DRAWINGS

[0020] The accompanying drawings are included to provide a further understanding of the present application, and constitute a part of the specification, illustrate embodiments of the present application and are used to explain the present application, and do not constitute a limitation on the present application. In the drawings:

[0021] Figure 1 A flowchart of a cerium-containing ultra-thin glass cover plate strengthening, cleaning and coating production process according to an embodiment of the present application. DETAILED DESCRIPTION

[0022] The technical solutions in the embodiments of the present application will be described in detail below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, not all embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0023] In the description of the present application, it should be understood that the terms "upper", "lower", "front", "rear", "left", "right", "top", "bottom", "inner", "outer" and the like indicate the orientation or positional relationship based on the orientation or positional relationship shown in the drawings, and are only for the convenience of describing the present application and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, therefore it cannot be understood as a limitation on the present application.

[0024] Embodiment 1

[0025] Please refer to Figure 1 As shown in the drawings, a cerium-containing ultra-thin glass cover plate strengthening, cleaning and coating production process includes the following steps:

[0026] Step one, prepare No. 1 processing pool, inject pure water with resistivity > 30 MΩ·cm into it, place the cerium-containing ultra-thin glass sheet to be treated into No. 1 processing pool smoothly, ensure that the glass sheet is completely immersed in pure water, and control the soaking time to be 5-8 minutes. In this process, the dissolved and flushing effects of pure water can remove dust and cutting debris attached to the surface of the glass.

[0027] Specifically, No. 1 processing pool adopts countercurrent rinsing design, i.e. pure water flows into one end of the processing pool and flows out from the other end, and the glass sheet is placed in the water flow channel. At the same time, an ultrasonic wave generating device is installed in the processing pool, and the frequency is set to 40 kHz. The newly injected pure water continuously cleans the glass sheet, and the cavitation effect generated by the ultrasonic wave can more efficiently strip stubborn impurities from the surface of the glass. Compared with traditional static soaking cleaning, the impurities can be more completely removed under the same amount of water, the cleaning efficiency and effect are improved, and water resource waste is reduced.

[0028] It should be noted that the countercurrent rinsing + ultrasonic auxiliary technology of pure water pre-cleaning utilizes the flushing effect of water flow and the cavitation effect of ultrasonic waves. Compared with traditional cleaning methods, it can more efficiently and completely remove dust, cutting debris and stubborn impurities on the surface of cerium-containing ultra-thin glass while saving water, thereby providing an ultra-clean surface for subsequent processes.

[0029] Step two, prepare No. 2 processing pool, mix 40% barium sulfate solution, 0.5% nano-silica dispersion liquid and water according to the volume ratio of 1:0.1:3, ultrasonic disperse for 30 minutes, and configure into a composite working solution for softening treatment. The particle size of nano-silica is controlled to be 20-50 nm, which utilizes its small size effect and surface activity to assist in filling micro-defects. The temperature of No. 2 processing pool is adjusted to 50°C, and an ultrasonic oscillation device is installed in the processing pool with the ultrasonic oscillation frequency set to 2.3 Hz. The cerium-containing ultra-thin glass sheet pre-cleaned by pure water is taken out from No. 1 processing pool and transferred into No. 2 processing pool, ensuring that the glass sheet is immersed in the above-mentioned composite working solution, maintaining the ultrasonic oscillation state, and the treatment time is 8-10 minutes.

[0030] It should be noted that under the condition of 50°C and ultrasonic oscillation, the microcrystals of barium sulfate and nano-silica cooperate with each other. The barium sulfate microcrystals fill larger size microcracks, and the nano-silica enters more subtle defects to perform multi-level “repair” on the microcracks and edge collapse generated by cutting on the surface of the glass, further reducing the stress concentration degree of the glass surface and edge, enhancing the softening effect of the cutting edge micro-collapse, improving the surface integrity and strength of the glass, and at the same time, the nano-silica can preliminarily construct a nano-scale rough structure on the surface of the glass, which is beneficial to subsequent film coating.

