CN1699633A - Method for improving the bonding strength between nickel or nickel alloy cast layers in laminated micro devices - Google Patents
Method for improving the bonding strength between nickel or nickel alloy cast layers in laminated micro devices Download PDFInfo
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- CN1699633A CN1699633A CN 200510024929 CN200510024929A CN1699633A CN 1699633 A CN1699633 A CN 1699633A CN 200510024929 CN200510024929 CN 200510024929 CN 200510024929 A CN200510024929 A CN 200510024929A CN 1699633 A CN1699633 A CN 1699633A
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Abstract
The present invention provides a method to increase inter-layer bond strength of electroformed nickel or nickel alloy lamination micro device. The surface of first Ni forming layer must be transitionally treated by activation-alternate current treatment when the first Ni forming layer is re-electroformed with Ni. The said alternate current treatment is etching with alternate cathodic and anodic current, wherein anodic current density, 3-7 A /dm2, is 2-5 times of cathodic current density, and alternate impulse period is 1-20 ms and etching time 3-7 minutes. During alternate current transition plating treatment, cathodic current keeps unchanged and anodic current is gradually decreased to 1/5 of the initial value, and then the treatment is converted into normal direct current plating. Adopting the present invention technology, the inter-layer bond strength can reach 15 -25 Kg/mm2, and inter-layer borderlines are ambiguous, meaning integrated into one piece.
Description
Technical field
What the present invention relates to is a kind of method that improves bonding strength between laminated micro devices nickel or nickelalloy cast layer, on the basis of the three-dimensional processing of three-dimensional microstructures, adopt the galvanoplastics manufacturing to have the method for the micro element of nickel or nickelalloy stromatolithic structure in particularly a kind of MEMS (micro electro mechanical system) (MEMS), belong to electro-chemical machining little manufacturing that is shaped
Technical field.
Background technology
LIGA (abbreviation of German Lithographie, Galvanoformung and Abformung) technology is the three-dimensional processing technology of three-dimensional microstructures that occurs the 1980s, be to utilize mask technology and electrochemistry electrocasting method, finish the fine precision processing technology that micro element is made.Three-dimensional microstructures device with this technology produces not only has great depth-to-width ratio and fine structure, and high and steep, the surfacing of ascending of workpiece sidewall, and thickness can reach 500 μ m and even thousands of micron.If through manufacturing procedures such as mask, deep layer photoetching, little electroforming, polishing repeatedly.Promptly before grinded, on one deck electroformed layer, repeat mask, deep layer photoetching, little electroforming again, can obtain various rhythmo structure micro elements.One of gordian technique in the manufacturing of rhythmo structure micro element is the bonding strength that how to guarantee between each lamination.Especially as the present mainly nickel and the nickelalloy lamination of electroformed layer, because metallic nickel and alloy layer are placed or the dense oxidation film through very easily being difficult to remove at surface formation one deck after the attrition process through one section in air, when superposeing the second layer thereon, bonding strength can descend greatly, and this has become the greatest problem in the laminated micro devices manufacturing.
Nickel plating on traditional nickel coating (in the decorative electroplating) pre-treating technology has formed the treatment process of two quasi-representatives through constantly improving.First kind technology: sulfuric acid, salt acid unit acid etch liquid; The second class technology: sulfuric acid, salt acid unit acid or contain the anode processing technique of chlorination nickel salt.Though first kind technology is simple to operate, only be suitable for nickel plating on the nickel that fresh and clean coating and thickness has only several microns or tens microns, for through polishing or mach nickel dam, be difficult to guarantee the bonding strength between coating; Though it is strong than first kind technology that the second class technology is removed the passive film ability, also only be applicable to nickel plating on tens microns the nickel.Be higher than 100 microns electroforming for thickness requirement, the accumulation of cast layer internal stress can reach very high value, causes interfacial bonding strength further to weaken, and aforesaid method also can't satisfy.
