CN104909335A - Preparation method of high depth to width ratio micro electric spark array electrode - Google Patents

Preparation method of high depth to width ratio micro electric spark array electrode Download PDF

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CN104909335A
CN104909335A CN201510209963.7A CN201510209963A CN104909335A CN 104909335 A CN104909335 A CN 104909335A CN 201510209963 A CN201510209963 A CN 201510209963A CN 104909335 A CN104909335 A CN 104909335A
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micro
tungsten
electrode
electroforming
tungsten substrate
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CN104909335B (en
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陈兢
陈献
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Peking University
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Suzhou Is Containing Light Micro-Nano Science And Technology Ltd
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Abstract

The invention relates to a preparation method of a high depth to width ratio micro electric spark array electrode, the method comprises the following steps: making a protective layer, an adhesive layer and an electroformed seed layer on the back side of a tungsten substrate, and making a hard mask on the front side of the tungsten substrate; coating the hard mask with a photoresist, and exposing and developing, then etching the hard mask to realize mask graphical transfer, and coating the surface with a photoresist protective layer; using the seed layer for electroforming on the back side of the tungsten substrate for formation of a micro electrode supporting structure, preferably using UV-LIGA process for the preparation of the supporting structure; removing the photoresist protective layer on the front side of the tungsten substrate, and using plasma deep etching method for preparation of a tungsten microelectrode; removing the hard mask on the front side of the tungsten substrate and the excess protective layer, adhesive layer and seed layer on the back side of the tungsten substrate to obtain the high depth to width ratio micro electrode comprising the tungsten microelectrode and the micro electrode supporting structure. The actual depth of the micro electrode can be increased by the method, the tungsten electrode is fully used, and the depth width ratio of micro electric spark processing is improved.

