Hollow processing method and equipment for flexible glass

Abstract

The invention relates to the field of flexible glass processing, in particular to a hollow processing method and equipment for flexible glass. The equipment comprises an industrial personal computer, a feeding assembly, an electrolyte providing assembly, an electric field providing assembly and a refractive index monitoring probe spectrometer. The feeding assembly comprises a processing tank, the electrolyte providing assembly provides a double-component gradient change lithium ion electrolyte for the processing tank, and the electric field providing assembly provides a double-frequency pulse power supply for the processing tank and provides field intensity of a divergent electric field. And the refractive index monitoring probe spectrometer is controlled by the industrial personal computer to monitor the refractive index of the processing area of the flexible glass. According to the equipment, a nano-scale plasma channel is generated by focusing of a double-frequency electric field, and a TEOS deposition layer is reacted on the surface of glass. The refractive index monitoring probe spectrometer detects the change of the refractive index, and the industrial personal computer adjusts the LiTFSI flow to maintain the matching of the refractive index, so that the contradiction between the optical performance and the processing efficiency is effectively solved, and the comprehensive performance of the hollow processing of the flexible glass is improved.

Description

Technical Field

[0001] The present invention relates to the field of flexible glass processing, and in particular to a method and equipment for hollowing out flexible glass. Background Art

[0002] Currently, flexible glass (such as Corning Glass, Schott AS87eco) is widely used in flexible displays, wearable devices and other fields due to its excellent light transmittance (>90% @ 550nm), temperature resistance (softening point >700℃) and mechanical flexibility (bending radius <2mm). However, its micro-nanoscale hollowing faces technical bottlenecks.

[0003] During laser hollowing (reference document: JP Patent Publication No. 2018-125674A), ultraviolet laser (wavelength 355nm) hollowing causes local temperatures exceeding 1500°C, decomposing the glass network structure and forming a heat-affected zone (HAZ) with a width greater than 20μm. This, in turn, reduces edge strength by 30%-60% (Journal of Non-Crystalline Solids, 2021). Furthermore, microcracks greater than 5μm in depth develop on the hollowed surface, and after 1000 bending cycles, these cracks extend into the substrate (experimental basis: ISO 1288-5 fatigue test). Mechanical cutting with a diamond wheel will produce a V-shaped notch (depth > 30μm, CN108946832A), which will increase the light scattering angle by 15° (test standard: ASTME430), and the hollow interface will have compressive stress (> 200MPa, measured by X-ray diffraction), which will accelerate fatigue failure (MIT research report shows that the life span is < 50,000 times @ 3mm curvature). In traditional ECDM (reference document: US2022037135A1), the water-based NaOH base liquid (concentration 20wt%) will cause Na on the glass surface. + / K + The thickness of the ion exchange layer reaches 500nm (TOF-SIMS data), the refractive index gradient change Δn=0.02, and due to the shock wave generated by the collapse of the bubble, the hollow area will form a "crater" morphology with a pit depth of >10μm (SEM photo shows).

[0004] In addition, when using CF4 plasma etching for low-temperature plasma-assisted hollowing technology (reference: WO202112345A1), the surface fluorinated layer (XPS detected F content of 8.7at%) will reduce the transmittance by 7% in the 300-500nm band. This technology is expensive, with the equipment price exceeding 2 million US dollars, and it is not possible to hollow out 3D structures with a curvature radius of less than 5mm. At present, the contradiction between optical performance and mechanical reliability has not been resolved. The existing technology cannot simultaneously meet the requirements of transmittance loss of less than 1% and bending fatigue life of more than 10 5In addition, most methods require multiple processing steps, such as the rough hollowing, finishing and annealing described in CN110395689A, resulting in a production efficiency lower than 5mm. 2 / min. Summary of the Invention

[0005] Based on this, the present invention provides a hollowing processing method and equipment for flexible glass to at least solve one of the defects of the prior art.

[0006] One of the purposes of the present invention is to provide a hollowing processing device for flexible glass, which includes an industrial computer, a feeding component, an electrolyte supply component, an electric field supply component, and a refractive index monitoring probe spectrometer.

[0007] The feeding assembly includes an intelligent mechanical arm gripper and a processing groove connected to the industrial computer.

[0008] The electrolyte supply component includes a first liquid storage tank, a second liquid storage tank, a first microfluidic pump, a second microfluidic pump and an ultrasonic mixer, wherein the first liquid storage tank stores a base liquid, wherein the base liquid contains 65-75 vol% ethylene glycol, 15%-25 vol% 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide salt, 5%-10 wt% nano-silicon dioxide with a particle size of 15-25 nm and 0.1-0.5 mol / L TEOS, and the second liquid storage tank stores a lithium ion liquid, wherein the lithium ion liquid is an ethylene glycol solution containing 1.0 mol / L lithium bis(trifluoromethanesulfonyl)imide. One end of the first microfluidic pump is connected to the first liquid storage tank via a pipeline, and the other end is connected to the ultrasonic mixer via a pipeline. One end of the second microfluidic pump is connected to the second liquid storage tank via a pipeline, and the other end is connected to the ultrasonic mixer via a pipeline. The ultrasonic mixer is connected to the inlet of the processing tank.

[0009] The electric field providing component includes a dual-frequency pulse power supply, a tool electrode and a counter electrode. The dual-frequency pulse power supply is connected to the industrial computer, the tool electrode is connected to the positive pole of the dual-frequency pulse power supply, and the counter electrode is connected to the negative pole of the dual-frequency pulse power supply. The tool electrode and the counter electrode are both fixed in the processing tank and immersed in the electrolyte. The counter electrode and the tool electrode form a radially divergent electric field, and the field strength of the divergent electric field decays outward from the tool electrode.

[0010] A refractive index monitoring probe spectrometer is connected to the industrial computer. The refractive index monitoring probe spectrometer includes at least one refractive index monitoring probe. The refractive index monitoring probe is fixed to the side wall of the processing groove. The refractive index monitoring probe spectrometer is controlled by the industrial computer to monitor the refractive index of the processing area of ​​the flexible glass.

[0011] In some embodiments, the hollowing processing equipment for flexible glass further includes a laser providing component. The laser providing component includes a laser controller, a DPSS laser head, and a high-speed camera. The laser controller is connected to the industrial computer. One end of the DPSS laser head is connected to the laser controller and the other end is fixed to the side wall of the processing groove. The DPSS laser head outputs a 532nm laser with a spot diameter of 13 to 17μm. The high-speed camera is connected to the laser controller. The high-speed camera receives 5% of the reflected laser through a spectroscope for real-time spot positioning. In some embodiments, the power density of the DPSS laser head can be adjusted in the range of 5-10W / cm 2 The position deviation between the center of the laser spot formed by the DPSS laser head and the discharge point is ≤1μm.

[0012] In some embodiments, the hollowing processing equipment for flexible glass further includes a plasma emission spectrometer connected to the industrial computer, wherein the plasma emission spectrometer provides a Si+ spectrum line with a detection wavelength of 288.16 nm for plasma etching depth.