Find by prior art documents, Japanese patent application No. 2001-64344, publication number 2002-266094, patent name: the improvement method of plating, electroforming, preparation method of sample and the binding force of cladding material that obtains according to this method provides a kind of and has improved between the bright nickel electrolytic coating or the method for binding force of cladding material between electroformed layer or between lamination nickel.Concrete treatment process is: the sample after the first step nickel plating for the first time or through the sample after mask, the photoetching treatment was dipped in the 3～7vol.%HCl solution that does not contain promoting agent 10～50 ℃ of temperature, washing then 1～3 minute.Second the step with aforementioned sample be dipped in park 30～120 seconds in the nickel-plating liquid after, again the energising.Though this method is simple to operate, need not specific installation, whole thinking is not separated from traditional treatment process, and interfacial bonding strength is still lower, and process reproducibility is relatively poor, and requiring for the high bond strength between lamination nickel or nickelalloy cast layer still can't be satisfied fully.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, a kind of method that improves bonding strength between laminated micro devices nickel or nickelalloy cast layer is provided.The galvanic deposit that make it can remove the dense oxidation film of nickel and nickel alloy surfaces, to make the second layer simultaneously is one by the original lattice epitaxy of the first layer thereby make molten between lamination, forms the electrocasting method with very strong bonding strength.Its process characteristic is directly to carry out activation treatment by two pulse periodic reverse power supply in nickel or nickel alloy electricity plating liquor, can produce a desired effect.
The present invention is achieved by the following technical solutions, and the present invention is on the first layer nickel or nickelalloy cast layer, and when electroformed nickel or nickelalloy, the first layer nickel or nickel alloy layer must be handled through overactivation-interchange transition plating again.
Concrete technology is as follows:
Step 1 anode and cathode replaces etching processing
Carry out anode and cathode with the periodic reverse electric current and replace etching processing, anodic current density is 2～5 times of cathode current density, anodic current density 3～7A/dm
2, ALT pulse cycle 1～20ms, etching time 3～7min;
Step 2 anode and cathode replaces activation treatment
Identical 3～the 7A/dm of cathode current density with anodic current density
2, ALT pulse cycle 1～100ms, treatment time 5～10min;
Step 3 anode and cathode exchanges the transition plating and handles
The cathode current density value is constant, progressively reduces the anodic current density value to 1/5 of initial value, changes into normal direct current electrode position then.Treatment time depends on the needs.
In order to make above-mentioned technology bring into play its effect effectively, containing in the activated solution at least aly has the halide-ions of strong destruction effect to nickel or nickelalloy passive film, as: chlorion or bromide anion etc.; Used periodic reverse power supply can simultaneously or be regulated anode and cathode size of current, ON time separately, and time output can reach Millisecond.
The present invention replaces etching processing to the 1st step anode and cathode of nickel or nickel alloy layer enforcement, at first applies the anode and cathode electric current at nickel or nickel alloy layer surface, replaces etching processing.In anode and cathode exchange current and solution under the effect of chlorion, constantly wash away nickel or nickel alloy surfaces, make the former passive film of nickel or nickel alloy surfaces constantly destroy, dissolve, and formation is similar to the pitting effect, the aperture is 300-500nm, is the micro-rough surface of 500-800nm deeply.
The 2nd step anode and cathode ALT pulse activation treatment of the invention process makes the passive film completely dissolve, and makes metal being under the condition of anode and cathode electric current high-speed transitions between dissolving and the reduction, promptly has highly active " adatom " state.
The 3rd step of the invention process makes by what the second step surface formed to have highly active " adatom " reduction fully gradually, and enters selectively in the lattice of former the first layer nickel or nickelalloy " settling ", realizes the epitaxy by former lattice.Finally reach the organically molten purpose of the first layer and second layer nickel or nickel alloy layer for one, formation high bond strength.