[0031] In the barium sulfate-nano silica composite solution softening process, the synergistic filling effect of barium sulfate microcrystals and nano silica enables multi-level repair of micro-defects of different scales, significantly reducing stress concentration, effectively repairing cutting defects, improving the strength and breakage resistance of the glass itself, and constructing a preliminary nanostructure that is conducive to subsequent coating.

[0032] Step 3: Prepare Processing Tank No. 3. Accurately weigh each reagent according to the mass ratio of nitric acid, sodium bicarbonate, sodium hydrofluoric acid, and water (1:0.6:0.4:5) and add them to Processing Tank No. 3. Stir thoroughly to prepare a mixed acid polishing working solution. Configure a temperature control system to precisely control the temperature of the mixed acid solution in Processing Tank No. 3 at 30℃. Install an ultrasonic vibration device in the processing tank and set the frequency to 30kHz. Place the cerium-containing ultrathin glass slide, softened by the barium sulfate-nano silica composite solution, into Processing Tank No. 3, ensuring the glass slide is fully immersed in the mixed acid solution. The treatment time is 8 minutes. Then, heat the glass slide in a high-frequency furnace at 260-300 MPa and 350-400℃ for 90-120 minutes to completely immerse the glass slide in the potassium nitrate solution, fully coating it and displacing the sodium ions in the glass slide. Cool to 60-100℃ and proceed to the subsequent cleaning steps.

[0033] Specifically, nitric acid in the mixed solution in processing tank No. 3 ionizes to produce H+. + Lowering the pH of the solution promotes the dissolution of oxides on the glass surface, creating acidic conditions for chemical polishing. Dilute nitric acid has a certain oxidizing and dissolving ability for cerium oxides on the glass surface, which can remove the surface oxide layer and improve the smoothness of the glass surface. At the same time, sodium bicarbonate reacts with nitric acid to produce CO2 and water, neutralizing excess H2. + To prevent excessive corrosion of the glass due to overly acidic solution and to maintain pH stability during the polishing process; sodium hydrofluoric acid dissociates into HF and F in aqueous solution. - HF reacts chemically with SiO2 in the glass: SiO2 + 4HF → SiF4↑ + 2H2O. The generated SiF4 gas escapes from the glass surface and selectively dissolves surface protrusions, reducing surface roughness and achieving optical-grade polishing. This chemical polishing removes microscopic surface irregularities and, in turn, HF... - Can react with Ce in glass 3+ / Ce 4+ Forming stable complexes promotes uniform corrosion of cerium-containing glass surfaces and improves polishing consistency; cerium ions react with F... - The complexation effect can inhibit the uneven dissolution of cerium-enriched phases on the glass surface, avoid the appearance of "white fog" or etching spots on the surface after polishing, and ensure the uniformity of polishing.

[0034] It should be noted that the temperature control system accurately maintains the temperature of the mixed acid solution, avoids the influence of temperature fluctuation on the polishing uniformity, cooperates the ultrasonic oscillation with the mixed acid solution, accelerates the chemical reaction of the acid solution and the glass surface by the ultrasonic cavitation effect, provides an acidic environment by nitric acid, realizes chemical polishing by the reaction of sodium hydrofluoride and glass, buffers and adjusts the solution properties by sodium bicarbonate, and guides the acid solution to act more uniformly by the preliminary rough structure constructed by nano-silicon dioxide, so as to realize the super-uniform polishing of the surface of the cerium-containing ultra-thin glass, remove the tiny unevenness on the surface, further improve the flatness and smoothness of the glass surface, and the formed surface microstructure is more conducive to the adhesion of the subsequent strengthening film layer and coating layer, thereby providing a better surface state for the subsequent process.

[0035] The mixed acid solution-ultrasonic cooperative polishing process realizes the super-uniform polishing of the surface of the cerium-containing ultra-thin glass by accurate temperature control, ultrasonic and acid solution cooperation and nano-structure guidance, improves the surface flatness and smoothness, optimizes the surface microstructure, avoids the influence of uneven polishing on the subsequent strengthening and coating effect, greatly improves the quality and performance of the final product of the cerium-containing ultra-thin glass cover sheet, enhances the film layer adhesion, and helps the product to have better application quality and market competitiveness in the fields of electronics and optics.