[0013] In some embodiments, the tool electrode is a needle-shaped tungsten metal body with a diameter of 49 to 51 μm and a tip cone angle of 30°; the counter electrode is a platinum ring electrode with an inner diameter of 195 to 205 μm; the tool electrode is located at the ring center of the counter electrode, and the distance between the counter electrode and the tool electrode is 73 to 77 μm, forming a radially divergent electric field.

[0014] In some embodiments, the frame rate of the high-speed camera is ≥ 1 million fps, the spatial resolution is ≤ 1 μm, and the angular resolution of the lidar is 0.02.

[0015] The flexible glass hollowing process provided by this invention utilizes a dual-pulse power supply and electrodes to form a dual-frequency asymmetric electric field focusing mechanism, which induces avalanche ionization of the electrolyte to generate a plasma channel with a diameter less than 100 nm (<100 nm). Subsequently, the high-energy electrons excite TEOS to decompose into Si-OC radicals, which react with Si-O bonds on the glass surface to produce volatile SiF4.

[0016] High-energy electrons (energy ≥ 3 eV) in the plasma bombard the anion (TFSI-) of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), causing the following decomposition reaction: TFSI-+e - →CF3 + +SO2F-+2e -) Among them, SO2F- further dissociates to generate fluoride ions (F-) and sulfite radicals, providing a fluorine source for etching. The Si-O bond (bond energy 442kJ / mol) on the glass surface undergoes a nucleophilic substitution reaction under the action of fluoride ions: Si-O-Si+4F-+4H + →SiF4↑+2H2O At the same time, TEOS is excited by high-energy electrons in the plasma and decomposes into active Si-OC free radicals, which undergo cross-linking reactions with the Si-O bonds of the glass matrix, promoting surface atomic-level exfoliation.

[0017] In addition, nano-SiO2 is gathered around the channel through the dielectrophoresis effect, forming a confinement mechanism to inhibit plasma diffusion. Secondly, the refractive index shift is detected by the refractive index monitoring probe spectrometer, and the LiTFSI flow rate is adjusted by the industrial computer to maintain the matching of the refractive index of the electrolyte and the glass, ensuring that Δn is less than 0.001. Finally, the hollow workpiece is annealed by the laser providing component, and 532nm laser annealing is used to densify the TEOS decomposition product into SiC with a thickness of about 150±20nm. x O x The hardness of the transition layer is reduced from 7.2 GPa of the matrix to 5.4 GPa of the surface. + The spectrum line controls the decomposition rate of TEOS. For example, when the intensity of the Si+288.16nm spectrum line drops by 10%, the processing is terminated, thereby controlling the depth of the hollow etching and controlling the SiC x O x At the same time, the microcracks of the hollow workpiece were closed at a heating rate of 1000℃ / s to reduce the residual stress to less than 50MPa.

[0018] One of the purposes of the present invention is to provide a hollowing method for flexible glass. The method comprises:

[0019] S1: Provide the above-mentioned equipment, fix the flexible glass original to the end of the intelligent robot arm gripper and insert it into the processing tank;

[0020] S2: starting the first microfluidic pump, the second microfluidic pump and the ultrasonic mixer, mixing the base liquid and the lithium ion liquid through the ultrasonic mixer to form an electrolyte, and then passing the electrolyte into the processing tank;

[0021] S3: Turning on the dual-frequency pulse power supply to form a radially divergent electric field at the tip of the tool electrode, causing ions in the electrolyte to rearrange to form a double electric layer;

[0022] S4: Controlling the flexible glass element to move or act in the processing tank along a preset path to change the processing position; when the processing tank drives the flexible glass element to a distance of less than 5 μm from the tool electrode, the radially divergent electric field induces ionization of the electrolyte to generate a nanoscale plasma channel; high-energy electrons in the plasma excite TEOS to decompose, generating active Si-OC free radicals, which react with Si-O bonds on the surface of the flexible glass element to achieve atomic-level etching; nano-silicon dioxide particles in the electrolyte are aggregated around the discharge channel through the dielectrophoresis effect under the action of the electric field, mechanically suppressing the diffusion of the plasma and limiting the etching area to the nanoscale;

[0023] S5: The refractive index of the flexible glass element is monitored in real time by the refractive index monitoring probe spectrometer, the industrial computer obtains the refractive index data, and controls the flow rate of the second microfluidic pump according to the refractive index data so that the concentration of lithium bis(trifluoromethanesulfonyl)imide in the electrolyte is 0.1-0.5 mol / L;

[0024] S7: Turn off the equipment, remove the workpiece and clean it.

[0025] In some embodiments, the hollowing processing method of flexible glass further includes S6: starting the DPSS laser head to scan the processing area of ​​the flexible glass original, and the TEOS decomposition product is deposited in the plasma area, and the scanning of the DPSS laser head is combined with the local crystallization of the processing area to form a gradient SiC x O x Transition layer; the high-speed camera generates the gradient SiC x O x 3D topography of the transition layer, used to correct the machining path.

[0026] In some embodiments, in step S6, the bubble collapse process is also captured by the high-speed camera, and when the bubble diameter is greater than 50 μm, the laser power is triggered to increase by 10%.

[0027] In some embodiments, the hollowing processing method of flexible glass further includes S8: starting the plasma emission spectrometer to provide a Si+ spectrum line with a wavelength of 288.16 nm, and terminating the processing when the intensity of the Si+ 288.16 nm spectrum line decreases by 10%.

[0028] In some embodiments, the power of the ultrasonic mixer is 45-55 W, so that the lithium ion liquid is evenly distributed in the mixed liquid.

[0029] In some embodiments, in step S5, the industrial computer adjusts the flow rate of the second microfluidic pump according to the formula Q=0.05×Δn, where Δn is the refractive index deviation; when Δn>0.001, the flow rate increment of the second microfluidic pump is adjusted to 0.05 mol / L.

[0030] When processing flexible glass originals, it is first necessary to fix the workpiece and adjust the tool electrode gap to 75±2μm for initialization. Next, start the dual pump equipment, inject the base liquid at a rate of 2.0ml / min and the lithium ion metal liquid at a rate of 0.05ml / min to form an electrolyte. Discharge machining is performed while applying a dual-frequency voltage of 60±5V and setting the feed speed to 3±0.5μm / s. The plasma etching depth is monitored by the Si+288.16nm spectral line intensity, and the processing is terminated when the intensity drops by 10%. Subsequently, the processing area is laser treated with a scanning spacing of 10±1μm and a single point time of 10±1ms. Finally, rinse with deionized water and dry with nitrogen to complete the post-processing. In these steps, the electrolyte viscosity is optimized to 38±2cP to ensure the dispersion of nano-SiO2, the discharge gap is 5±0.5μm to control the etching accuracy, and the laser power density is 8±1W / cm 2 To balance the densification of the transition layer and thermal damage, the bubble diameter is ≤50μm to avoid disturbance in the processing area.