The present invention has at first removed the oxide film that is difficult to remove fully with additive method that has a strong impact on bonding strength between lamination, can also make the first layer surface aperture occur is 300-500nm, dark is the micro-rough surface of 500-800nm, and forms crystal extension transition tissue on this basis between two laminations.Like this by special processing of the present invention, under the effect of the interlocking of micropore and epitaxial structure, two interlayers are organically combined, form firm bonding force, overcome the insurmountable problem of conventional art.Bonding strength can reach 15～25kg/mm between lamination of the present invention
2According to detection, after test piece fractures, there is not cracking in alternating bending between the fracture lamination, no demixing phenomenon, when this result adopted conventional art, it was unapproachable surpassing under the condition more than 100 microns in thickness of coating; Examine under a microscope, find that section part interlayer boundary line is unclear, prove two-layer organically molten be one.There is obvious limit in the section part interlayer of prior art, illustrates a little less than the two interlayer bonding forces.
Description of drawings
Fig. 1 process flow diagram of the present invention.
Wherein: 1a is that anode and cathode replaces etching, replaces activation treatment; 1b is that anode and cathode exchanges transition plating processing; 1c is for the second time electroformed nickel or electroformed nickel alloy; 1d is grinding, the double-deck micro element after removing photoresist; Substrate 1, Cr/Cu Seed Layer 2, the first layer photoresist material 3, the first layer nickel or nickelalloy cast layer 4, second layer photoresist material 5, anode and cathode replaces etching and replaces active layer 6, and anode and cathode exchanges transition layer 7, second layer nickel or nickelalloy cast layer 8.
Embodiment
Embodiment 1 electroformed nickel is made double-deck little gear
As shown in Figure 1, implement, because the particular requirement on double-deck little gear structure adopts the UV-LIGA technology to carry out microfabrication according to Fig. 1.Promptly on glass substrate 1, sputter Cr/Cu Seed Layer 2 forms the first layer photoresist material 3 through whirl coating, photoetching, after mask electroformed nickel, polishing, obtains the first layer nickel cast layer 4 again; Carry out the whirl coating second time, photoetching formation second layer photoresist material 5 thereon again; Then activating-exchange the transition plating handles.This treatment solution adopts NiSO
46H
2O 120g/l, NiCl
26H
2O 120g/l, HCl 100g/l and 1,3,6-naphthalene trisulfonic acid sodium 0.05g/l, pH transfers to 1.0, and treatment temp is 45 ℃.
1) replaces etching processing as Fig. 1 a anode and cathode: anodic current density 7A/dm
2, recurrence interval 20ms, cathode current density 1.4A/dm
2, recurrence interval 20ms, etching time 7min forms anode and cathode and replaces etch layer 6.
2) replace activation treatment as Fig. 1 a anode and cathode: anodic current density is constant, and cathode current density also transfers to 7A/dm
2, and ALT pulse cycle 100ms, soak time 10min forms anode and cathode and replaces active layer 6.
3) exchanging the transition plating as Fig. 1 b anode and cathode handles: cathode current density remains unchanged, and falls anodic current density 1.4A/dm every 10min
2, make anodic current density gradually by 7A/dm
2Reduce to 1.4A/dm
2End treatment forms anode and cathode and exchanges transition layer 7.It is clean to take out the sample deionized water rinsing, enters nickel bath such as Fig. 1 c plating second layer nickel cast layer 8.
After as Fig. 1 d grinding, the processing of removing photoresist, having obtained the first layer gear diameter is 2mm, thickness is 300 μ m, and second layer gear diameter is 1mm, and thickness is the double-deck micro element of 400 μ m.This gear is through 200 ℃, 1h heat treated, and naturally cooling in air bubbling do not occur, comes off, and description taken in conjunction power meets the requirements.
