CN101110355A - Method for minute graphic representation of metal with non-plane surface - Google Patents
Method for minute graphic representation of metal with non-plane surface Download PDFInfo
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- CN101110355A CN101110355A CNA2007100451078A CN200710045107A CN101110355A CN 101110355 A CN101110355 A CN 101110355A CN A2007100451078 A CNA2007100451078 A CN A2007100451078A CN 200710045107 A CN200710045107 A CN 200710045107A CN 101110355 A CN101110355 A CN 101110355A
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Abstract
A non-plane surface metallic fine pattern method is provided, which is characterized in that: form an upper metallic sacrifice layer and a lower sacrifice layer on a surface of basal piece with non-plane structure, make the potential of the standard electrode on the lower metallic sacrifice layer higher than that for the standard electrode on the upper metallic sacrifice layer, then form a patterned upper metallic sacrifice layer with spin coating lightscribing glue and wet method erosion, make the patterned upper layer metallic sacrifice layer only cover the surface of the non-plane structure to be metalized, then form a polymer layer on the upper metallic sacrifice layer with spin coating of polymer, then form a patterned lightscribing glue layer on the polymer layer with spin coating of lightscribing glue, then erode the upper layer metallic sacrifice layer with electric chemical anode to remove the residual lightscribing glue on it, finally remove the lower layer metallic sacrifice layer, deposit a metallic layer on the surface with a lightscribing glue layer, then remove the lightscribing glue layer with stripping technique to form a patterned metallic layer, so as to effectively remove the residual lightscribing glue in the non-plane structure.
Description
Technical field
The present invention relates to a kind of method of minute graphic representation of metal with non-plane surface.
Background technology
Peeling off is technology commonly used in the micro-processing technology, is mainly used in the minute graphic representation (as gold, platinum, tantalum, superconductor etc.) of realizing various difficult corroding metals.The key step of this technology is: spin coating photoresist on substrate at first, exposure, development form patterned photoresist, plated metal then, remove photoresist at last, the metal that deposits on the photoresist in this process is stripped from photoresist, and do not have the metal that the zone deposited of photoresist to be retained on the substrate, thereby on substrate, realize metal patternization.So far lift-off technology is being used widely aspect the minute graphic representation of metal of planar structure, yet, in micro-processing technology, usually need realize metal patternization (the three-dimensional protruding microelectrode in such as the microfluid pipeline in processing Electrochemical Detection microelectrode, the vision prosthesis etc.) on the nonplanar structure surface, photoresist often can not distribute on this structure uniformly, post-develop glue at quarter has residual in some pit areas, thereby has restricted the utilization of this technology.For this reason, some development in laboratory (see also document: Schnupp R. such as the electro-deposition photoresist, et al. " Electrodeposition of photoresist-optimizationof deposition conditions; investigation of lithographic processes and chemicalresistance ", Sensors and Actuators A, 2000,85:310-315.), jet-coating photoresit (sees also document: Pham N.P., et al. " Direct spray coating of photoresist-a new method forpatterning 3-D structures ", In the 16th European Conference on Solid-StateTransducers, September 15-18,2002, Prague, Czech Republic) etc. technology is finished the even coating of photoresist.Yet, these methods or need specific expensive device, or the graphical back of the photoresist institute graphics resolution that obtains is undesirable, so how effectively to remove photoresist residual in the nonplanar structure and become the technical task that those skilled in the art need to be resolved hurrily in fact.
Summary of the invention
The object of the present invention is to provide a kind of method of minute graphic representation of metal with non-plane surface, with residual photoresist in effective removal nonplanar structure.