Description

A kind of preparation method of high depth-to-width ratio micro electric spark array electrode
Technical field
The invention belongs to Micro-EDM Machining Technology field, be specifically related to a kind of preparation method of high depth-to-width ratio micro electric spark array electrode.
Background technology
Micro EDM (Micro-EDM) has noncontact processing, is easy to the features such as control without obvious macroscopical active force and discharge energy, be particularly suitable for the difficulty processing conductive material of various high rigidity, high strength, high-wearing feature and corrosion resistance (as stainless steel, carbide alloy etc.) microfabrication, play a significant role in the processing of micro rod, minute aperture and complicated micro-structure.
But the preparation of micro-electrode is the key factor of restriction fine electric spark technical development always.Adopt traditional wire electrode EDM Grinding technology (WEDG), the micro-electrode that diameter is 5 to 300 μm can be prepared.But thisly utilize unipolar serial processing mode efficiency very low, in the independent preparation process of electrode, its uniformity is difficult to ensure, therefore machining accuracy is very limited.
For the problems referred to above, people propose fine electric spark batch machining technology (Batch mode micro-EDM), and its main feature utilizes array electrode to realize fine electric spark parallel fabrication, improve working (machining) efficiency.Wherein, Electric Discharge Wire-cutting Technology (WEDM) can prepare square array electrode, but cannot realize the electrode machining of arbitrary shape, and therefore, this technology range of application is very limited.And utilize the LIGA technique of photoetching technique, can prepare the array electrode of arbitrary shape, in addition, the application of synchrotron radiation X-ray can realize high-aspect-ratio electroplated structural.But the electrode material of plating processing is limited, and based on nickel and copper, its fusing point is lower; And due to the restriction of electroplating technology self and the non-uniform Distribution of electric field, it is more loose that its material behavior of structure that plating obtains compares hot worked metallic body materials, and be difficult to avoid the defects such as cavity.In micro EDM process, not only loss is very large to electroplate the tool-electrode obtained, and easily deformation occurs, and has a strong impact on machining accuracy.
Summary of the invention
For the problems referred to above, the present invention proposes a kind of preparation method of high depth-to-width ratio micro electric spark array electrode, utilize dual surface lithography technology, plasma deep etching definition micro-electrode figure is adopted in tungsten substrate front, UV-LIGA technique (Ultraviolet-Lithographie Galvanoformung Abformung) is preferably utilized at tungsten substrate back, preparation has the supporting construction of high-aspect-ratio, to increase the actual grade of micro-electrode, and then make full use of tungsten electrode, improve the depth-to-width ratio of micro EDM.
For achieving the above object, the technical solution used in the present invention is as follows:
A preparation method for high depth-to-width ratio micro electric spark array electrode, its step comprises:
1) Seed Layer of protective layer, adhesion layer and electroforming is made successively at the back side of tungsten substrate;
2) the hard mask of tungsten etching is made in tungsten substrate front;
3) on hard mask, apply photoresist and exposure imaging, complete the graphical of photoresist;
4) hard mask is etched to realize the transfer of mask pattern, and at surface coating photoresist as protective layer;
5) utilize described Seed Layer to carry out electroforming at tungsten substrate back, form micro-electrode supporting construction;
6) remove the photoresist protective layer in tungsten substrate front, adopt plasma deep etching method to prepare tungsten micro-electrode;
7) remove the hard mask in tungsten substrate front and unnecessary protective layer, adhesion layer and the Seed Layer of tungsten substrate back, obtain the high depth-to-width ratio micro electrode be made up of tungsten micro-electrode and micro-electrode supporting construction.
Further, step 1) in, the material of described protective layer is Al, AlN, Cr, Ni etc., and thickness is 0.5 ~ 2 μm; The material of described adhesion layer is Ti, TiW, Au, Co, Ta etc., and thickness is 50 ~ 200nm, and the material of described Seed Layer is consistent with electroforming material, and as Cu etc., thickness is 100 ~ 500nm.
Further, step 2) in, the material of described hard mask is Al, AlN, Cr, Ni etc., and thickness is 2 ~ 5 μm.
Further, step 5) preferably adopt UV-LIGA technique to prepare micro-electrode supporting construction, LIGA technique also can be adopted in addition to prepare this supporting construction, but LIGA process costs is higher.The step that employing UV-LIGA technique prepares micro-electrode supporting construction is as follows:
A) adopt injecting type gluing method to be coated with SU-8 glue to tungsten substrate, obtain smooth glued membrane, then carry out front baking, after completing, taking-up tungsten substrate, is placed to room temperature;
B) adopt the method for dual surface lithography, realization is aimed at tungsten substrate front description, and the mode that after exposure, utilization heats up gradually carries out rear baking, carries out ultrasonic development after being cooled to room temperature;
C) adopt corresponding electroforming solution to carry out electroforming according to the difference of electroforming material, then utilize chemically mechanical polishing by electroforming material surface attenuated polishing, form micro-electrode supporting construction.
Further, step a) in the thickness of SU-8 glue be 0.1 ~ 1.5mm, the substrate coating SU-8 glue is placed on the glue evenning table of leveling, relies on SU-8 glue obtaining smooth glued membrane higher than the mobility had during its glass transition temperature; The temperature of described front baking is 80 ~ 120 DEG C, and the time is 5 ~ 20h.
Further, step b) mode that heats up gradually of described utilization carries out rear baking, and be first slowly be warming up to 50 ~ 70 DEG C by room temperature, keep 5 ~ 20min, be then warming up to 90 ~ 95 DEG C, keep 30 ~ 60min, then naturally cool to room temperature.
Further, step c) in electroforming material can be copper, nickel, gold, silver, iron, iron-nickel alloy etc.For copper electroforming, conventional copper plating solution has hydrosulphate plating solution, cyanide bath and pyrophosphate plating solution; For electroformed nickel, conventional electroforming solution has nickel sulfamic acid, nickelous sulfate, nickel chloride and its mixed solution.Electroforming temperature is set as 10 ~ 60 DEG C, and current density is 100 ~ 500A/m 2.
Further, utilize microwave plasma body method removal step 5) in SU-8 glue, to discharge supporting construction.Preferably, the reacting gas that described microwave plasma body method adopts is CF 4and O 2.
Compared with prior art, beneficial effect of the present invention is as follows:
(1) utilize UV-LIGA technique to prepare supporting construction for tungsten electrode, improve the physical length of micro-electrode, and in micro EDM process, electroforming supporting construction participates in pulsed discharge hardly, does not therefore affect machining accuracy.Meanwhile, in the continuous feeding of micro-electrode, make full use of the advantage of tungsten electrode low-loss rate, improve the depth-to-width ratio of micro EDM;
(2) the supporting construction size that prepared by UV-LIGA can be smaller than tungsten electrode, and bottom space is comparatively large, is conducive to the eliminating of galvanic corrosion product in electric discharge machining process, thus improve the efficiency and precision of microfabrication;
(3) compared with tungsten direct etching high depth-to-width ratio micro electrode, the method working (machining) efficiency is high, and there will not be metal mask adhesiveness and verticality of side wall to be deteriorated, and the problem such as horizontal undercutting is serious.
Accompanying drawing explanation
Fig. 1 is that tungsten substrate back sputtered aluminum crosses the schematic diagram carving protective layer, adhesion layer and copper seed layer.
Fig. 2 is the schematic diagram of tungsten substrate front sputtering Al.
Fig. 3 is the schematic diagram carrying out photoetching and etch aluminium.
Fig. 4 is the schematic diagram of the SU-8 glue at front Coating glue protect and the back side.
Fig. 5 is the schematic diagram of SU-8 glue exposure imaging.
Fig. 6 is the schematic diagram of copper electroforming.
Fig. 7 removes photoresist and etch the schematic diagram of tungsten electrode in front.
Fig. 8 is that wet etching goes aluminium to cross the schematic diagram carving protective layer, adhesion layer and Seed Layer.
Fig. 9 removes the schematic diagram that SU-8 glued membrane obtains high depth-to-width ratio micro electrode.
Detailed description of the invention
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, and below by specific embodiments and the drawings, the present invention will be further described.
The preparation method of the high depth-to-width ratio micro electric spark array electrode of the present embodiment, specifically comprises the steps:
1. select thickness to be 4 cun of tungsten substrates of 200 μm of twin polishings, successively through watery hydrochloric acid, NaOH solution, acetone and washed with de-ionized water, ensure that tungsten substrate surface does not have impurities left.Then put into vacuum drying oven baking, remove substrate surface moisture.
2. as shown in Figure 1; at the aluminium film that the back spatter thickness of tungsten substrate 1 is 1 μm, as the barrier layer (i.e. protective layer) 2 of tungsten over etching, sputter the thick Ti of 100nm afterwards again as adhesion layer 3; then the thick Cu of 300nm is sputtered, as the Seed Layer 4 of electro-coppering.
3. sputter the hard mask 5 that 4 μm of thick Al etch as tungsten in the front of tungsten substrate 1, meet the requirement (as Fig. 2) of the degree of depth 200 μm of tungsten electrodes.Afterwards, aluminium mask applies photoresist, as the mask of etching aluminium.Then exposure imaging, completes the graphical of photoresist, then adopts dry etching metallic aluminium, realizes the transfer of mask pattern, finally at surface coating photoresist, as protective layer 6 (as Fig. 3, Fig. 4).
4. utilize UV-LIGA technique to prepare micro-electrode supporting construction at tungsten substrate back, concrete steps are as follows:
A () be glue and front baking: adopt injecting type gluing method to obtain the SU-8 glue 7 that thickness is 1.2mm.Then glue-coated substrate is placed on the glue evenning table of leveling, because SU-8 glue is higher than its glass transition temperature T gtime (55 DEG C), there is good mobility, rely on the mobility of himself can obtain smooth glued membrane, front baking 12h under 110 DEG C of conditions; then tungsten substrate is taken out; be placed to room temperature (as Fig. 4, its front Coating glue protect 6, the back side is SU-8 glue 7).
B () exposes, rear baking and development: the method adopting dual surface lithography, realization is aimed at tungsten substrate front description, the mode that after exposure, utilization heats up gradually carries out rear baking, first slowly be warming up to 60 DEG C by room temperature, keep 10min, be then warming up to 90 DEG C, keep 30min, then naturally cool to room temperature.Adopt ultrasonic development, assisting ultrasonic vibration 30min, then uses isopropyl alcohol (IPA) to clean, finally with after washed with de-ionized water, and post bake 15min (as Fig. 5) at 150 DEG C.
(c) micro-electroforming: adopt CuSO 4and H 2sO 4the electroforming solution of composition carries out electroforming Cu, and electroforming temperature is set as 35 DEG C, and current density is 200A/m 2, then utilize chemically mechanical polishing (CMP) by electroforming Cu surface attenuated polishing (as Fig. 6, wherein 8 is electroforming material).
5. in tungsten substrate front surface, first utilize acetone to remove the photoresist protective layer of aluminium mask surface, then utilize aluminium as mask, adopt plasma deep etching method to prepare tungsten micro-electrode 9 (as Fig. 7).When carrying out plasma deep etching, SF6 can be adopted as etching gas, passivation gas adopts CHF3 or C4F8, total flow is 50 ~ 200sccm, passivation gas accounts for 50%-70%, air pressure >=25mTorr, RF power≤40W, ICP power >=1500W, the etch rate of employing is 0.5 ~ 2 μm/min.
In the present embodiment, the etching depth of tungsten micro-electrode is 200 μm.For avoiding etching heteropical impact, cross 10min at quarter, to ensure that the degree of depth of all regions tungsten electrode all reaches 200 μm.Meanwhile, because there is the protection of Al film at the back side, cross and carve and can not impact the electroformed structure at back.Then wet etching removes aluminium mask, and the unnecessary aluminium in the back side crosses protective layer at quarter, adhesion layer and Seed Layer (as Fig. 8).
6. because the method for conventional physical and chemistry removes the combination that SU-8 glue can affect tungsten electrode and copper supporting construction, here utilize microwave plasma body method to remove SU-8 glue, release supporting construction, obtains micro-electrode (as Fig. 9), here, reacting gas is CF 4and O 2, remove speed and can reach 20 μm/min.
7. the high depth-to-width ratio micro electrode utilizing 200 μm of tungsten electrodes and 1200 μm of copper supporting constructions to form carries out micro EDM.Here, for the tungsten electrode micro EDM proportion of goods damageds 20%, if back does not have supporting construction, the maximum machining depth of 200 μm of tungsten micro-electrodes is 120 μm, and the maximum of this high depth-to-width ratio micro electrode can working depth be 1000 μm, depth-to-width ratio improves more than 8 times.
With embodiment above unlike, the present invention also can adopt LIGA technique to prepare micro-electrode supporting construction at tungsten substrate back.This method cost is higher, and need to use synchronous X-ray, photoresist uses PMMA usually, electroforming step and UV-LIGA technique similar.
Above embodiment is only in order to illustrate technical scheme of the present invention but not to be limited; those of ordinary skill in the art can modify to technical scheme of the present invention or equivalent replacement; and not departing from the spirit and scope of the present invention, protection scope of the present invention should be as the criterion with described in claims.