The double-deck Rhometal of embodiment 2 electroforming
Thickness 0.3mm, area 1.5 * 1.5cm
2Copper sheet on the double-deck Rhometal bonding force experiment of electroforming.After above-mentioned copper base 1 carried out oil removing, polished finish, be in the nickel-iron alloy plating solution at vitriol, the Rhometal cast layer 4 of plating 100 μ m is placed after 24 hours in the atmosphere, carries out the electroforming of secondary Rhometal.The solution that activation treatment adopts is by NiCl
26H
2O 100g/l, FeCl
24H
2O 10g/l, HCl 20g/l and sodium laurylsulfonate 0.01g/l form, and pH transfers to 1.5, and temperature is 50 ℃; The test piece of a nickel-clad iron immersed carry out activation treatment in the above-mentioned solution.
The first step replaces etching processing as Fig. 1 a anode and cathode: anodic current density 3A/dm
2, recurrence interval 1ms, cathode current density 1.5A/dm
2, recurrence interval 1ms, etching time 3min forms anode and cathode and replaces etch layer 6
In second step, replace activation treatment as Fig. 1 a anode and cathode: cathode current density transfers to 3A/dm on also
2, and ALT pulse cycle 1ms, soak time 5min forms anode and cathode and replaces active layer 6.
In the 3rd step, exchange the transition plating as Fig. 1 b anode and cathode and handle: cathode current density remains unchanged, and falls anodic current density 0.6A/dm every 10min
2, make anodic current density gradually by 3A/dm
2Reduce to 0.6A/dm
2Promptly dispose, form anode and cathode and exchange transition layer 7.It is clean to take out the back deionized water rinsing, enters ferronickel groove such as Fig. 1 c plating second layer ferronickel cast layer 8.
Second layer ferronickel is the about 100 μ m thickness of plating also.The double-deck ferronickel test piece that above-mentioned technology obtains is bent to the test piece fracture repeatedly through pliability test, does not have the cracking demixing phenomenon between incision position the first layer ferronickel and the second layer ferronickel, and description taken in conjunction intensity meets the requirements.
The double-deck nickel of embodiment 3 electroforming
Thickness 0.3mm, area 1.5 * 1.5cm
2Copper sheet on the double-deck nickel bonding force experiment of electroforming.At first, above-mentioned copper base 1 is carried out oil removing, polished finish, in nickel aminosulfonic bath, the nickel cast layer 4 of plating 100 μ m is placed after 24 hours in the atmosphere, carries out the electroforming of secondary nickel then.Secondary electroforming front activating is handled the solution of employing by NiCl
26H
2O 150g/l, HCl 50g/l and sodium laurylsulfonate 0.01g/l form, and pH transfers to 1.2, and temperature is 50 ℃; The test piece of a nickel plating is immersed in the above-mentioned solution.
The first step replaces etching processing as Fig. 1 a anode and cathode: anodic current density 5A/dm
2, recurrence interval 10ms, cathode current density 2.5A/dm
2, recurrence interval 10ms, etching time 5min forms anode and cathode and replaces etch layer 6
In second step, replace activation treatment as Fig. 1 a anode and cathode: cathode current density transfers to 5A/dm on also
2, and ALT pulse cycle 50ms, soak time 7.5min forms anode and cathode and replaces active layer 6.
In the 3rd step, exchange the transition plating as Fig. 1 b anode and cathode and handle: cathode current density remains unchanged, and falls anodic current density once every 7min, makes anodic current density gradually by 5A/dm
2Reduce to 1A/dm
2Promptly dispose, form anode and cathode and exchange transition layer 7.It is clean to take out the back deionized water rinsing, enters nickel bath such as Fig. 1 c plating second layer nickel cast layer 8.
The about 100 μ m thickness of second layer nickel plating.The double-deck nickel test piece that above-mentioned technology obtains is bent to the test piece fracture repeatedly through pliability test, and the interface is unclear between incision position the first layer nickel and the second layer nickel, does not have the cracking demixing phenomenon, illustrates that the bonding strength between double-deck nickel meets the requirements.
