CN1547079A - Quasi-molecule laser electrochemical microstructure manufacturing method and equipment - Google Patents
Quasi-molecule laser electrochemical microstructure manufacturing method and equipment Download PDFInfo
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Abstract
The invention belongs to micro manufacturing field, pointing to the deficiency of traditional method, the quasimolecule laser, integrated circuit producing and etching, electric chemical and scanning probe micro technology are integrated together into a new process method. The steps are: (1) produces micro probe array at first; (2) the base is fixed between the plane electrode and the micro probe array, generates the negative voltage, pours in the protection gas; (3) adds in voltage between the two polars after pouring the electrolyte liquid, at the same time, the quasimolecule laser are poured in to control the electrochemical reaction, completes the process. the correspondent device sets an electrochemical reaction room on the laser microprocess machine platform, it includes a laser air moving window, an inlet of protection air, a vacuum pump interface, an electrolyte liquid inlet, a microprobe array, a plane electrode, an assistant electrochemical reaction air inlet and the waste outlet. The invention can acquires microstructure with width-depth ratio 5-50, the character size 1-50 micro meter on the semiconductor base.
Description
Technical field
The invention belongs to the little manufacturing field in the manufacturing technology, relate to integrated circuit plate-making photoetching, excimer laser processing and electrochemical machining process method.
Background technology
Existing little manufacture method generally adopts photoetching process gluing on substrate to make micro structured pattern, makes three-dimensional microstructures with the chemical micro fabrication of chemical micro fabrication or induced with laser again.Yet, because the vertical corrosion depth of microstructure that chemical micro fabrication forms equates (depth-to-width ratio is 1) substantially with the lateral encroaching width, thereby be difficult to make that vertical degree of depth is big, the less microstructure of transverse width, and unnecessary " lateral encroaching problem " appear easily.The lateral encroaching influence that the chemical micro fabrication of induced with laser can reduce to be harmful to improves the microstructure depth-to-width ratio, but adopts CO2 laser instrument (10.6 micron wave length) or Ar usually
+Laser instrument (as 488 nanometers) is as light source, and because of being subjected to the restriction of optical maser wavelength, often difficulty tackles the problem at its root.
Compare with chemical micro fabrication, the micro-machined temperature of galvanochemistry is lower, little to the sample characteristics of for example damage, processing speed can improve several times, and it is less to the damage ratio of environment, particularly between electrode, apply the electric field of assisted electrochemical reaction, can make depth-to-width ratio improve several times, and can effectively control micro-machined vertical degree of depth and transverse width
[2]People such as M.Datta are obtaining bigger progress aspect the little processing of galvanochemistry, and IBM Corporation obtained 3 related U.S. patent thus in 1996.The R.Schuster research group of Germany and France's cooperation applies ultrashort pulse voltage, available galvanochemistry micro fabrication machining 3 D conductive material between tool-electrode and workpiece to be machined.
Laser Micro-Machining is the clean manufacturing technology of a kind of numerical control, and technological parameter can accurately be controlled, and is easy and simple to handle, also very little to the pollution of environment.The J.Brannon of IBM Corporation in 1997 adopt the operating room of vacuum-pumping, injection reacting gas, explore excimer laser and melt (Ablation) technology and etching technics.People such as the marine systems research centre S.D.Russell of USN invent and a kind ofly are applicable to that the excimer laser under halocarbon (halocarbon) atmospheric condition induces chemical etching technology, obtain three corresponding US power 1994 and nineteen ninety-five respectively by USN.
In the later stage nineties, people begin to utilize catalysis and the control action of laser to electrochemical reaction, explore the new technology that Laser Micro-Machining technology combines with the galvanochemistry micro fabrication.IBM Corporation succeeds in developing a kind of little manufacturing process of galvanochemistry of laser enhancing photo-thermal process, obtains to use in spraying plating and etching process.P.A.Kohl furthers investigate distribution of space charge state on semiconductor/electrolyte solution interface and charge carrier current density in the process of research optical semiconductor electrochemical etching technology.California, USA university strengthens oxidation, reduction reaction in the electrochemical reaction cell with 4.5 milliwatts, 442 nanometer HeCd laser instruments, be made into temperature with potassium hydroxide or hydrochloric acid and water and be lower than 40 ℃ electrolyte solution, make the order of magnitude of III group-III nitride (as gallium nitride) film etch rate reach 10 nm/min～100 nm/min, obtained United States Patent (USP) and weigh in 1998.