Reach other purposes in order to achieve the above object, the method of minute graphic representation of metal with non-plane surface provided by the invention, it comprises step: 1) form two sacrificial metal layer up and down at a substrate surface that contains nonplanar structure, wherein, the lower metal sacrifice layer covers the whole metalized surface for the treatment of of described substrate, and makes its standard electrode EMF be higher than the standard electrode EMF of upper strata sacrificial metal layer; 2) by spin coating photoresist, exposure, development and wet etching forming graphical upper strata sacrificial metal layer, and make that described graphical upper strata sacrificial metal layer only covers described substrate wait to metallize the surface of nonplanar structure; 3) on the sacrificial metal layer of described upper strata, pass through spin on polymers, exposure and development to form polymer layer; 4) spin coating photoresist, exposure and develop on described polymer layer to form the graphical photoresist layer in the stripping technology; 5) adopt the described upper strata of electrochemistry anodic attack sacrificial metal layer to remove residual photoresist attached to it; 6) remove described lower metal sacrifice layer, and at surface deposition one metal level that is formed with graphical photoresist layer, and adopt stripping technology to remove described graphical photoresist layer to form corresponding graphical metal level.
Can comprise step in step 6): (1) adopts wet etching to remove described lower metal sacrifice layer; (2) surface deposition one metal level that is being formed with graphical photoresist layer; (3) adopt stripping technology to remove the graphical photoresist layer that has deposited metal.
Also can comprise step in step 6): surface deposition one metal level that (1) is being formed with graphical photoresist layer; (2) adopt stripping technology to remove the graphical photoresist layer that has deposited metal; (3) be that mould is being removed the surface casting polymer of described graphical photoresist layer with described substrate, and make its curing; (4) adopt wet method or electrochemical erosion method to remove described lower metal sacrifice layer to form the nonplanar structure surface metal patternization of counter-rotating.
In addition, preferable, described lower metal sacrificial layer material can be a kind of in gold, copper, nickel, chromium and the titanium, corresponding described upper strata metallic sacrificial layer material can be selected in copper, nickel, chromium, titanium and aluminium according to the material of described lower metal sacrifice layer, and described polymer can be polyimides, Parylene or dimethyl silicone polymer.
In sum, the method of minute graphic representation of metal with non-plane surface of the present invention is thoroughly removed photoresist residual in the nonplanar structure by utilization electrochemistry releasing sacrificial layer technology in stripping technology, effectively finish the graphical of photoresist, and then guaranteed the effective utilization of stripping technology at nonplanar structure.
Description of drawings
Fig. 1 is that the method for minute graphic representation of metal with non-plane surface of the present invention forms the structural representation of two sacrificial metal layer up and down on substrate.
Fig. 2 is the structural representation of the formed graphical upper strata of the method for minute graphic representation of metal with non-plane surface of the present invention sacrificial metal layer.
Fig. 3 peels off the schematic diagram of residual photoresist in the preceding pit for the method for minute graphic representation of metal with non-plane surface of the present invention.
Fig. 4 is that the method for minute graphic representation of metal with non-plane surface of the present invention adopts electrochemical process to remove the structural representation of upper strata sacrificial metal layer.
Fig. 5 is the structural representation of the formed metal electrode of method of minute graphic representation of metal with non-plane surface of the present invention.
Fig. 6 is the structural representation of the method curing metal electrode of minute graphic representation of metal with non-plane surface of the present invention.
Fig. 7 is the structural representation that the method for minute graphic representation of metal with non-plane surface of the present invention is removed the lower metal sacrifice layer.
Embodiment
Embodiment one:
Below will be used to make the flexible projection microelectrode with the method for minute graphic representation of metal with non-plane surface of the present invention be that example further specifies concrete characteristics of the present invention.
See also Fig. 1 to Fig. 7, the method for minute graphic representation of metal with non-plane surface of the present invention, it mainly may further comprise the steps:
1) clean＜100〉crystal orientation silicon chips, oxidation forms thick 1 micron oxide layer.
2) spin coating 6809 photoresists (3000 rev/mins, 30 seconds) on described silicon chip, baking is 20 minutes before 80 ℃, and exposure is developed, and baking is 30 minutes after 120 ℃.The cushioning liquid of hydrofluoric acid (BOE, HF: NH4F: DI=3: 6: 9) soaked silicon chip 10 minutes, and transition diagram is to silicon dioxide layer.
3) described silicon chip immerses sonicated in the acetone again, removes the photoresist on the silicon chip, and ethanol cleans then, and dries up with nitrogen.
4) silicon chip places the KOH solution of 50wt.%, and wet etching silicon chip (50 ℃, 6 hours) forms the about 54 microns pit of the degree of depth.