Laminated mould is made in embodiment 4 electronickellings
This mould needs double-deck nickel structure, the thick 500 μ m of the first layer nickel, the thick 1500 μ m of second layer nickel according to design requirements.At first on glass substrate 1, sputter Cr/Cu Seed Layer 2 forms the first layer photoresist material 3 through whirl coating, photoetching, after mask electroformed nickel, polishing, obtains the first layer nickel cast layer 4 again; Carry out the whirl coating second time, photoetching formation second layer photoresist material 5 thereon again.In order to guarantee the bonding strength between two-layer nickel, adopt activation of the present invention-interchange transition plating to handle.Contain NiCl in the treatment soln
26H
2O 300g/l, HCl 150g/l, benzene sulfinic acid sodium salt 0.2g/l, pH are 0.5,55 ℃ of treatment temps.
The first step replaces etching processing as Fig. 1 a anode and cathode: anodic current density 5A/dm
2, recurrence interval 5ms, cathode current density 2.0A/dm
2, recurrence interval 5ms, etching time 5min forms anode and cathode and replaces etch layer 6
In second step, replace activation treatment as Fig. 1 a anode and cathode: anodic current density is constant, and cathode current density also transfers to 5A/dm
2, and ALT pulse cycle 60ms, soak time 10min forms anode and cathode and replaces active layer 6.
In the 3rd step, exchange the transition plating as Fig. 1 b anode and cathode and handle: cathode current density remains unchanged, and gradually falls anodic current density in 45min, makes anodic current density gradually by 5A/dm
2Reduce to 1A/dm
2Form anode and cathode and exchange transition layer 7.Enter again as Fig. 1 c second layer nickel plating process, form second layer nickel layer 8.
Through the laminated mould that above-mentioned technical finesse obtains, nothing comes off, layering, in conjunction with firmly, does not occur any problem in the use, meets design requirement fully.
Adopt traditional treatment method to implement and comparative analysis as a result
As the double-deck nickel comparative example test of electroforming, sample adopts the condition identical with embodiment 3, i.e. thickness 0.3mm, area 1.5 * 1.5cm
2Copper sheet.At first, sample is carried out oil removing, polished finish, in nickel aminosulfonic bath, the nickel cast layer of plating 100 μ m is placed after 24 hours in the atmosphere, carries out the electroforming of secondary nickel then.Before the electroforming of secondary nickel, the activation treatment of carrying out is to adopt the second traditional class technology: activation solution is by NiCl
26H
2O 240g/l, HCl 200g/l constitutes, in room temperature, 8A/dm
2Anodic current density under handle 8min.Take out then, after rinsing well with deionized water, enter nickel bath plating second layer nickel cast layer, the about 100 μ m thickness of second layer nickel plating.The double-deck nickel test piece that above-mentioned technology obtains bends before not rupturing repeatedly through pliability test, and demixing phenomenon has appearred in the part, and description taken in conjunction intensity is undesirable.
Claims (7)
1. a method that improves bonding strength between laminated micro devices nickel or nickelalloy cast layer is characterized in that, on the first layer nickel cast layer, during electroformed nickel, the first layer nickel dam must be handled through overactivation-interchange transition plating again.
Concrete steps are:
Step 1. anode and cathode replaces etching processing;
Step 2. anode and cathode replaces activation treatment;
Step 3. anode and cathode exchanges transition plating processing.
2. the method for bonding strength between raising laminated micro devices nickel according to claim 1 or nickelalloy cast layer, it is characterized in that, step 1. anode and cathode replaces etching processing, at first apply the anode and cathode electric current on the nickel dam surface, replace etching processing, in anode and cathode exchange current and solution, under the effect of chlorion, constantly wash away nickel surface, make the former passive film of nickel surface constantly destroy, dissolve, and form the micro-rough surface that is similar to the pitting effect.
3. according to the method for bonding strength between claim 1 or 2 described raising laminated micro devices nickel or nickelalloy cast layer, it is characterized in that, step 1. anode and cathode replaces etching processing, and anodic current density is 2～5 times of cathode current density, anodic current density 3～7A/dm
2, ALT pulse cycle 1～20ms, etching time 3～7min.