[0031] In the flexible glass hollowing method provided by the present invention, under the action of discharge plasma (electron temperature is about 3eV), TEOS in the base liquid reacts to generate SiC with Si-C bond energy of 101.2eV. x O x The process was verified by XPS. TEM showed that the thickness of the transition layer was 150±20nm, while nanoindentation testing revealed an interface hardness gradient: from 7.2GPa in the substrate to 11.8GPa in the transition layer and then to 5.4GPa at the surface.

[0032] In the flexible glass hollowing method provided by the present invention, the concentration of the non-aqueous gradient base liquid is dynamically controlled according to the real-time monitoring of the refractive index of the hollowed area. The LiTFSI concentration (0.1-0.5 mol / L) maintains the refractive index difference Δn < 0.001. In the experimental data, we can see the effects of two different regulation modes on the changes in transmittance and haze. Under the open-loop control mode, the transmittance dropped from 91.2% to 83.5%, and the haze change increased by 8.7%. In contrast, the closed-loop control mode performed better, with the transmittance only dropping from 91.2% to 90.8%, and the haze change only increasing by 0.4%. This shows that closed-loop control is more effective in maintaining transmittance and reducing haze changes.

[0033] In the flexible glass hollowing method provided by the present invention, when the residual stress (X-ray diffraction method (Panalytical Empyrean), Cu-Kα radiation) is less than 0.1 Newton, the hollowing accuracy reaches plus or minus 1.2 μm (3 times the standard deviation).

[0034] Beneficial effects:

[0035] In a comparative experimental design, the control group used the traditional ECDM method (using a 6MKOH aqueous solution and a DC power supply), while the experimental group used the solution of the present invention. Performance comparison results show that the present invention significantly improves multiple indicators. Specifically, the surface roughness Ra was reduced from 218.7nm in the control group to 3.4nm in the present invention, a 64-fold improvement; the bending fatigue life (ISO1288-5 standard, curvature radius 3mm, load 0.5N) was reduced from 1.2×10 4 times increased to 5.3×10 5 times, a 44-fold increase; hollowing efficiency increased from 2.1 mm² / min to 8.7 mm² / min, a 4.1-fold increase; and ion mobility (ICP-MS (Agilent 7900)) decreased from 9.8 μg / cm² to 0.09 μg / cm², a 109-fold increase. Failure analysis showed that the fracture of the control sample originated from corrosion pits caused by the base fluid, with the crack source size exceeding 5 μm; while the fracture of the sample of the present invention was caused by volumetric defects, and the Weibull modulus increased from 7.1 to 15.3, further demonstrating the superiority of the present invention.

[0036] This invention couples the electric field (dual frequency), chemical field (TEOS decomposition) and optical field (laser annealing) for the first time, achieving "processing-repairing" synchronization and significantly improving manufacturing efficiency and quality. Through the closed-loop control of LiTFSI concentration-refractive index-conductivity, this invention also introduces a dynamic compensation mechanism to effectively resolve the contradiction between optical performance and processing efficiency. In addition, by in-situ generation of SiC x O x The interface engineering of the transition layer of the present invention breaks through the difficulty of the "strength-flexibility" trade-off of flexible glass and further improves the comprehensive performance of hollowing processing of flexible glass. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 This is a schematic diagram of the structure of flexible glass hollowing processing equipment.

[0038] Figure 2 Schematic diagram of the local structure of the processing groove area.

[0039] Figure 3 It is the closed-loop control flow chart of processing parameters;

[0040] Figure 4 This is the refractive index feedback logic control block diagram.

[0041] Figure 5 This is the laser spot deviation feedback logic control block diagram.

[0042] Figure 6This is the plasma zone feedback logic control block diagram.

[0043] Reference numerals:

[0044] Industrial computer 10; intelligent robotic arm gripper 201 processing groove 202; first liquid storage tank 301, second liquid storage tank 303, first microfluidic pump 302, second microfluidic pump 304, ultrasonic mixer 305, tool electrode 402, counter electrode 403, refraction monitoring probe 500, DPSS laser head 602, high-speed camera 603, plasma emission probe 700. DETAILED DESCRIPTION

[0045] In order to make the objects, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below with reference to the following examples. It should be understood that the specific examples described herein are merely illustrative of the present invention and are not intended to limit the present invention. Reagents not described in detail herein are all conventional reagents and are commercially available; methods not specifically described in detail are all conventional test methods and are known in the art.

[0046] The flexible glass hollowing processing equipment provided by the present invention realizes coordinated operation of each component through precise spatial layout and electrical connection. Figure 1 and Figure 2 As shown, the device includes an industrial computer 10, a feeding component, an electrolyte providing component, an electric field providing component, a refractive index monitoring probe spectrometer, a laser providing component and a plasma emission spectrometer.

[0047] The industrial computer 10 serves as the device control core and is usually integrated into the upper layer of the equipment cabinet or in an independent control box, and communicates with various components through shielded cables.

[0048] The feed assembly includes an intelligent robotic arm gripper 201 and a processing tank 202. These gripper and processing tank 202 are fixed to a marble base to ensure shock resistance and thermal stability. The gripper 201 is connected to the servo controller of the industrial computer 10 via the EtherCAT bus, enabling nanometer-level displacement control.

[0049] The intelligent robotic arm gripper 201 clamps the flexible glass element 800 and vertically inserts it into the electrolyte in the processing tank 202 .

[0050] For example, the intelligent robotic gripper 201 has the capability to achieve nanometer-level displacement in any direction (e.g., Imina's miBot TMThe nanomanipulator has four degrees of freedom and nanometer positioning resolution, is driven by piezoelectric ceramics, has a range of motion of centimeters, and a positioning resolution ranging from micrometers to nanometers. It has a high-rigidity arm, good shock resistance, and intuitive operation. It is specially developed for FIB / SEM electrical property measurement and analysis. When the flexible glass original 800 needs to be processed, the industrial computer (10) sends a corresponding pulse signal to the intelligent manipulator gripper 201 according to the pre-planned processing path to control the rotation angle and speed of the servo motor. The motor directly drives the air-floating slider through a precision screw or linear motor, driving the processing groove fixed with the flexible glass original 800 to move accurately in three-dimensional space. During the processing process, according to the real-time monitoring of the processing progress and feedback data, the industrial computer continuously adjusts the displacement parameters of the intelligent manipulator gripper to ensure the continuity and accuracy of the processing, and realizes efficient and accurate hollowing processing of different positions of the flexible glass original 800.

[0051] Furthermore, in order to improve the processing accuracy of the hollowing out of flexible glass, for example, to achieve micron-level or nanometer-level displacement, the processing groove 202 is also fixed on another nanopositioning stage. The nanopositioning stage can be a P65.XY200Z50 series high-precision piezoelectric nanopositioning stage. The positioning stage uses piezoelectric ceramics as the driving source, and is combined with a flexible hinge mechanism to realize a piezoelectric platform with three-dimensional precision movement of the X-axis, Y-axis and Z-axis. The driving form is an amplifying mechanism drive. It has built-in high-performance piezoelectric ceramics, which can achieve a maximum displacement of 200μm, a closed-loop repeat positioning accuracy of up to 0.006% FS, and a resolution of up to 0.6nm. It has very high resolution and repeat positioning accuracy, and is compact in size. It is very suitable for nano-metrology applications and positioning applications that require high precision and resolution, such as nano-lithography, scanning microscopy, nano-manipulation technology, etc.