Little manufacturing process has also obtained bigger progress at home over nearly 10 years.People such as Xiamen University's Tian Zhaowu propose to study a kind of MEMS galvanochemistry micro-processing technology, and with the Harbin Institute of Technology cooperation research and development go out galvanochemistry little/receive system of processing.People such as Yang Yong, Lin Zugeng is used for electrochemical research with nonlinear optics, research laser scanning Optical Electro-Chemistry microtechnic.People such as Beijing University of Technology's left side iron bracelet develop domestic first little processing machine of practical excimer laser that has the even device of two-stage compound eye type laser beam shaping, adopt corrosivity reacting gas (as chlorine) to carry out excimer laser and induce the chemical etching machining experiment, manufacture experimently out multiple three-dimensional microstructures sample.The electrochemical fine machining method that the Zhang Haijun of Zhejiang University, Huang Feng proposition is led microscopy based on the scan ion electricity.In addition, a kind of new method of carrying out the integrated circuit microfabrication based on scanning tunnel microscopy and electrochemical techniques, with kapillary microprobe (in most advanced and sophisticated the order of magnitude of external diameter from sub-micron to tens micron) is also proposed.Institute of Chemistry, Academia Sinica ten thousand upright fine horses, Wang Chen, Bai Chunli are studying the galvanochemistry scanning probe microscopy that the electrochemical research system combines with scanning probe microscopy.
In sum, the galvanochemistry micro fabrication is compared with chemical micro fabrication, and orientable control etching size obtains bigger depth-to-width ratio.Yet, the micro-machined tool-electrode manufacturing cost of galvanochemistry is higher, pollution problem to environment just makes moderate progress than chemical little processing, but also there is bigger problem of environmental pollution, and be easy to generate technological problemses such as passivating film, hinder or delay carrying out smoothly of the little process of galvanochemistry, cause the micro-machined production efficiency of galvanochemistry also not high, thereby be difficult on production line, generally promote.Existing induced with laser galvanochemistry micro fabrication can partly solve the harmful passivation film problem in the electrochemical reaction process.But, the laser wavelength that existing induced with laser galvanochemistry micro fabrication uses is grown (as 1.06 microns or 442 nanometers), the also difficult yardstick that reaches the sub-micron order of magnitude of power less (as 4.5 milliwatts), machinable characteristic dimension, and the scope of using is also very limited.For example, the patented technology of California, USA university only is applicable to the etching of III group-III nitride (as gallium nitride) film, and is also powerless to the sub-micron processing of other materials.
Summary of the invention
The invention provides a kind of excimer laser galvanochemistry method for manufacturing microstructure and device thereof, make a plate photoetching process, excimer laser micro fabrication, galvanochemistry micro fabrication and scanning probe microscopy of integrated circuit combined, and overcome the problem that they exist separately, form a kind of new excimer laser method for electrochemical machining.
A kind of excimer laser galvanochemistry method for manufacturing microstructure of the present invention, order comprises the steps:
(1) at first prepares the microprobe array: on quartz glass plate, generate metal level with chemical method or electrochemical method, layer on surface of metal coating photoresist, with integrated circuit sub-micron mask-making technology in photoresist copying surface micro structured pattern to be processed, carry out corrosion treatment again after the photoetching treatment, remove photoresist promptly;
(2) substrate to be processed is fixed in the indoor plate electrode of electrochemical reaction, the microprobe array is put in its top, makes electrochemical reaction room produce negative pressure with vacuum pump, the window blanket gas that reinjects forms the gas shield barrier at the window lower surface;
(3) inject electrolyte solution, make the upper surface of substrate just immerse electrolytic solution, between microprobe array and plate electrode, apply voltage then, feed excimer laser through the electrochemical reaction chamber window simultaneously, control electrochemical reaction, finish little process of microstructure substrate.
Described excimer laser galvanochemistry method for manufacturing microstructure, the technological parameter that adopts is: excimer laser wavelength 193 nanometers or 248 nanometers, pulse energy≤450 milli Jiao, 12～20 nanoseconds of pulse width, number of pulses 10-3000, pulse repetition rate≤200 hertz, electrolyte solution acid-base solution, supply voltage is that 3-15V, electrode separation are 0.2-2mm.