Claims (10)

1. a preparation method for high depth-to-width ratio micro electric spark array electrode, its step comprises:
1) Seed Layer of protective layer, adhesion layer and electroforming is made successively at the back side of tungsten substrate;
2) the hard mask of tungsten etching is made in tungsten substrate front;
3) on hard mask, apply photoresist and exposure imaging, complete the graphical of photoresist;
4) hard mask is etched to realize the transfer of mask pattern, and at surface coating photoresist as protective layer;
5) utilize described Seed Layer to carry out electroforming at tungsten substrate back, form micro-electrode supporting construction;
6) remove the photoresist protective layer in tungsten substrate front, adopt plasma deep etching method to prepare tungsten micro-electrode;
7) remove the hard mask in tungsten substrate front and unnecessary protective layer, adhesion layer and the Seed Layer of tungsten substrate back, obtain the high depth-to-width ratio micro electrode be made up of tungsten micro-electrode and micro-electrode supporting construction.
2. the method for claim 1, is characterized in that: step 1) material of described protective layer is Al, AlN, Cr or Ni, thickness is 0.5 ~ 2 μm; The material of described adhesion layer is Ti, TiW, Au, Co or Ta, and thickness is 50 ~ 200nm, the material of described Seed Layer and step 5) in carry out the material of electroforming consistent, thickness is 100 ~ 500nm.
3. the method for claim 1, is characterized in that: step 2) material of described hard mask is Al, AlN, Cr or Ni, thickness is 2 ~ 5 μm.
4. the method for claim 1, is characterized in that, step 5) adopt UV-LIGA technique to prepare micro-electrode supporting construction, comprise the steps:
A) adopt injecting type gluing method to be coated with SU-8 glue to tungsten substrate, obtain smooth glued membrane, then carry out front baking, after completing, taking-up tungsten substrate, is placed to room temperature;
B) adopt the method for dual surface lithography, realization is aimed at tungsten substrate front description, and the mode that after exposure, utilization heats up gradually carries out rear baking, carries out ultrasonic development after being cooled to room temperature;
C) adopt corresponding electroforming solution to carry out electroforming according to the difference of electroforming material, then utilize chemically mechanical polishing by electroforming material surface attenuated polishing, form micro-electrode supporting construction.
5. method as claimed in claim 4, it is characterized in that: step a) in the thickness of SU-8 glue be 0.1 ~ 1.5mm, the substrate coating SU-8 glue is placed on the glue evenning table of leveling, relies on SU-8 glue obtaining smooth glued membrane higher than the mobility had during its glass transition temperature; The temperature of described front baking is 80 ~ 120 DEG C, and the time is 5 ~ 20h.
6. method as claimed in claim 5, is characterized in that: step b) mode that heats up gradually of described utilization carries out rear baking, is first slowly be warming up to 50 ~ 70 DEG C by room temperature, keep 5 ~ 20min, then be warming up to 90 ~ 95 DEG C, keep 30 ~ 60min, then naturally cool to room temperature.
7. method as claimed in claim 6, is characterized in that: step c) electroforming material that adopts is copper, nickel, gold, silver, iron or iron-nickel alloy; Electroforming temperature is set as 10 ~ 60 DEG C, and current density is 100 ~ 500A/m 2.
8. the method according to any one of claim 4 ~ 7, is characterized in that: after electroforming, utilizes microwave plasma body method to remove SU-8 glue, to discharge supporting construction.
9. the method for claim 1, is characterized in that: step 5) adopt LIGA technique to prepare micro-electrode supporting construction.
10. the high depth-to-width ratio micro electric spark array electrode that according to any one of claim 1 ~ 9 prepared by method.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106702439A (en) * 2016-12-22 2017-05-24 南京理工大学常熟研究院有限公司 Directional electrocasting method of miniature metal tube
CN110970147A (en) * 2019-11-07 2020-04-07 复旦大学 High-resolution hard X-ray tungsten/gold Fresnel zone plate and preparation method thereof
CN112981470A (en) * 2021-02-05 2021-06-18 吉林大学 Electroforming copper solution, preparation method and application thereof, and copper electrode