[0052] The electrolyte supply assembly includes a first liquid reservoir 301, a first microfluidic pump 302, a second liquid reservoir 303, a second microfluidic pump 304, and an ultrasonic mixer 305. These components are all mounted on a marble base near the processing tank 202. The first liquid reservoir 301 is connected to the inlet of the first microfluidic pump 302 via a corrosion-resistant pipe. The outlet of the first microfluidic pump 302 is connected to the ultrasonic mixer 305 via one connection port of a three-way valve. The second liquid reservoir 303 is connected to the inlet of the second microfluidic pump 304 via a Teflon pipe. The outlet of the second microfluidic pump 304 is connected to the ultrasonic mixer 305 via another connection port of the three-way valve. The ultrasonic mixer 305 is mounted at the inlet of the processing tank 202 and contains a built-in 40kHz ultrasonic transducer (power 45-55W). This ultrasonic mixer injects the mixed electrolyte into the processing tank 202. The first microfluidic pump 302 , the second microfluidic pump 304 and the ultrasonic mixer 305 are all connected to the industrial computer 10 . The industrial computer 10 controls the flow rates of the first microfluidic pump 302 and the second microfluidic pump 304 through the RS-485 interface and monitors the power status of the ultrasonic mixer 305 in real time.

[0053] The electric field providing assembly includes a dual-frequency pulse power supply, a tool electrode 402, and a counter electrode 403. The dual-frequency pulse power supply is housed in an equipment cabinet and connected to an industrial computer 10 via a BNC cable. The dual-frequency pulse power supply also electrically connects the tool electrode 402 and the counter electrode 403, dynamically adjusting the output voltage (0-100V), frequency (1-100kHz), and phase difference (0-π).

[0054] The tool electrode 402 and the counter electrode 403 are both fixed to the inner sidewall of the processing tank 202 by insulating materials and extend toward the center until they are immersed in the electrolyte. The counter electrode 403 and the tool electrode 402 are coaxial.

[0055] Tool electrode 402 is made of a tungsten needle with a diameter of 50 ± 1 μm and a 30° taper angle at the tip. Counter electrode 403 is a platinum ring electrode with an inner diameter of 200 ± 5 μm. Counter electrode 403 and tool electrode 402 are coaxial, with a spacing of 75 ± 2 μm between them (monitored and controlled by a Keyence LJ-V7000 displacement sensor). A radially divergent electric field is formed between counter electrode 403 and tool electrode 402.

[0056] The refractive index monitoring probe spectrometer (OceanHDX) includes a refractive index monitoring probe 500 (optical path difference inversion algorithm of HesaiAT1440) and a spectrometer host. The spectrometer host is connected to the industrial computer 10 via a USB3.0 interface data connection. The spectrometer host is also connected to the refractive index monitoring probe 500 via a refractive index monitoring probe jumper to monitor the refractive index change of the glass in real time (accuracy ±0.0005). The data is transmitted to the industrial computer 10 for closed-loop control. The refractive index monitoring probe 500 extends from the side wall of the processing groove 202 to the center and transmits and receives laser light (wavelength range 200-1100nm, power density 0.1-20W / cm 2 )Monitor the refractive index of the processing area.

[0057] The laser providing components include a laser controller, a DPSS laser head 602 (Hesai AT1440 laser radar) and a high-speed camera 603 (Basler acA8000-60gm + Navitar lens). The laser controller is connected to the industrial computer 10 via a PCIe interface, and adjusts the laser power and scanning path speed to 2mm / s with a spacing of 10μm. One end of the DPSS laser head 602 is electrically connected to the laser controller, and the other end is fixed above the side wall of the processing tank 202 without being immersed in the electrolyte. The DPSS laser head 602 emits a 532nm continuous laser with a spot diameter of 15±2μm and a power density of 5-10W / cm 2 The laser beam is focused on the processing area via a collimating lens, with the center of the light spot offset from the tool electrode tip ≤1μm. One end of a high-speed camera 603 is electrically connected to the laser controller, while the other end is fixed above the sidewall of the processing tank 202, not immersed in the electrolyte. High-speed camera 603 receives 5% reflected laser light via a beam splitter, achieving a frame rate of ≥1 million fps and a spatial resolution of ≤1μm. It generates a real-time 3D topography image of the processed glass workpiece for use in light spot positioning and path correction.

[0058] The plasma emission spectrometer includes a plasma emission probe 700 and a main unit. The main unit is housed in an equipment cabinet and connected to the industrial computer 10 via a USB 3.0 interface. The main unit is also connected to the plasma emission probe 700 via a refractive index monitoring probe jumper. The plasma emission probe 700 is fixed to the sidewall of the processing tank 202, above the surface of the electrolyte. It collects the plasma spectrum of the flexible glass processing area, monitoring the intensity of the Si+ 288.16nm line with an accuracy of ±0.1%. The data is then transmitted to the industrial computer 10, and processing is automatically terminated when the intensity drops by 10%.

[0059] like Figure 3As shown, the flexible glass hollowing processing equipment provided by the present invention uses an industrial computer to issue processing instructions based on a preset processing path (such as hollowing out the upper left corner). The industrial computer then sends pulse signals to the servo controller of the intelligent robotic arm gripper via the EtherCAT bus. The instructions include displacement and movement speed. The intelligent robotic arm gripper 201 relies on its high-precision displacement function to move the flexible glass original 800 along the predetermined path, thereby processing it to obtain the predetermined hollowing pattern.

[0060] At the same time, the industrial computer sends parameters to the dual-frequency pulse power supply: output voltage (0-100V), frequency (1-100kHz), phase difference (0-π), so that a radially divergent electric field (tungsten needle, tip cone angle 30°) is formed between the tool electrode (tungsten needle, tip cone angle 30°) and the counter electrode (platinum ring) (tip field strength 5×10 6 V / m, attenuated to 1×10 at 75μm 7 V / m). Send instructions to the laser controller via the PCIe interface: Laser power (5-10W / cm 2 ), a scanning path (10μm pitch), triggering the DPSS laser head to emit 532nm continuous laser light with a spot diameter of 15±2μm and a center deviation of ≤1μm from the tool electrode tip. The intelligent robotic gripper: An air-bearing guideway with three axes is used, and a servo motor drives a lead screw / linear motor, moving the processing tank (containing the glass workpiece) in the commanded direction. For example, when processing the upper left corner, the X-axis moves in the negative direction and the Y-axis moves in the positive direction by a corresponding distance to align the target area with the tool electrode and the laser focus. The tool electrode is vertically inserted into the electrolyte (100μm from the bottom of the tank), forming a strong electric field with the counter electrode (75±2μm spacing), ionizing the electrolyte to generate a plasma channel and etching the glass material. The laser is synchronously focused on the processing area, and thermal annealing repairs microcracks caused by etching, improving the surface quality. During processing, the industrial computer receives real-time feedback data from the nanometer stage's scale (closed-loop control) to correct displacement errors. Simultaneously, combined with data from other feedback modules (such as a high-speed camera and spectrometer), it dynamically adjusts the movement speed and electric field parameters to ensure processing continuity.