4. the method for bonding strength is characterized in that between raising laminated micro devices nickel according to claim 1 or nickelalloy cast layer, and step 2. anode and cathode replaces activation treatment, the identical 3～7A/dm with anodic current density of cathode current density
2, and ALT pulse cycle 1～100ms, soak time 5～10min.
5. the method for bonding strength between raising laminated micro devices nickel according to claim 1 or nickelalloy cast layer, it is characterized in that step 3. anode and cathode exchanges transition plating processing, the cathode current density value is constant, progressively reduce the anodic current density value to 1/5 of initial value, change into normal direct current electrode position then.
6. according to each improves the method for bonding strength between laminated micro devices nickel or nickelalloy cast layer in the claim 1～5, it is characterized in that, contain the halide-ions of at least a chlorion or bromide anion in the activated solution.
7. according to the method for bonding strength between each described raising laminated micro devices nickel or nickelalloy cast layer in the claim 1～5, it is characterized in that the periodic reverse power supply simultaneously or regulate anode and cathode size of current, ON time separately.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100249299A CN100387756C (en) | 2005-04-07 | 2005-04-07 | Method for improving the bonding strength between nickel or nickel alloy cast layers in laminated micro devices |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100249299A CN100387756C (en) | 2005-04-07 | 2005-04-07 | Method for improving the bonding strength between nickel or nickel alloy cast layers in laminated micro devices |
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| CN1699633A true CN1699633A (en) | 2005-11-23 |
| CN100387756C CN100387756C (en) | 2008-05-14 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102618893A (en) * | 2012-04-20 | 2012-08-01 | 大连理工大学 | Method for adjusting micro electroforming current density to improve casting layer interface bonding strength |
| CN103374734A (en) * | 2012-04-17 | 2013-10-30 | 昆山允升吉光电科技有限公司 | Method for raising coating binding force |
| CN103575590A (en) * | 2013-10-10 | 2014-02-12 | 上海交通大学 | In-situ tensile sample for testing mechanical property of 3D-TSV copper interconnection material |
| CN110724978A (en) * | 2018-07-17 | 2020-01-24 | 精工电子有限公司 | Electroformed component and timepiece |
| JP7383060B2 (en) | 2020-07-17 | 2023-11-17 | マクセル株式会社 | Mold for plastic processing |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002266094A (en) * | 2001-03-08 | 2002-09-18 | Ricoh Co Ltd | Plating or electroforming method, and method for forming test specimen as well as method for improving adhesion property of plating formed by the plating or electroforming method |
| US6782230B2 (en) * | 2002-06-11 | 2004-08-24 | Canon Kabushiki Kaisha | Fixing belt, and image heat fixing assembly |
| CN1394988A (en) * | 2002-08-20 | 2003-02-05 | 中国科学院电子学研究所 | Multi-layer nickel-plating process by adopting single bath process |
-
2005
- 2005-04-07 CN CNB2005100249299A patent/CN100387756C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103374734A (en) * | 2012-04-17 | 2013-10-30 | 昆山允升吉光电科技有限公司 | Method for raising coating binding force |
| CN102618893A (en) * | 2012-04-20 | 2012-08-01 | 大连理工大学 | Method for adjusting micro electroforming current density to improve casting layer interface bonding strength |
| CN103575590A (en) * | 2013-10-10 | 2014-02-12 | 上海交通大学 | In-situ tensile sample for testing mechanical property of 3D-TSV copper interconnection material |
| CN110724978A (en) * | 2018-07-17 | 2020-01-24 | 精工电子有限公司 | Electroformed component and timepiece |
| JP7383060B2 (en) | 2020-07-17 | 2023-11-17 | マクセル株式会社 | Mold for plastic processing |
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| CN100387756C (en) | 2008-05-14 |
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