CN1081246C - Multiple elements chemical etching agent for nickel-titanium alloy film - Google Patents
Multiple elements chemical etching agent for nickel-titanium alloy film Download PDFInfo
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- CN1081246C CN1081246C CN99113924A CN99113924A CN1081246C CN 1081246 C CN1081246 C CN 1081246C CN 99113924 A CN99113924 A CN 99113924A CN 99113924 A CN99113924 A CN 99113924A CN 1081246 C CN1081246 C CN 1081246C
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Abstract
The present invention relates to a multi-element chemical etching agent for a nickel-titanium alloy film, which is composed of 1% to 25%(V) of hydrofluoric acid, 0.5% to 15%(V) nitric acid, 2% to 20%(V) hydrochloric acid and an etching speed rate accelerant, wherein the main components of the etching speed rate accelerant is one kind or many kinds of mixtures made of potassium iodate, sodium hypochlorite, peroxy acetic acid or oxydol. The service performance can be maintained by replenishing consumed active components. The multi-element chemical etching agent has high stability for photoresist and organic compounds, the precision of pattern transfer can be ensured, the replication capacity for a complex fine masking figure is improved, simultaneously the rate of finished products processed in batches can also be improved, and processing cost and liquid waste disposal cost are low.
Description
The present invention relates to a kind of chemical etchant, especially a kind of to the stable multiple elements chemical etching agent for nickel-titanium alloy film of photoresist material, being mainly used in NiTi is the graphical chemical etching of shape memory alloy film, belongs to technical field of chemistry.
In the prior art, shape memory alloy film (particularly NiTi series) is considered to preferably one of selection of millimeter microdrive driving mechanism to the micro-meter scale.With common electromagnetism, static, piezoelectricity, the microactrator that principles such as thermal expansion and sosoloid phase transformation drive is compared, the driving energy height and the displacement of unit volume shape memory alloy film are big, in addition, have also that recovery stress is big, operating voltage is low, simple in structure, the life-span long, to advantages such as human body toxicological harmlesss.Owing to can on silicon substrate, make Ni-Ti alloy thin film shape memory microdrive spare, therefore be easy to become one with control loop, carry out the batch low cost production.So, driving mechanism as microdrive, shape memory alloy film has extremely tempting prospect, yet, NiTi is the graphical relatively difficulty of alloy firm, and Nakamura thinks that this is one of the major technique obstacle (Proc.of the conf.On energing technologies and factory automation.1996:262～266) that hinders its widespread use.
Wet chemical etch is one of the most common film material graphics technique means, Krulevitch etc. once made chemical etchant (the J.ofMicroelectromechanical systems of nickel-titanium alloy film with the dilute solution that contains hydrofluoric acid and nitric acid, 1996, Vol 5, No.4:270～281), baking was solidified after the used photoresist material mask of this method need be made high temperature, to improve mask stability, but it is still stable inadequately in above-mentioned etching agent, the mask lithography glue agent etch phenomenon that is etched is obvious, add the etch rate of nickel-titanium alloy film soon inadequately, cause mask lithography glue early failure easily, graphical effect is not ideal enough.Be difficult to obtain under the situation of satisfactory result at chemical etching, block the formula mask technique in early days with having risen again, yet this is helpless selection really, mask manufacture difficulty not only, and be difficult to obtain the figure of trickle exquisiteness, also might sputtering sedimentation cause during than thick film mask up and down metallic membrane adhesion and lead demoulding failure.
Use the direct etching nickel-titanium alloy film of dry etching technology also relatively more difficult to solve graphical problem, because if with general ion milling process (Ion milling), the etching of finishing several micron (generally greater than 5 microns) thick Ni-Ti alloy films needs for a long time, and mask material is also difficult to be selected; If use reactive ion etching, be difficult to find to Ni and the simultaneously effective reactant gases of two kinds of elements of Ti.But, Nakamura etc. (Proc.of the conf.On energing technologies and factory automation.1996:262～266) make the transition mask material with the chromium metal film, make the mask of shape memory alloy film of the reactive ion etching Kapton, in the blank space nickel deposited titanium alloy thin films of mask graph, remove the polyimide that remains in the figure is peeled off (Lift-Off) to reach effect with KOH solution more at last then.Though this method utilizes the etching polyimide to avoid the difficult problem of direct etching nickel-titanium alloy film, the precision of graph copying has reduced, and processing step is also more complex, and cost is very high; Also have a kind of may, in Ni-Ti alloy sputter deposition process, may pollute the memorial alloy film as the polyimide of memorial alloy mask, influence its shape memory characteristic, so this neither a kind of good selection.