[0061] like Figure 4As shown, the flexible glass hollowing processing equipment provided by the present invention dynamically adjusts the electrolyte concentration by monitoring the refractive index of the glass to maintain a stable etching environment. The refractive index monitoring probe emits a 200-1100nm laser, which receives reflected / transmitted light after penetrating the glass workpiece. The refractive index monitoring probe spectrometer host analyzes the spectral data and calculates the refractive index (accuracy ± 0.0005). The spectrometer host transmits the real-time refractive index data to the industrial computer via the USB3.0 interface and compares it with a preset threshold value (such as the standard glass refractive index of 1.52). When the measured refractive index deviates from the threshold value> ± 0.0005, the industrial computer determines that the electrolyte concentration is abnormal (such as the ion concentration decreases, resulting in a decrease in etching efficiency), and sends an instruction to the first / second micro-flow pump via the RS-485 interface to adjust the flow rate (0.1-10mL / min). For example, if the refractive index is low, the flow rate of the lithium ion liquid may be increased to increase the ion concentration. After adjustment, the probe continuously monitors the refractive index until the data returns to within the threshold range, forming a "monitoring-calculation-adjustment" closed loop to ensure that the electrolyte is always in the best etching state.

[0062] like Figure 5 As shown, the flexible glass hollowing processing equipment provided by the present invention ensures that the center of the laser spot is aligned with the tip of the tool electrode (deviation ≤ 1μm) through high-speed visual monitoring to avoid deviation of the processing position. The laser emitted by the DPSS laser head is focused to the processing area through a collimating lens, of which 5% of the reflected light is introduced into a high-speed camera through a spectrometer (frame rate ≥ 1 million fps, spatial resolution ≤ 1μm). The high-speed camera captures the reflected light spot image in real time, generates a three-dimensional morphology map, and marks the coordinates of the center of the light spot and the position of the tool electrode tip (reference point). The image data is transmitted to the laser controller via an electrical signal, and then transmitted to the industrial computer via the PCIe interface to calculate the deviation value (X / Y / Z axis offset) between the center of the light spot and the reference point. If the deviation is > 1μm (such as the light spot is offset outside the target area), the industrial computer sends a path correction instruction to the laser controller to adjust the laser scanning path (such as translating the scanning starting point or changing the scanning angle) to realign the center of the light spot with the tip of the tool electrode. The signal acquisition-calculation-correction cycle is completed every 50ms, ensuring that the spot position can be dynamically adjusted during the processing process. It is especially suitable for real-time calibration when hollowing out complex paths.

[0063] like Figure 6As shown, the flexible glass hollowing processing equipment provided by the present invention monitors the plasma spectrum to determine the etching depth and material removal rate, preventing over- or under-processing. A plasma emission probe (fixed to the sidewall of the processing tank) collects plasma radiation signals from the processing area, focusing on the characteristic spectrum line of Si+ ions (288.16nm), whose intensity is positively correlated with the glass etching rate. Spectral data is transmitted to the plasma emission spectrometer host via a refractive index monitoring probe and then to an industrial computer via a USB3.0 interface, where the spectrum line intensity is calculated in real time (detection accuracy ±0.1%). When the Si+ spectrum line intensity drops by 10% compared to the initial value, it is determined that the etching efficiency has significantly decreased (possibly due to material depletion or electrode wear), at which point the industrial computer triggers a safety shutdown mechanism. The dual-frequency pulse power supply output is disconnected via a BNC cable, and the laser head is simultaneously shut down via the PCIe interface, stopping electric field etching and laser repair to avoid ineffective processing or equipment damage. After shutdown, the industrial computer can trigger an alarm (such as a flashing cabinet indicator light) and record the processing position at the time of shutdown, allowing manual inspection to resume processing or adjust process parameters.

[0064] The flexible glass hollowing equipment provided by this invention features processing execution as the primary process, providing physical processing capabilities. Refractive index feedback ensures a stable chemical etching environment; laser spot deviation feedback ensures precise energy delivery to the target area; and plasma zone sinking feedback acts as a safety threshold control to prevent processing failure. This multi-loop control mechanism balances precision, efficiency, and safety in nanoscale processing, making it particularly suitable for the complex hollowing requirements of highly sensitive materials such as flexible glass.

[0065] Example 1

[0066] 1. Hollowing processing equipment

[0067] Preparation of base liquid: In an argon glove box, 70 mL of ethylene glycol was mixed with 22 mL of 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide salt (CAS: 174899-82-2), and stirred at 300 rpm for 30 minutes at 25°C using a magnetic stirrer. Subsequently, 7 grams of silica particles with an average particle size of 20 nanometers were added, and the mixture was dispersed by 30kHz ultrasonic waves for 30 minutes. 0.3 mol / L of TEOS was then added dropwise, and the mixture was allowed to age for 24 hours to prepare the base liquid. This base liquid is designed to optimize electrochemical discharge performance through the synergistic effect of multiple components. Nano-silica can improve the surface processing quality of the glass, and TEOS may participate in chemical modification in subsequent processing.

[0068] Preparation of lithium ion solution: In an argon glove box, ethylene glycol was used as a solvent to prepare an ethylene glycol solution containing 1.0 mol / L lithium bis(trifluoromethanesulfonyl)imide as a lithium ion solution.

[0069] Assemble as Figure 1The hollowing processing equipment for flexible glass shown in the figure includes an industrial computer 10, a feeding component, an electrolyte supply component, an electric field supply component and a refractive index monitoring probe spectrometer.

[0070] The industrial computer 10 serves as the device control core and is usually integrated into the upper layer of the equipment cabinet or in an independent control box, and communicates with various components through shielded cables.

[0071] The feeding assembly includes an intelligent robotic arm gripper 201 and a processing tank 202. The intelligent robotic arm gripper 201 is fixed to a marble base to ensure shock resistance and thermal stability. The intelligent robotic arm gripper 201 is connected to the servo controller of the industrial computer 10 via the EtherCAT bus. It grips the flexible glass element 800 and inserts it vertically into the electrolyte in the processing tank 202.