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CN101327537A (en) * 2008-07-09 2008-12-24 南京航空航天大学 Electrochemical processing method of high depth-to-width ratio micro metallic bundle pillar structure and special-purpose tool
CN103913789A (en) * 2014-04-03 2014-07-09 大连理工大学 Method for preparing high aspect ratio metal microgratings on metal substrate

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JPH07263379A (en) * 1994-03-23 1995-10-13 Sumitomo Electric Ind Ltd Method of forming fine structure
CN1335659A (en) * 2000-07-25 2002-02-13 中国科学院高能物理研究所 Fine electrospark process of forming electrode
CN1778505A (en) * 2004-11-19 2006-05-31 中国科学院高能物理研究所 Production of extremely profiled fine electrode for processing electric spark
CN1958862A (en) * 2006-10-13 2007-05-09 南京航空航天大学 Electroforming method suitable to fine structure with high depth-width ratio
CN101327537A (en) * 2008-07-09 2008-12-24 南京航空航天大学 Electrochemical processing method of high depth-to-width ratio micro metallic bundle pillar structure and special-purpose tool
CN103913789A (en) * 2014-04-03 2014-07-09 大连理工大学 Method for preparing high aspect ratio metal microgratings on metal substrate

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106702439A (en) * 2016-12-22 2017-05-24 南京理工大学常熟研究院有限公司 Directional electrocasting method of miniature metal tube
CN110970147A (en) * 2019-11-07 2020-04-07 复旦大学 High-resolution hard X-ray tungsten/gold Fresnel zone plate and preparation method thereof
CN110970147B (en) * 2019-11-07 2022-11-18 复旦大学 High-resolution hard X-ray tungsten/gold Fresnel zone plate and preparation method thereof
CN112981470A (en) * 2021-02-05 2021-06-18 吉林大学 Electroforming copper solution, preparation method and application thereof, and copper electrode
CN112981470B (en) * 2021-02-05 2022-03-08 吉林大学 Electroforming copper solution, preparation method and application thereof, and copper electrode

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