The objective of the invention is to deficiency at the prior art existence, seek a kind of chemical etchant of superior performance, is the patterned better selection of shape memory alloy film with wet chemical etch as Ni-Ti, simple to realize, low-cost, the graphical little processing of high precision.
For realizing such purpose, the present invention is to contain the hydrofluoric acid solution of specific oxygenant, be equipped with the mask stablizer that produces through a large amount of screenings, several functionalities additives such as etching rate accelerating material(RAM), form a kind of brand-new polynary Ni-Ti alloy chemical etchant, being used for NiTi is the graphical chemical etching of shape memory alloy film.
Etching agent of the present invention is by hydrofluoric acid, and nitric acid and an amount of mask stablizer, etching rate accelerating material(RAM) and water constitute.
Hydrofluoric acid is one of major ingredient of etching agent, and its content is between 0.95%-26.7%; Nitric acid is oxidisability composition main in the etching agent, and content can be between 0.5%-19.5%; The mask stablizer can significantly improve the stability of mask lithography glue, and its composition is a hydrochloric acid, and content can be between 2.0%-22.6%.Etch rate promotor can significantly improve the etch rate of Ni-Ti alloy, it can be a Potassium Iodate, clorox, one or more mixtures in Peracetic Acid or the hydrogen peroxide, content is between 1%-10%, wherein, Potassium Iodate content is between 1%-5%, clorox content is between 1%-4%, and Peracetic Acid content is between 1%-10%, and hydrogen peroxide content is between 1%-8%.The content of above-mentioned all compositions all be weight percentage (Wt%).
Mixing the etching agent that is constituted by above-mentioned each component by suitable order can at room temperature use easily, temperature range that can works better is 5-35 ℃, above-mentioned etching agent can be under multiple conventional agitation condition works better, as reciprocating motion type, the magnetic force rotation is stirred or spray-type etc.
In the above-mentioned etching agent, common unicircuit highly stable with photoresist (as Az series), the figure after the photoetching need not to dry by the fire behind the high temperature, brings obvious facility to subsequent disposal, can be complementary with custom integrated circuit technology.
The photoresist material etch rates that etching agent of the present invention is handled common process is very slow, soaks and can't see the etch sign in 10 minutes, and the rear surface showed coarse slightly in 20 minutes, and variation in thickness still is not enough to detect.And the time that is generally used for NiTi film etching can seldom not have an opportunity to want etching more than 15 minutes greater than 10 minutes.The aforementioned stable sexual clorminance can guarantee the precision of figure transfer, improves the replication to the trickle mask graph of complexity.The high stability of photoresist material can improve the yield rate of batch machining simultaneously.
The present invention is except stable to photoresist material, and many organic compound such as polyimide, PMMA etc. can long period of soaking and keep stable, can be with this class material as substrate.For gold, the inert metal of platinum and so on does not produce obvious corrosive nature equally, can be used as substrate layer yet and uses.The reaction of the present invention and silicon is slower, generally can not have a negative impact as substrate material to silicon.Convenient integrated with traditional IC technology.
The present invention is very fast to the silicon-dioxide etch rate, but for SiO
2The above nickel-titanium alloy film etching of figure live width 5-10 micron can not cause difficulty on the substrate, when live width during less than film thickness, if can not accurately control etching terminal, might cause figure to be peeled off.
The present invention can etch very level and smooth border to the nickel-titanium alloy film that promptly plates state, the etch rate that promptly plates the state film the 1-5 micron/minute between, the etching that the immersion type etching can realize is than between 1-2.