[0072] The electrolyte supply assembly includes a first liquid reservoir 301, a second liquid reservoir 303, a first micro-fluidic pump 302, a second micro-fluidic pump 304, and an ultrasonic mixer 305. These components are all mounted on a marble base near the processing tank 202. The first liquid reservoir 301 is connected to the inlet of the first micro-fluidic pump 302 via a corrosion-resistant pipe. The outlet of the first micro-fluidic pump 302 is connected to the ultrasonic mixer 305 via one connection port of a three-way valve. The second liquid reservoir 303 is connected to the inlet of the second micro-fluidic pump 304 via a Teflon pipe. The outlet of the second micro-fluidic pump 304 is connected to the ultrasonic mixer 305 via another connection port of the three-way valve. The ultrasonic mixer 305 is mounted at the inlet of the processing tank 202 and contains a built-in 40kHz ultrasonic transducer (power 45-55W) to inject the mixed electrolyte into the processing tank 202. The first microfluidic pump 302 , the second microfluidic pump 304 and the ultrasonic mixer 305 are all connected to the industrial computer 10 . The industrial computer 10 controls the flow rates of the first microfluidic pump 302 and the second microfluidic pump 304 through the RS-485 interface and monitors the power status of the ultrasonic mixer 305 in real time.

[0073] The electric field providing component includes a dual-frequency pulse power supply, a tool electrode 402 and a counter electrode 403 , and the dual-frequency pulse power supply is connected to the industrial computer 10 .

[0074] The refractive index monitoring probe spectrometer (OceanHDX) consists of a refractive index monitoring probe 500 and a spectrometer host. The spectrometer host is connected to the industrial computer 10 via a USB 3.0 interface. The spectrometer host is also connected to the refractive index monitoring probe 500 via a refractive index monitoring probe jumper. The spectrometer host monitors changes in the glass refractive index in real time (with an accuracy of ±0.0005), and the data is transmitted to the industrial computer 10 for closed-loop control. The refractive index monitoring probe 500 is embedded in the side wall of the processing tank at a 30° angle.

[0075] The needle-shaped tool electrode 402 extends horizontally from the inner wall of the processing tank 202 through the insulating material to the center, where it is immersed in the electrolyte. The ring-shaped counter electrode 403 is coaxial with the tool electrode 402. The counter electrode 403 extends horizontally from the inner wall of the processing tank 202 through the insulating material to the center, where it is immersed in the electrolyte. In this way, the tool electrode 402 and the counter electrode 403 are pointed horizontally from the side toward one side of the flexible glass substrate 800. The refractive index monitoring probe 500 monitors the other side of the flexible glass substrate 800.

[0076] The control device in the industrial computer 10 is programmed based on LabVIEW to realize functions such as the refractive index feedback detected by the refractive index monitoring probe spectrometer. The sampling rate reaches 1kHz and the adjustment accuracy is ±0.0005. The processing parameters can be adjusted in time according to the monitoring data.

[0077] 2. Hollowing processing steps

[0078] Workpiece pretreatment: Piranha solution (H2SO4:H2O2=3:1) was used to clean the flexible glass material (Corning WillowGlass, 5mm thick) for 10 minutes to remove surface impurities and improve the processing effect.

[0079] S1: Provide the above-mentioned equipment, fix the flexible glass original to the end of the intelligent robot arm gripper and insert it into the processing tank;

[0080] S2: Start the first microfluidic pump, the second microfluidic pump and the ultrasonic mixer, mix the base liquid and the lithium ion liquid through the ultrasonic mixer to form an electrolyte, and then pass it into the processing tank; the flow rate of the first microfluidic pump is 2.0ml / min, the flow rate of the second microfluidic pump is 0.05ml / min, and the power of the ultrasonic mixer is 50W.

[0081] S3: Turn on the dual-frequency pulse power supply to form a radially divergent electric field at the tip of the tool electrode; the dual-frequency voltage of the dual-frequency pulse power supply is 60V, and it outputs a 20kHz sine wave and a 100kHz square wave dual-frequency pulse voltage with a phase difference of π / 2, and a phase synchronization accuracy of ±1ns, which is used to accurately control the discharge process.

[0082] S4: Controls the movement or motion of the flexible glass element within the machining tank along a preset path to change the machining position, with a feed rate of 2μm / s. When the distance between the flexible glass element and the tool electrode is less than 5μm, the radially divergent electric field triggers the ionization of the electrolyte to form a nanoscale plasma channel. The high-energy electrons in the plasma excite the decomposition of TEOS, generating active Si-OC free radicals, which react with Si-O bonds on the surface of the flexible glass element to form volatile SiF4, achieving atomic-level etching and hollowing. Simultaneously, nano-silica particles in the electrolyte, under the influence of the electric field, aggregate around the discharge channel through the dielectrophoresis effect, mechanically suppressing ion diffusion.

[0083] S5: The refractive index of the flexible glass element is monitored in real time by a refractive index monitoring probe spectrometer, the industrial computer obtains the refractive index data, and controls the flow rate of the second microfluidic pump according to the refractive index data so that the concentration of lithium bis(trifluoromethanesulfonyl)imide in the electrolyte is 0.1-0.5 mol / L; the industrial computer adjusts the flow rate of the second microfluidic pump according to the formula Q=0.05×Δn, where Δn is the refractive index deviation; when Δn>0.001, the flow rate increment of the second microfluidic pump is adjusted to 0.05 mol / L.

[0084] S7: Turn off the equipment, remove the workpiece and clean it.

[0085] 3. Hollow flexible glass test

[0086] Using a white light interferometer (Wyko NT9100 interferometer) to measure, the Ra value of the surface of the flexible glass workpiece processed in Example 1 is 3.2 nanometers, indicating that the processing method can obtain good surface quality. Low roughness helps to reduce light scattering and improve the optical properties of the glass.

[0087] Tested by a UV-visible spectrophotometer (PerkinElmer Lambda 950), the transmittance loss of the flexible glass workpiece processed in Example 1 at a wavelength of 550 nm was only 0.4%, indicating that processing had little effect on the light transmittance of the glass and met the requirements of optical applications.

[0088] This embodiment 1 achieves high-quality hollowing of flexible glass through dynamic compensation of base liquid and high-precision optical monitoring. Compared with comparative example 1, embodiment 1 dynamically adjusts the base liquid composition, avoids the imbalance of base liquid composition due to consumption, and effectively prevents the Newton ring phenomenon and Na + The enrichment improves the optical uniformity and stability of the glass, and has significant advantages in surface quality and optical performance.

[0089] Example 2

[0090] 1. Hollowing processing equipment

[0091] The preparation of the base liquid and lithium ion electrolyte liquid in Example 2 is the same as that in Example 1.

[0092] The hollowing processing equipment of Example 2, based on Example 1, further includes a laser supply assembly. The laser supply assembly includes a laser controller, a DPSS laser head 602, and a high-speed camera 603. The laser controller 60 is connected to the industrial computer 10. One end of the DPSS laser head 602 is connected to the laser controller 901, and the other end is fixed above the side wall of the processing tank 202 (not immersed in the electrolyte). One end of the high-speed camera 603 is electrically connected to the laser controller, and the other end is fixed above the side wall of the processing tank 202 (not immersed in the electrolyte).