Described excimer laser galvanochemistry method for manufacturing microstructure, described electrolyte solution can also adopt the 5%-30% salt solusion for metal material for the KOH solution of 10%-40% or the HCl solution of 10%-40%.
A kind of device that excimer laser galvanochemistry microstructure is made that is used for of the present invention, comprise the little processing machine of excimer laser that constitutes by excimer laser, optical system and X-Y diaxon worktable, it is characterized in that: on the little processing machine X-Y of the described excimer laser diaxon worktable, electrochemical reaction room is housed, its surface equipment Pneumatic air adjusting, gas atmosphere inlet, vacuum pump interface, electrolyte solution inlet, assisted electrochemical reaction gas inlet and Waste outlet; The electrochemical reaction chamber interior microprobe array is housed and have the plate electrode of anchor clamps, they are connected to form electrode pair with the two ends of power supply respectively.
The described device that is used for the manufacturing of excimer laser galvanochemistry microstructure, described microprobe array tie up to generate on the quartz glass plate metal level, and the layer on surface of metal shape is identical with micro structured pattern to be processed; Distance can be finely tuned between microprobe array and the plate electrode.
The present invention substitutes the long laser instrument of HeCd laser instrument equiwavelength with 248 nanometers (or 193 nanometers or 157 nanometers) excimer laser, the advantage of integrated circuit plate-making photoetching process, excimer laser micro fabrication, galvanochemistry micro fabrication and scanning probe microscopy is organically combined, and these four kinds of existing micro-fabrication technologies are replenished mutually.Compare with Deep Reaction ion etching (DRIE) technology, it is cheap relatively that the little manufacturing process of excimer laser galvanochemistry has equipment cost, can eliminate the damage problem of DRIE technology energetic ion to sample again.Outstanding feature of the present invention is to adopt quartz base plate manufacturing and the corresponding microprobe array of processing graphic pattern; The microprobe array is one of electrode of electrochemical reaction, also is the optical waveguide of excimer laser.Excimer laser is passed the space in the middle of the microprobe array, be radiated at processed surface of the work, like this, under the interaction of excimer laser, electrochemical reaction and substrate surface atom, can on substrate, produce depth-to-width ratio and be 5～50, characteristic dimension is 0.5～50 micron microstructure.The present invention applicable to metal, semiconductor, etc. the little processing of sub-micron of material, environment is not being had substantially finish little process under the condition of polluting, improve the depth-to-width ratio of microstructure, inject new vitality for the little manufacturing process of MEMS.Because the quasi-molecule laser pulse energy is absorbed by electrolyte solution easily, thereby triggers, activates electrochemical reaction apace.As long as the electrochemical reaction room (as shown in Figure 2) of self-loopa is installed on the little processing machine worktable of excimer laser, then can use electrolyte (as neutral salt such as NaNO3, K2SO4 or the NaCl) solution of lower concentration, the electrochemical reaction that excimer laser triggers takes place under lower temperature, produces needed three-dimensional microstructures on the silicon chip specimen material.Obviously, adopt the neutral salt electrolyte solution of low concentration in technological process, can reduce environmental pollution, reaching clean the manufacturing is the purpose of green manufacturing; Low temperature laser electrochemical reaction can reduce the influence that process for making causes sample characteristics of for example to change.In above-mentioned new technology process, if constantly replenish fresh electrolyte solution, the discharging waste liquid, processing effect will be better.Because this new technology makes full use of the interaction of excimer laser, electrochemical reaction and specimen material, can solve on the one hand problem of passivation in the little process of galvanochemistry and the non-volatile product problem in the Laser Micro-Machining process, strictly control the electrochemical reaction process that laser triggers, accurately control the vertical degree of depth and the transverse width of silicon chip sample microstructure; Can directly use the original hot spot (as 12 millimeters * 24 millimeters) of excimer laser on the other hand again, perhaps adopt beam expander (a kind of optical devices that enlarge hot spot) to obtain bigger hot spot, sample surfaces is scanned, improve disposable machinable region area.
Description of drawings
Fig. 1 is that the present invention is used for the device synoptic diagram that excimer laser galvanochemistry microstructure is made.
Fig. 2 is the electrochemical reaction room structural representation.
Fig. 3 is the synoptic diagram of microprobe array annexation in electrochemical reaction room.
Fig. 4 is the manufacturing process synoptic diagram of microprobe array.