[0036] Step four, prepare processing pools 4, 5 and 6, and inject pure water with a resistivity of > 30 MΩ·cm into the processing pools 4, 5 and 6 respectively, and use the processing pools 4, 5 and 6 as pure water cleaning standby units. In normal production, the No. 4 pool is used to accommodate the glass sheet polished in the No. 3 pool, and the residual acid solution is neutralized with 0.3% ammonia water; the No. 5-6 pool is used to overflow rinse the glass sheet treated in the No. 4 pool with pure water with a resistivity of > 30 MΩ·cm for 3-5 minutes to completely remove impurities and ensure the surface cleanliness.

[0037] Specifically, when the production capacity increases, the mixed acid polishing working solution (consistent with the No. 3 pool formula: nitric acid, sodium bicarbonate, sodium hydrofluoride, water, prepared according to the mass ratio of 1:0.5:0.3:5) can be added to the No. 4-6 processing pool to transform it into an additional mixed acid polishing pool. By increasing the parallel processing capacity of the polishing process, the number of glass sheets that can be processed per unit time is increased. Specifically, one or more of the No. 4-6 pools can be flexibly activated according to the actual production capacity demand to expand the polishing process capacity and meet large-scale production tasks, thereby realizing the dynamic adjustment of production capacity.

[0038] Step five, prepare the No. 7 processing pool, inject pure water with a resistivity of > 30 MΩ·cm, and use the pulse bubbling (1 Hz) + 45 kHz ultrasonic cooperative technology to immerse and treat the glass sheet for 5 minutes. The pulse bubbling disturbs the water flow, and the ultrasonic cavitation deeply cleans the residual impurities to provide a clean base for the cleaning of the reagent.

[0039] Step six, prepare No. 8 processing pool, configure with 3% potassium hydroxide as the main body, compound 0.5% AES surfactant, 0.3% EDTA-2Na chelating agent alkaline cleaning solution (pH 9.5-10.5), 50°C, double frequency ultrasonic (2.5kHz+35kHz) treatment for 12 minutes; main body alkaline hydrolysis of organic matter, AES enhances oil stripping, EDTA-2Na chelating metal impurities; double frequency ultrasonic coordination, low frequency vibration falls macro impurities, high frequency cleaning micro gap, depth activation of glass surface.

[0040] Step seven, prepare No. 9 and No. 10 processing pools, set up arc-shaped reflective ultrasonic vibration plate to form a focused oscillation field, and pass the glass sheet at an angle of 15° for 8 minutes; 2.3Hz low frequency ultrasonic pre-activation of cerium ion active sites, preparation for chemical strengthening.

[0041] Prepare No. 11, No. 12 and No. 13 processing pools, use flexible suspension tooling, and suspend the glass sheet, and treat it at a gradient frequency of 3.5Hz→4Hz→5Hz for 4 minutes each time; high frequency ultrasonic refines the surface micro morphology, promotes the ordered arrangement of ions, and improves the strengthening uniformity; wherein the flexible suspension tooling is made of silica gel wrapped polytetrafluoroethylene.

[0042] Step eight, prepare No. 14 processing pool, use servo motor driven lifting mechanism, and match laser displacement sensor to lift the glass sheet at a constant speed of 0.4mm / s±0.02mm / s, vertically separate from pure water with resistivity>30MΩ·cm, avoid water mark residue, and ensure surface cleanliness.

[0043] Step nine, prepare No. 15 and No. 16 processing pools, in No. 15 processing pool, use 60°C±2°C, 1.5m / s hot air circulation+2.5-5μm wavelength infrared radiation composite heating, and treat for 8 minutes to quickly remove the surface free water.

[0044] It should be noted that through multi-process collaborative innovation, the surface is super clean and the defects are fully repaired in the pretreatment stage by using countercurrent rinsing+ultrasonic assistance, composite solution multilayer repair and mixed acid- ultrasonic synergistic polishing, laying the foundation for subsequent processes; the surface activity and cleanliness are improved by means of pulse cleaning, composite alkali activation, multi-stage hertz ultrasonic and precise slow pull drying in the pre-strengthening process; the multifunctional reuse of No. 4-6 pool adapts to different production scales and enhances flexibility; in the chemical strengthening, coating and post-treatment links, stress control, functional film integration and performance guarantee are realized, and the glass surface quality, strengthening performance and coating function are significantly improved in the whole process.