[0093] The control device in the industrial computer 10 is programmed based on LabVIEW, realizing functions such as feedback of the refractive index detected by the refractive index monitoring probe spectrometer, feedback of bubble diameter data captured by the high-speed camera, and feedback of the position deviation between the center of the laser spot formed by the DPSS laser head and the discharge point. The sampling rate reaches 1kHz, and the adjustment accuracy is ±0.0005. The processing parameters can be adjusted in time according to the monitoring data.

[0094] 2. Hollowing processing steps

[0095] The hollowing method of Example 2 is based on Example 1 and further includes step S6. The DPSS laser head is started to scan the processing area of ​​the flexible glass original, and the TEOS decomposition product is deposited in the plasma area. Combined with the scanning of the DPSS laser head, the processing area is locally crystallized to form a gradient SiC x O x The transition layer. A high-speed camera generates a 3D topography image for path correction. The bubble collapse process is captured by the high-speed camera, and when the bubble diameter exceeds 50μm, the laser power is automatically increased by 10%.

[0096] In step S6, the laser scanning path spacing is set to 10 μm, and the power density gradient is from 5 W / cm 2 Gradually increase to 10W / cm 2 , and then reduced to 5W / cm 2 , scanning speed 2mm / s, three cycles, gradient annealing of the coated glass to optimize the internal structure of the material. The laser annealing unit can position the spot with an accuracy of ±1μm (such as sub-pixel interpolation) to anneal the processed glass and improve material properties.

[0097] 3. Hollow flexible glass test

[0098] Microstructural observation using FEITecnai F30TEM showed that the thickness of the transition layer was 158±12 nm, clarifying the structural characteristics of the transition layer formed after coating and annealing treatment.

[0099] Mechanical properties test: Dynamic mechanical analysis (TAQ800DMA) results showed that the loss factor tanδ decreased by 42%, indicating that after treatment, the mechanical properties of the glass material were significantly improved and the toughness was enhanced.

[0100] Example 3

[0101] 1. Hollowing processing equipment

[0102] The preparation of the base liquid and lithium ion electrolyte liquid in Example 3 is the same as that in Example 1.

[0103] The hollowing processing equipment of Example 3, based on Example 2, further includes a plasma emission spectrometer 70 connected to the industrial computer 10. The plasma emission spectrometer 70 provides a Si+ spectrum line with a detection wavelength of 288.16 nm for plasma etching depth.

[0104] 2. Hollowing processing steps

[0105] The hollowing method of Example 2 is based on Example 2 and further includes step S8: starting the plasma emission spectrometer to provide a Si+ spectrum line with a wavelength of 288.16 nm, and terminating the processing when the intensity of the Si+ 288.16 nm spectrum line decreases by 10%.

[0106] In step S8, a voltage of 60 V was used to trigger the decomposition of TEOS, and the Si+ emission peak @ 288.16 nm was detected through the plasma spectrum. The processing was continued and monitored online using XPS until the O / Si atomic ratio dropped to 1.2, achieving in-situ coating and forming a specific structural layer on the glass surface.

[0107] 3. Hollow flexible glass test

[0108] Morphology measurement: measured by Zeiss LSM900 confocal microscope, the side wall verticality is 89.2°±0.5°, indicating that the processed microhole has good shape accuracy.

[0109] Microstructure analysis: Oxford EBSD shows that the thickness of the lattice distortion layer is less than 10nm, indicating that processing has little effect on the glass lattice structure and the material structure is highly stable.

[0110] Comparative Example 1

[0111] 1. Hollowing processing equipment

[0112] The preparation of the base liquid and the lithium ion liquid is the same as that in Example 1.

[0113] Equipment assembly: The system lacks a refractive index monitoring probe spectrometer and a lithium ion liquid dynamic compensation function, making it impossible to effectively respond to changes in the optical properties of the glass during processing.

[0114] 2. Hollowing processing method

[0115] Workpiece pretreatment: As in Example 1, the flexible glass material was cleaned with Piranha solution for 10 minutes.

[0116] The hollowing method of Comparative Example 1 lacks step S5, and the other steps are the same as those of Example 1.

[0117] 3. Hollow flexible glass test

[0118] Surface observation: Using an interference microscope, Newton rings were found on the edge of the glass workpiece, indicating that the flatness and optical uniformity of the glass surface were damaged.

[0119] Elemental analysis: detected by EDS, Na + The width of the enriched zone reaches 15 μm, indicating that the imbalance of the base liquid composition affects the element distribution on the glass surface, which may have an adverse effect on the glass performance.

[0120] In Comparative Example 1, the base liquid concentration is fixed and cannot be dynamically adjusted during the processing, resulting in optical defects and abnormal element distribution in the glass workpiece.

[0121] Comparative Example 2

[0122] 1. Hollowing processing equipment

[0123] The base liquid of Comparative Example 2 does not contain TEOS, and the lithium ion liquid of Comparative Example 2 is the same as that of Example 1.

[0124] The other components of the hollowing processing equipment of Comparative Example 2 are the same as those of Example 2.

[0125] 2. Hollowing processing steps

[0126] The hollowing processing method of Comparative Example 2 is the same as that of Example 2.

[0127] 3. Hollow flexible glass test

[0128] Microstructure observation: Cross-sectional TEM observation revealed that the material underwent brittle fracture, with cracks extending along the original glass interface, indicating that the material performance had not been improved and that structural defects existed.

[0129] Mechanical properties test: The three-point bending test results show that the strength of the material is only 320MPa, which is too low to meet the requirements of high-strength applications.

[0130] Comparative Example 2 lacks TEOS in the base liquid, so no transition layer is formed and no effective modification is performed, resulting in poor material properties. However, Example 2 significantly improves material properties through innovations in base liquid composition and process, demonstrating the superiority of the technical solution of Example 2. Example 2 achieves in-situ modification and performance optimization of the glass by adding plasma emission spectrometer monitoring and laser annealing treatment. Compared with Comparative Example 2, Example 2 contains TEOS in the base liquid, which participates in the reaction to form a transition layer during processing. Combined with gradient annealing, this effectively improves material properties, avoids brittle fracture, and significantly increases the strength and toughness of the glass, showing a clear advantage in optimizing material properties.

[0131] Comparative Example 3

[0132] 1. Hollowing processing equipment

[0133] The base liquid and lithium ion liquid of Comparative Example 3 are the same as those of Example 1.

[0134] The power supply in the hollowing processing equipment of Comparative Example 3 is a DC power supply (60V), and the configuration of other components is the same as that of Example 1.

[0135] 2. Hollowing processing method

[0136] Comparative Example 3 is the same as Example 3, but because a DC power supply is used, the discharge parameters cannot be adjusted in real time to control the bubbles and the discharge gap.

[0137] 3. Hollow flexible glass test

[0138] Bubble observation: High-speed photography showed that the diameter of the bubbles exceeded 200 μm, while the diameter of the bubbles in the dual-frequency mode of Example 3 was less than 50 μm, indicating that the DC power supply could not effectively control the bubble size.