Fig. 5 is that microprobe array A is to view.
Embodiment
Of the present inventionly a kind ofly be used for device that excimer laser galvanochemistry microstructure makes as shown in Figure 1, comprise the little processing machine of excimer laser that constitutes by excimer laser 1, optical system and X-Y diaxon worktable, optical system comprises catoptron 2,3,4,5,6,7,8 and lens 9, X-Y diaxon worktable comprise X to worktable 10 and Y to worktable 11; Can on the little processing machine worktable of existing excimer laser, the electrochemical reaction room 13 in charged source 12 be housed.
Fig. 2 is the structural representation of electrochemical reaction room 13, it comprises parts such as Pneumatic air adjusting 14, gas atmosphere inlet 15, vacuum pump interface 16, electrolyte solution inlet 17, assisted electrochemical reaction gas inlet 18 and Waste outlet 19, gas atmosphere inlet 15, assisted electrochemical reacting gas 18 link to each other with corresponding source of the gas, vacuum pump interface 16 links to each other with vacuum pump, and electrolyte solution inlet 17 links to each other with electrolyte solution preparation container; Electrochemical reaction room 13 inside microprobe array 20 is housed and have the plate electrode 21 of anchor clamps, they are connected to form electrode pair with the two ends of power supply 12 respectively.Microprobe array 20 can be finely tuned with relative vertically (Z direction) distance between the plate electrode 21.Electrochemical reaction room 13 is fixed together with work on hand platform 10, can move horizontally in the X-Y direction with worktable.The characteristics of this electrochemical reaction room have: may command Laser Micro-Machining technological parameter; The prescription of scalable electrolyte solution, flow velocity and flow; Prescription, flow velocity and the flow of scalable laser Pneumatic air adjusting blanket gas and assisted reaction gas; Distance between probe array electrode and the plate electrode can be finely tuned; At substrate/electrolyte solution interface, the interaction between excimer laser photon, excimer laser plasma, electrochemical reaction generation microscopic particle and the matrix atom can take place.
Fig. 3 is the synoptic diagram of microprobe array annexation in electrochemical reaction room, microprobe array 20 is loaded on the support 22, support 22 is fixed in the cover plate 24 of electrochemical reaction room and regulates its vertical direction position by setting nut 25 by four adjusting screw(rod)s 23, thereby regulate relative vertical (Z direction) distance between microprobe array 20 and the plate electrode 21, add man-hour substrate P to be processed and plate electrode 21 fixing, laser passes the gap of window 14, probe array 20, incides substrate P to be processed surface.
Prepare the microprobe array with little manufacturing process, its process as shown in Figure 4.Go up with chemical method or electrochemical method generation layer of metal layer 20-2 (shown in Fig. 4 .b) at synthetic quartz glass sheet 20-1 (shown in Fig. 4 .a), apply one deck photoresist 20-3 (shown in Fig. 4 .c) at layer on surface of metal then, again it is carried out photoetching treatment, obtain the figure shown in Fig. 4 .d, again it is carried out corrosion treatment, obtain the figure shown in Fig. 4 .e, remove photoresist 3 at last, can obtain the microprobe array 20-4 shown in Fig. 4 .f.
Fig. 5 be the microprobe array A shown in Fig. 4 .f to view, be microwell array, consistent with the micro structured pattern of needs processing.
Embodiment 1: the processing of metal micro-holes array
At first adopt the method for chemogenic deposit to form the layer of copper conductive layer at glass surface, then, on the copper conductive layer, be coated with photoresist, then, adopt photoetching technique with figure transfer to photoresist, then, it is carried out dry etching, and removal photoresist, the glass sheet that has the copper conductive layer that will constitute the microprobe array again is installed in the negative electrode position in the laser electrochemical reaction room, makes the copper layer down, and connects with cathode terminal wherein, work metal copper base material places anode position, and connects by plate electrode and anode terminal wherein.Electrode separation is 0.2mm, and electrolytic solution adopts 5% NaCl solution, and liquid level is fallen into oblivion workpiece 1mm, and supply voltage is 12V, and it is 248 nanometers that excimer laser adopts wavelength, pulse energy 300mJ, and umber of pulse is 50.Can etch spacing on the metallic copper base material of thick about 1mm through 2 minutes is 15 microns, and diameter is 0.5 micron a microwell array.