[0045] Example 2

[0046] The surface reflectivity of cerium-containing glass is reduced by using magnesium fluoride as an antireflection film to enhance the weather resistance of the glass. The cerium-containing ultra-thin glass sheet is fixed to the inner wall of the top of the dome of a vacuum chamber. An inverted layout is adopted, i.e., the workpiece is upward and the evaporation source is downward. The geometric constraint of the dome surface is used to make the vapor molecules uniformly deposit along the radial direction, thereby solving the problem of film thickness deviation at the edge of the traditional planar coating. The film thickness uniformity is controlled within ±1%.

[0047] Step ten, open the coating vacuum chamber, heat to 80℃ and vacuum to 5×10 -4 Pa, remove the residual water vapor and impurity gas in the chamber, start the chamber wall ion bombardment device, and clean the inner wall of the dome under the condition of Ar + ion with an energy of 100eV; the cerium-containing ultra-thin glass sheet processed by No. 1-16 processing pool (size ≤150mm×150mm, thickness 0.1-0.3mm) is subjected to edge inspection to ensure that there is no chipping, and the size of the chipping is ≤5μm; a clamping plate is provided on the inner wall of the top of the dome, and the glass sheet is fixed by the clamping plate to completely fit the dome curve, the fitting gap is ≤20μm, and the glass coating surface faces downward and faces the lower evaporation source, the curvature radius of the dome is R=500mm, and the spacing between the glass sheets is ≥20mm to avoid mutual shielding of the film material vapor; high-purity Ar gas is introduced into the chamber to maintain a working pressure of 2Pa, a radio frequency power source is turned on, the frequency is 13.56MHz, and the power is 150W to generate Ar + plasma; the plasma bombards the downward coating surface of the glass for 10 minutes to remove the residual organic contaminants and adsorbed water on the surface, increase the surface energy to ≥75mN / m, and enhance the adhesion of the film layer.

[0048] A power 0-5kW electron beam evaporation source is used, the crucible is filled with MgF2 particles with a purity of 99.99% and a particle size of 1-3mm to ensure that the particles are not agglomerated, the power is gradually increased to 1kW and maintained for 30 minutes to remove the crystal water and volatile impurities in MgF2, and it is observed that the vacuum degree is considered qualified when it rises to ≤2×10 -4 Pa; the deposition parameters are set as follows: vacuum degree: 5×10 -5 Pa maintained by a molecular pump group; electron beam power: 2.5kW, evaporation rate stabilized at 0.5nm / s, real-time feedback by a quartz crystal film thickness monitor; deposition temperature: the glass sheet temperature is controlled at 150℃±5℃ by the heating wire built in the dome to avoid high temperature leading to glass stress release; deposition time: calculated according to the target film thickness, for example, 120nm film thickness corresponds to a deposition time of 240 seconds.

[0049] After the evaporation source is started, MgF2 vapor diffuses radially along the dome, and because the glass sheet is attached to the top of the dome, the vapor molecules are uniformly deposited on the glass surface at an incident angle of 45°-60° to form a dense film layer; the film thickness deviation is recorded every 60 seconds, and through the multi-point monitoring instrument: one monitoring point is arranged at the center and the edge of the dome respectively to ensure that the film thickness uniformity is ≤±1%; after the deposition is completed, the electron beam evaporation source is turned off, the vacuum state is maintained, the temperature of the glass sheet is raised to >200℃, and the annealing process is maintained for 30 minutes; during the annealing process, a small amount of O2 gas is introduced, and the flow rate is 5sccm to promote the crystallization of the MgF2 film layer, convert it from an amorphous state to a tetragonal crystal system, and improve the hardness and friction resistance of the film layer.