The present invention carries out etching to the nickel-titanium alloy film that promptly plates state, and etching interface is very smooth, and roughness only is a tens nanometer.
The present invention can carry out graphical etching equally for the later nickel-titanium alloy film of thermal treatment, but etching interface and lines border present the complications suitable with grain-size, and hachure has been duplicated certain influence.
Etching agent of the present invention can be kept its reactive behavior by adding effective active components at regular time and quantity, operation and maintenance correctly can make the etching agent effective ingredient upgrade and need not waste mother liquor more than 20 times, thereby the tooling cost of making and treatment cost of waste liquor are very low.
Mask lithography glue need not behind the high temperature baking and solidifies promptly very stablely in the etching agent of the present invention, can obtain and the on all four level and smooth etching of the mask graph of photoetching border the Ni-Ti alloy firm of sputter attitude.
Etching agent of the present invention can be used for the graphical chemical etching that NiTi is a shape memory alloy film, in mask stability, etch rate, the level and smooth degree of etched surface, the figure transfer accuracy of repetition, aspects such as batch machining reliability and tooling cost significantly are better than used before this chemical etchant.
Further specify technical scheme of the present invention and high-performance that etching agent of the present invention embodied below by two application examples.
The homogeneity of embodiment 1, batch machining
Mask lithography glue: AZ4620, thickness 3-4 micron, 100 ℃ of back baking temperature, 30 minutes back baking time.
Mask graph: the pattern that vertical element constituted of one group of different live width, live width is from 5 microns to 50 microns, and 2500 microns of length repeat to be distributed on whole 3 inches silicon chips, have 30 patterns.
Nickel-titanium alloy film thickness to be etched is 3.2 microns, without thermal treatment.
Etching agent is formed (Wt%): hydrofluoric acid 5.5%, and nitric acid 2.7%, hydrochloric acid 5.8%, clorox 2%, all the other are water.
20 ℃ of room temperatures, reciprocating motion type stirs.
Etching effect:
1.2 microns/minute of etch rates, all graphic limits are clear, lines are level and smooth, in full accord with mask lithography glue border tendency, choose the lines measuring resistance of 15 microns of live widths to estimate consistence in 30 groups of identical patterns on the same silicon chip, all lines deviations in ± 1%, triplicate, consistence is like this without exception.
Embodiment 2, the graphical etching of Micropump driving mechanism
Mask lithography glue: AZ4620, thickness 3-4 micron, 100 ℃ of back baking temperature, 30 minutes back baking time.
Mask graph is the tortuous loop line that is used for the Micropump driving of particular design, and line thickness is 50 microns, 40 microns at interval of adjacent lines, about 10000 microns of loop line total length, reversed turning bending 12 times.
Conventional drying glue technology is made.
Nickel-titanium alloy film thickness 8-10 micron to be etched is without thermal treatment.
Etching agent is formed (Wt%): hydrofluoric acid 7.9%, and nitric acid 1.8%, hydrochloric acid 6.3%, Peracetic Acid 10%, all the other are water.
20 ℃ of room temperatures, reciprocating motion type stirs
Etching effect:
2.2 microns/minute of etch rates, all graphic limits are clear level and smooth, and are in full accord with mask lithography glue border tendency, by resistivity measurement each cell resistance bar uniformity as can be known, are 1.5 with the lateral etching ratio vertically through scanning electron microscopy measurement.
Claims (5)
1, a kind of multiple elements chemical etching agent for nickel-titanium alloy film is characterized in that being the hydrofluoric acid of 0.95%-26.7% by weight percent (Wt%), the nitric acid of 0.5%-19.5%, and the hydrochloric acid of 2.0%-22.6%, the etch rate promotor of 1%-10% and water are formed.
2, as the said multiple elements chemical etching agent for nickel-titanium alloy film of claim 1, it is characterized in that wherein etch rate promotor is Potassium Iodate, content is between 1%-5%.
3, as the said multiple elements chemical etching agent for nickel-titanium alloy film of claim 1, it is characterized in that wherein etch rate promotor is clorox, content is between 1%-4%.