Embodiment 2: the processing of metal micro-holes array
The microprobe array is made and the same example is installed.Electrode separation is 2mm, and electrolytic solution adopts 30% NaCl solution, and liquid level is fallen into oblivion workpiece 2.5mm, and supply voltage is 3V, and it is 248 nanometers that excimer laser adopts wavelength, pulse energy 100mJ, and umber of pulse is 1000.Promptly etching spacing on the metallic copper base material of thick about 0.5mm through 1 minute is 15 microns, and diameter is 5 microns a microwell array.
Embodiment 3: the processing of metal micro-holes array
The microprobe array is made and the same example is installed.Electrode separation is 2mm, and electrolytic solution adopts 10% NaCl solution, and liquid level is fallen into oblivion workpiece 2.5mm, and supply voltage is 6V, and it is 248 nanometers that excimer laser adopts wavelength, pulse energy 250mJ, and umber of pulse is 500.Promptly etching spacing through 1 minute on the stainless steel substrate of thick about 0.5mm is 50 microns, and diameter is 50 microns a microwell array.
Embodiment 4: the processing of metal micro-holes array
The microprobe array is made and the same example is installed.Electrode separation is 2mm, and electrolytic solution adopts 10% NaCl solution, and liquid level is fallen into oblivion workpiece 2.5mm, and supply voltage is 6V, and it is 193 nanometers that excimer laser adopts wavelength, pulse energy 250mJ, and umber of pulse is 500.Promptly etching spacing through 1 minute on the stainless steel substrate of thick about 0.5mm is 15 microns, and diameter is 5 microns a microwell array.
Embodiment 5: the processing of semiconductor micropore array
At first adopt the method for chemogenic deposit to form one deck gold or silver conductive layer at glass surface, then, on conductive layer, be coated with photoresist, then, adopt photoetching technique with figure transfer to photoresist, then, it is carried out dry etching, and removal photoresist, the glass sheet that has conductive layer that will constitute the microprobe array again is installed in the negative electrode position in the laser electrochemical reaction room, makes conductive layer down, and connects with cathode terminal wherein, processed silicon chip places anode position, and connects by plate electrode and anode terminal wherein.Electrode separation is 0.2mm, and electrolytic solution adopts 10% HCl solution, and liquid level is fallen into oblivion workpiece 1mm, and supply voltage is 12V, and it is 248 nanometers that excimer laser adopts wavelength, pulse energy 400mJ, and umber of pulse is 1500.Promptly etching spacing through 10 minutes on the silicon chip of thick about 0.5mm is 15 microns, and diameter is 0.5 micron a microwell array.
Embodiment 6: the processing of semiconductor micropore array
The microprobe array is made and the same example is installed.Electrode separation is 2mm, and electrolytic solution adopts 30% NaOH solution, and liquid level is fallen into oblivion workpiece 2.5mm, and supply voltage is 6V, and it is 248 nanometers that excimer laser adopts wavelength, pulse energy 100mJ, and umber of pulse is 3000.Promptly etching spacing through 20 minutes on the silicon chip of thick about 0.5mm is 15 microns, and diameter is 1 micron a microwell array.
Embodiment 7: the processing of semiconductor micropore array
The microprobe array is made and the same example is installed.Electrode separation is 2mm, and electrolytic solution adopts 30% HCl solution, and liquid level is fallen into oblivion workpiece 2.5mm, and supply voltage is 6V, and it is 248 nanometers that excimer laser adopts wavelength, pulse energy 100mJ, and umber of pulse is 3000.Promptly etching spacing through 20 minutes on the silicon chip of thick about 0.5mm is 15 microns, and diameter is 5 microns a microwell array.
Embodiment 8: the processing of semiconductor micropore array
The microprobe array is made and the same example is installed.Electrode separation is 2mm, and electrolytic solution adopts 10% HCl solution, and liquid level is fallen into oblivion workpiece 2.5mm, and supply voltage is 6V, and it is 193 nanometers that excimer laser adopts wavelength, pulse energy 100mJ, and umber of pulse is 3000.Promptly etching spacing through 20 minutes on the silicon chip of thick about 0.5mm is 15 microns, and diameter is 1 micron a microwell array.