[0050] After the annealing is completed, the heating is stopped, the glass sheet is naturally cooled to below 60℃ for 2 hours, the temperature is prevented from changing suddenly to cause the film layer to crack, dry N2 is introduced to the normal pressure to release the clamping plate, the glass sheet is taken out, an anti-static chuck is used to avoid scratching the film surface; finally, the film layer performance is detected: thickness and uniformity: an ellipsometer is used for measurement, the film thickness deviation is <1.5nm, and the thickness difference between the center and the edge is ≤2nm; optical performance: an ultraviolet-visible spectrophotometer is used for testing, the reflectivity in the 400-700nm wave band is ≤0.5%, and the light transmittance is improved by >3% compared with the uncoated glass; adhesion: a 3M adhesive tape hatch test is performed, the grid is 1mm×1mm, and the film layer does not fall off.

[0051] Step eleven: film thickness and film adhesion test, the coated glass after processing is boiled in water for 20-30 minutes, after being taken out, high-adhesion tape is used to paste the coated glass for peeling test, and a chromatograph is used for observation to determine whether the magnesium fluoride film thickness meets the requirements.

[0052] It should be noted that by adopting the dome top attachment design, the incident angle of the vapor molecules is consistent, the "edge thinning" problem of traditional planar coating is solved, the uniformity is effectively improved, the demand of high-precision optical devices is met, the film-substrate adhesion reaches the ASTMD3359 standard 5B level, can withstand 1000 times of friction test without damage under the load of 500g, the glass sheet is tightly attached by the bolt clamping tool to avoid film thickness fluctuation caused by vibration, the batch qualification rate is ≥99%, and the method is suitable for large-scale production.

[0053] Meanwhile, the contents not described in detail in the specification all belong to the prior art known by those skilled in the art.

[0054] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0055] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered illustrative and non-limiting in all respects, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the scope of the invention. No reference numerals in the claims should be construed as limiting the scope of the claims.

[0056] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A process for strengthening, cleaning, and coating cerium-containing ultrathin glass coverslips, characterized in that, Includes the following steps: Step 1: Place the cerium-containing ultrathin glass sheet in the pure water of processing tank No. 1, and use countercurrent rinsing combined with 40kHz ultrasonic cleaning for 5-8 minutes. Step 2: Place the glass slide treated in Step 1 into the composite working solution in processing tank No. 2, and treat it under ultrasonic conditions of 50℃ and 2.3Hz for 8-12 minutes. The composite working solution is composed of 40% barium sulfate solution, 0.5% nano silica dispersion and water in a volume ratio of 1:0.1:

3. Step 3: Place the cerium-containing glass slide treated in Step 2 into the mixed acid solution in Processing Pool No. 3, and treat it under ultrasonic conditions of 30℃ and 30kHz for 8-12 minutes. Then, preheat it in a high-frequency furnace at 260-300 MPa and 0-120 degrees Celsius for 20-30 minutes. Then, heat the glass slide at 300-400 degrees Celsius. When the heating temperature is reached, inject it into potassium nitrate solution to fully cover it. Control the temperature at 350-400 degrees Celsius and immerse it for 90-120 minutes to displace sodium ions in the glass slide. Slowly cool it down to 100-60 degrees Celsius, remove the glass cover, and proceed to the subsequent cleaning steps. Step 4: The glass slides processed in Step 3 are sequentially cleaned in processing tanks 4-6. Processing tanks 4-6 are standby units for pure water cleaning, and a mixed special cleaning solution is added during production. Step 5: Place the glass slide treated in Step 4 into pure water in Processing Pool No. 7 and treat it with 1Hz pulse bubbling combined with 45kHz ultrasonic waves for 5 minutes. Step 6: Place the glass slide treated in Step 5 into the special cleaning solution in Processing Pool No. 8, and treat it under dual-frequency ultrasonic conditions of 50℃, 2.5kHz and 35kHz for 8-12 minutes. Step 7: The glass slides treated in Step 6 are sequentially subjected to ultrasonic treatment at 2.3Hz in processing tanks 9-10 for 8-12 minutes, and ultrasonic treatment at 3.5-5Hz gradient frequency in processing tanks 11-13 for 4-6 minutes each. Step 8: The glass sheet treated in Step 7 is slowly pulled and dehydrated in processing tank No. 14 at a speed of 0.4 mm / s ± 0.02 mm / s; Step 9: The glass slides treated in Step 8 are sequentially subjected to hot air and infrared combined heating treatment in Processing Pool No. 15 for 8 minutes to quickly remove free water from the surface. Step 10: Vacuum-coated with magnesium fluoride on the glass sheet processed in Step 9, wherein the coating is applied using a dome-top bonding method; Step 11: Film thickness and adhesion test. After processing, the coated glass is boiled in water for 20-30 minutes. After boiling, high-adhesion tape is used to stick the coated glass and a peel test is performed. The thickness of the magnesium fluoride film is observed using a chromatograph to see if it meets the requirements.