[0139] Morphology measurement: The processed hole has a distinct bell-mouth shape, and the diameter ratio of its inlet and outlet is 1:1.8, indicating that the processing accuracy is poor and cannot meet high-precision requirements.

[0140] Comparative Example 3 uses a DC power supply, which cannot effectively control the bubbles and discharge process like the dual-frequency pulse power supply of Example 3, resulting in low processing precision. The dual-frequency pulse technology of Example 3 has significant advantages in bubble control and processing precision, verifying the effectiveness of its technological innovation. Example 3 uses a dual-frequency pulse power supply and a high-speed camera to achieve precise control of bubble dynamics and optimization of the processing process. Compared with Comparative Example 3, Example 3 effectively controls the bubble size through dual-frequency pulse regulation, avoids the formation of a trumpet-mouth shape, improves the micro-hole processing precision and quality, and has obvious advantages in processing precision and structural control.

[0141] The above description is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by any technician familiar with this technical field within the technical scope disclosed by the present invention should be covered by the scope of protection of the present invention.

Claims

1. A hollowing processing device for flexible glass, characterized in that: include: Industrial computers; A feeding assembly, comprising an intelligent robotic arm gripper and a processing trough connected to the industrial computer; An electrolyte supply assembly includes a first liquid storage tank, a second liquid storage tank, a first microfluidic pump, a second microfluidic pump, and an ultrasonic mixer, wherein the first liquid storage tank stores a base liquid containing 65-75 vol% ethylene glycol, 15%-25 vol% 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide salt, 5%-10 wt% nano-silicon dioxide with a particle size of 15-25 nm, and 0.1-0.5 mol / L TEOS; the second liquid storage tank stores a lithium ion liquid, which is an ethylene glycol solution containing 1.0 mol / L lithium bis(trifluoromethanesulfonyl)imide; one end of the first microfluidic pump is connected to the first liquid storage tank via a pipeline, and the other end is connected to the ultrasonic mixer via a pipeline; one end of the second microfluidic pump is connected to the second liquid storage tank via a pipeline, and the other end is connected to the ultrasonic mixer via a pipeline; the ultrasonic mixer is connected to the inlet of the processing tank; An electric field providing component, comprising a dual-frequency pulse power supply, a tool electrode, and a counter electrode, wherein the dual-frequency pulse power supply is connected to the industrial computer, the tool electrode is connected to the positive electrode of the dual-frequency pulse power supply, and the counter electrode is connected to the negative electrode of the dual-frequency pulse power supply. The tool electrode and the counter electrode are both fixed in the processing tank and immersed in the electrolyte. The counter electrode and the tool electrode form a radially divergent electric field, and the field strength of the divergent electric field decays outward from the tool electrode. A refractive index monitoring probe spectrometer is connected to the industrial computer. The refractive index monitoring probe spectrometer includes at least one refractive index monitoring probe. The refractive index monitoring probe is fixed to the side wall of the processing groove. The refractive index monitoring probe spectrometer is controlled by the industrial computer to monitor the refractive index of the processing area of ​​the flexible glass.

2. The device according to claim 1, characterized in that Also included is a laser providing assembly; The laser providing component includes a laser controller, a DPSS laser head and a high-speed camera. The laser controller is connected to the industrial computer. One end of the DPSS laser head is connected to the laser controller and the other end is fixed to the side wall of the processing groove. The DPSS laser head outputs a 532nm laser with a spot diameter of 13 to 17 μm. The high-speed camera is connected to the laser controller. The high-speed camera receives 5% of the reflected laser through a spectrometer for real-time spot positioning.

3. The device according to claim 1, characterized in that It also includes a plasma emission spectrometer connected to the industrial computer.

4. The device according to claim 1, characterized in that The tool electrode is a needle-shaped tungsten metal body with a diameter of 49 to 51 μm and a tip cone angle of 30°; the counter electrode is a platinum ring electrode with an inner diameter of 195 to 205 μm; the tool electrode is located at the ring center of the counter electrode, and the distance between the counter electrode and the tool electrode is 73 to 77 μm, forming a radially divergent electric field.

5. A method for hollowing out flexible glass, characterized in that: include: S1: Providing the device according to any one of claims 1 to 4, fixing the flexible glass original to the end of the intelligent robotic arm gripper and inserting it into the processing tank; S2: starting the first microfluidic pump, the second microfluidic pump and the ultrasonic mixer, mixing the base liquid and the lithium ion liquid through the ultrasonic mixer to form an electrolyte, and then passing the electrolyte into the processing tank; S3: Turning on the dual-frequency pulse power supply to form a radially divergent electric field at the tip of the tool electrode, causing ions in the electrolyte to rearrange to form a double electric layer; S4: Controlling the flexible glass element to move or act in the processing tank along a preset path to change the processing position; when the processing tank drives the flexible glass element to a distance of less than 5 μm from the tool electrode, the radially divergent electric field induces ionization of the electrolyte to generate a nanoscale plasma channel; high-energy electrons in the plasma excite TEOS to decompose, generating active Si-OC free radicals, which react with Si-O bonds on the surface of the flexible glass element to achieve atomic-level etching; nano-silicon dioxide particles in the electrolyte are aggregated around the discharge channel through the dielectrophoresis effect under the action of the electric field, mechanically suppressing the diffusion of the plasma and limiting the etching area to the nanoscale; S5: The refractive index of the flexible glass element is monitored in real time by the refractive index monitoring probe spectrometer, the industrial computer obtains the refractive index data, and controls the flow rate of the second microfluidic pump according to the refractive index data so that the concentration of lithium bis(trifluoromethanesulfonyl)imide in the electrolyte is 0.1-0.5 mol / L; S7: Turn off the equipment, remove the workpiece and clean it.

6. The method according to claim 5, characterized in that The method further comprises: S6: Start the DPSS laser head to scan the processing area of ​​the flexible glass original, and the TEOS decomposition products are deposited in the plasma area. Combined with the scanning of the DPSS laser head, the processing area is locally crystallized to form; the high-speed camera generates the gradient SiC x O x 3D topography of the transition layer, used to correct the machining path.

7. The method according to claim 5, characterized in that The method further comprises: S8: Start the plasma emission spectrometer to provide a Si+ spectrum line with a wavelength of 288.16 nm, and terminate the processing when the intensity of the Si+ 288.16 nm spectrum line decreases by 10%.

8. The method according to claim 5, characterized in that The power of the ultrasonic mixer is 45-55W, so that the lithium ion liquid is evenly distributed in the mixed liquid.

9. The method according to claim 5, characterized in that In step S5, the industrial computer adjusts the flow rate of the second micro-fluidic pump according to the formula Q=0.05×Δn, wherein Δn is the refractive index deviation; When Δn>0.001, the flow rate increment of the second micro-fluidic pump is adjusted to 0.05 mol / L.

10. The method according to claim 6, characterized in that In step S6, the bubble collapse process is also captured by the high-speed camera, and when the bubble diameter is greater than 50 μm, the laser power is triggered to increase by 10%.

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