Claims (5)
1. an excimer laser galvanochemistry method for manufacturing microstructure comprises the steps: in proper order
(1) at first prepares the microprobe array: on quartz glass plate, generate metal level with chemical method or electrochemical method, layer on surface of metal coating photoresist, with integrated circuit sub-micron mask-making technology in photoresist copying surface micro structured pattern, carry out corrosion treatment again after the photoetching treatment, remove photoresist promptly;
(2) substrate to be processed is fixed in the indoor plate electrode of electrochemical reaction, the microprobe array is put in its top, makes electrochemical reaction room produce negative pressure with vacuum pump, the window blanket gas that reinjects forms the gas shield barrier at the window lower surface;
(3) inject electrolyte solution, make the upper surface of substrate just immerse electrolytic solution, between microprobe array and plate electrode, apply voltage then, feed excimer laser through the electrochemical reaction room Pneumatic air adjusting simultaneously, control electrochemical reaction, finish little process of microstructure substrate.
2. excimer laser galvanochemistry method for manufacturing microstructure as claimed in claim 1, it is characterized in that the technological parameter that adopts is: excimer laser wavelength 193 nanometers or 248 nanometers, pulse energy≤450 milli Jiao, 12～20 nanoseconds of pulse width, number of pulses 10-3000, pulse repetition rate≤200 hertz, electrolyte solution are acid-base solution, and supply voltage is that 3-15V, electrode separation are 0.2-2mm.
3. excimer laser galvanochemistry method for manufacturing microstructure as claimed in claim 1 or 2 is characterized in that described electrolyte solution is the KOH solution of 10%-40% or the HCl solution of 10%-40%, can also adopt the 5%-30% salt solusion for metal material.
4. one kind is used for the device that excimer laser galvanochemistry microstructure is made, comprise the little processing machine of excimer laser that constitutes by excimer laser, optical system and X-Y diaxon worktable, it is characterized in that: on the little processing machine X-Y of the described excimer laser diaxon worktable, electrochemical reaction room is housed, its surface equipment Pneumatic air adjusting, gas atmosphere inlet, vacuum pump interface, electrolyte solution inlet, assisted electrochemical reaction gas inlet and Waste outlet; The electrochemical reaction chamber interior microprobe array is housed and have the plate electrode of anchor clamps, they are connected to form electrode pair with the two ends of the pulse power respectively.
5. the device that is used for the manufacturing of excimer laser galvanochemistry microstructure as claimed in claim 4 is characterized in that: described microprobe array ties up to generate on the quartz glass plate metal level, and the layer on surface of metal shape is identical with micro structured pattern to be processed; Distance can be finely tuned between microprobe array and the plate electrode.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101511525B (en) * | 2006-07-13 | 2011-11-30 | 邦及奥卢夫森公司 | Combined electrochemical and laser micromachining process for creating ultra-thin surfaces |
| CN102324447A (en) * | 2011-09-19 | 2012-01-18 | 南通大学 | Method and device for preparing polycrystalline silicon solar cell texture |
| CN103706901A (en) * | 2013-12-30 | 2014-04-09 | 江苏大学 | Method and device for machining micro annular grooves through hollow laser and electrolysis in combined mode |
| CN105206553A (en) * | 2015-08-28 | 2015-12-30 | 京东方科技集团股份有限公司 | Etching device, etching method of electric conduction layer and preparation method of array substrate |
-
2003
- 2003-12-12 CN CN 200310111573 patent/CN1259598C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101511525B (en) * | 2006-07-13 | 2011-11-30 | 邦及奥卢夫森公司 | Combined electrochemical and laser micromachining process for creating ultra-thin surfaces |
| CN102324447A (en) * | 2011-09-19 | 2012-01-18 | 南通大学 | Method and device for preparing polycrystalline silicon solar cell texture |
| CN102324447B (en) * | 2011-09-19 | 2013-03-27 | 南通大学 | Method and device for preparing polycrystalline silicon solar cell texture |
| CN103706901A (en) * | 2013-12-30 | 2014-04-09 | 江苏大学 | Method and device for machining micro annular grooves through hollow laser and electrolysis in combined mode |
| CN103706901B (en) * | 2013-12-30 | 2016-03-02 | 江苏大学 | A kind of hollow laser combines the method and apparatus processing miniature annular groove with electrolysis |
| CN105206553A (en) * | 2015-08-28 | 2015-12-30 | 京东方科技集团股份有限公司 | Etching device, etching method of electric conduction layer and preparation method of array substrate |
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