4, as the said multiple elements chemical etching agent for nickel-titanium alloy film of claim 1, it is characterized in that wherein etch rate promotor is Peracetic Acid, content is between 1%-10%.
5, as the said multiple elements chemical etching agent for nickel-titanium alloy film of claim 1, it is characterized in that wherein etch rate promotor is hydrogen peroxide, content is between 1%-8%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113924A CN1081246C (en) | 1999-07-29 | 1999-07-29 | Multiple elements chemical etching agent for nickel-titanium alloy film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113924A CN1081246C (en) | 1999-07-29 | 1999-07-29 | Multiple elements chemical etching agent for nickel-titanium alloy film |
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| Publication Number | Publication Date |
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| CN1242438A CN1242438A (en) | 2000-01-26 |
| CN1081246C true CN1081246C (en) | 2002-03-20 |
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| CN99113924A Expired - Fee Related CN1081246C (en) | 1999-07-29 | 1999-07-29 | Multiple elements chemical etching agent for nickel-titanium alloy film |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102154649A (en) * | 2011-03-31 | 2011-08-17 | 贵州大学 | Polishing solution for medical NiTi shape memory alloy |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040035717A1 (en) * | 2002-08-21 | 2004-02-26 | Casio Micronics Co. , Ltd. | Chemical treatment method and chemical treatment apparatus |
| KR100536593B1 (en) * | 2002-12-05 | 2005-12-14 | 삼성전자주식회사 | Cleaning solution for selectively removing a layer and method for selectively removing the layer in silicide process using the cleaning solution |
| CN100455700C (en) * | 2004-08-13 | 2009-01-28 | 上海埃蒙迪材料科技有限公司 | Chemical process of nickel-titanium alloy material |
| CN101139713B (en) * | 2006-09-07 | 2010-06-09 | 台湾薄膜电晶体液晶显示器产业协会 | Etching liquid and method for manufacturing patterned conductive layer using the same |
| CN103087718B (en) * | 2013-01-16 | 2014-12-31 | 四川大学 | Etching solution for performing wet etching on lanthanum nickelate film and ferroelectric film/lanthanum nickelate composite film and preparation method thereof |
| CN105256315A (en) * | 2015-09-16 | 2016-01-20 | 昆山全亚冠环保科技有限公司 | Metallographic corrosive agent and method for nickel-vanadium alloy |
| CN110923714A (en) * | 2019-09-26 | 2020-03-27 | 宁波福至新材料有限公司 | Etching solution and etching method for titanium foil micropore pattern |
| CN113969403B (en) * | 2021-10-27 | 2023-10-31 | 湖南工程学院 | Etching solution and method for nickel-titanium superalloy |
Citations (4)
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|---|---|---|---|---|
| CN1047115A (en) * | 1989-05-11 | 1990-11-21 | 郑小达 | Remove the pickling agent of oxide layer on stainless steel surface |
| CN1053647A (en) * | 1990-12-29 | 1991-08-07 | 孙永春 | The chemical stripping method of oxidizing layer of stainless steel |
| CN1078430A (en) * | 1993-02-23 | 1993-11-17 | 万冬英 | Marble and granite picture and text etching technics |
| CN1148637A (en) * | 1995-07-18 | 1997-04-30 | 三星航空产业株式会社 | Figure forming method |
-
1999
- 1999-07-29 CN CN99113924A patent/CN1081246C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1047115A (en) * | 1989-05-11 | 1990-11-21 | 郑小达 | Remove the pickling agent of oxide layer on stainless steel surface |
| CN1053647A (en) * | 1990-12-29 | 1991-08-07 | 孙永春 | The chemical stripping method of oxidizing layer of stainless steel |
| CN1078430A (en) * | 1993-02-23 | 1993-11-17 | 万冬英 | Marble and granite picture and text etching technics |
| CN1148637A (en) * | 1995-07-18 | 1997-04-30 | 三星航空产业株式会社 | Figure forming method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102154649A (en) * | 2011-03-31 | 2011-08-17 | 贵州大学 | Polishing solution for medical NiTi shape memory alloy |
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| CN1242438A (en) | 2000-01-26 |
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