2. The process for strengthening, cleaning, and coating a cerium-containing ultrathin glass cover sheet according to claim 1, characterized in that, The resistivity of the pure water mentioned in step one is >30MΩ·cm. Countercurrent rinsing is a cleaning method in which pure water flows in from one end of the processing tank and flows out from the other end, which prevents the residue after cleaning from contaminating the cleaned product.

3. The process for strengthening, cleaning, and coating a cerium-containing ultrathin glass cover sheet according to claim 1, characterized in that, In step two, the nano-silica has a particle size of 20-50 nm and is prepared by ultrasonic dispersion for 10-30 minutes. In step three, the mixed acid solution is prepared by nitric acid, sodium bicarbonate, sodium hydrofluoric acid and water in a mass ratio of 1:0.6:0.4:

5.

4. The process for strengthening, cleaning, and coating a cerium-containing ultrathin glass cover sheet according to claim 1, characterized in that, In step four, the No. 4 processing tank is neutralized with 0.3% ammonia water to neutralize the residual acid, and the No. 5 and No. 6 processing tanks are rinsed with pure water with a resistivity >30MΩ·cm by overflow, with each rinse lasting 5-10 minutes.

5. The process for strengthening, cleaning, and coating a cerium-containing ultrathin glass cover sheet according to claim 1, characterized in that, The alkaline cleaning solution described in step six is ​​based on 3% potassium hydroxide, compounded with 0.5% sodium fatty alcohol polyoxyethylene ether sulfate and 0.3% disodium ethylenediaminetetraacetate, with a pH value of 9.5-10.

5.

6. The process for strengthening, cleaning, and coating a cerium-containing ultrathin glass cover sheet according to claim 1, characterized in that, In step seven, processing pools 9-10 are equipped with arc-shaped reflective ultrasonic plates, through which glass slides pass at a 15° angle; processing pools 11-13 employ flexible suspension fixtures made of silicone-coated polytetrafluoroethylene.

7. The process for strengthening, cleaning, and coating a cerium-containing ultrathin glass cover sheet according to claim 1, characterized in that, In step eight, the resistivity of the pure water in processing pool No. 14 is >30MΩ·cm. A servo motor drives the lifting mechanism and is equipped with a laser displacement sensor.

8. The process for strengthening, cleaning, and coating a cerium-containing ultrathin glass cover sheet according to claim 1, characterized in that, In step nine, the hot air temperature of processing tank No. 15 is >100℃±2℃, the wind speed is 1.5m / s, and the infrared radiation wavelength is 2.5-5μm; the vacuum degree of processing tank No. 16 is 3.0E-0.003Pa, and the temperature is 80℃±2℃.

9. The process for strengthening, cleaning, and coating a cerium-containing ultrathin glass cover sheet according to claim 1, characterized in that, Step 10, the magnesium fluoride vacuum coating, includes: fixing a glass slide to the inner wall of the top of the vacuum chamber dome, activating it with plasma, and then depositing a magnesium fluoride film by electron beam evaporation at a deposition temperature of >200℃±5℃. After deposition, the film is annealed at 200℃ for 30 minutes.

10. The process for strengthening, cleaning, and coating a cerium-containing ultrathin glass cover sheet according to claim 9, characterized in that, The vacuum chamber dome has a curvature radius of 500 mm, and the glass plates are fixed with clamps, with a spacing of ≥20 mm between the glass plates; the magnesium fluoride film has a thickness of 100-120 nm and a deposition rate of 0.5 nm / s.

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