5) washed with de-ionized water silicon chip, the cushioning liquid of hydrofluoric acid (BOE, HF: NH
4F: DI=3: 6: 9) silicon dioxide layer on the removal silicon chip contains the silicon chip of nonplanar structure with formation.
6) as shown in Figure 1, chromium of hydatogenesis layer of metal successively on described silicon chip (thick 0.5 micron) and layer of metal aluminium (thick 0.5 micron) are to form two sacrificial metal layer up and down, wherein, the lower metal sacrifice layer covers the whole metalized surface for the treatment of of described substrate, and its standard electrode EMF is higher than the standard electrode EMF of described upper strata sacrificial metal layer, in addition, because the standard electrode EMF of metal puts in order and is: gold (Au)＞copper (Cu)＞nickel (Ni)＞chromium (Cr)＞titanium (Ti)＞aluminium (Al), so described lower metal sacrificial layer material also can be copper, nickel, a kind of in chromium and the titanium, corresponding described upper strata metallic sacrificial layer material can be according to the material of described lower metal sacrifice layer at copper, nickel, chromium, selected in titanium and the aluminium, for example when lower floor's sacrificial metal layer material was copper, described upper strata metallic sacrificial layer material can be nickel, chromium, titanium or aluminium.
7) as shown in Figure 2, (3000 rev/mins of described upper strata sacrificial metal layer spin coating photoresist AZ4620,30 seconds), baking is 20 minutes before 80 ℃, exposure, develop, baking is 30 minutes after 130 ℃, then formed silicon chip is immersed in 10% the phosphoric acid solution, the described upper strata of wet etching sacrificial metal layer to be forming graphical upper strata sacrificial metal layer, and the upper strata sacrificial metal layer that residue is not corroded only cover described substrate wait to metallize the surface of nonplanar structure, again described silicon chip is immersed sonicated in the acetone, remove the photoresist on the silicon chip, ethanol cleans then, and dries up to form graphical upper strata sacrificial metal layer with nitrogen.
8) on the sacrificial metal layer of described upper strata, pass through spin on polymers, for example photo-sensistive polyimide Durimide 7510 is (3000 rev/mins, 30 seconds), baking is 5 minutes before 110 ℃, exposure is developed, and solidifies in 350 ℃ of nitrogen environments to form polymer layer, in addition, the polymer of spin coating also can adopt Parylene or dimethyl silicone polymer.
9) as shown in Figure 3, spin coating photoresist AZ4620 on described polymer layer (3000 rev/mins, 30 seconds), baking is 20 minutes before 80 ℃, and exposure is developed to form the graphical photoresist layer in the stripping technology.
10) as shown in Figure 4, formed silicon chip is placed 20%NaCl solution, and, adopting platinum to electrode by on described lower metal sacrifice layer, applying the voltage of 0.75V, the described upper strata of electrochemical corrosion sacrificial metal layer (12 hours) is to remove residual photoresist attached to it.
11) at the surface sputtering Titanium/platinum that is formed with graphical photoresist layer to deposit a metal level, in addition, also can deposit other metal, for example gold, silver, copper etc. according to the actual design needs.
12) as shown in Figure 5, adopt peel off (Lift-off) technology remove deposited metal graphical photoresist layer to form the corresponding metal electrode.
13) as shown in Figure 6, with formed silicon chip is mould at the surface casting polymer of having removed described graphical photoresist layer polyimides Durimide 7510 for example, when cast, adopt the technology that vacuumizes to enter pit to quicken polyimides, (3000 rev/mins of whirl coatings, 30 seconds), baking is 5 minutes before 110 ℃, exposure, development, make the pattern of windows of solder joint correspondence, cure polyimide in 350 ℃ of nitrogen environments, in addition, the polymer of cast also can adopt Parylene or dimethyl silicone polymer.
14) as shown in Figure 7, can adopt wet method or electrochemical erosion method to remove described lower metal sacrifice layer, for example formed silicon chip be immersed chromium etchant solution ((NH to form the nonplanar structure surface metal patternization of counter-rotating
4)
2Ce (NO
3)
6: CH
3COOH: DI=5: 1: 25) in, corrosion chromium sacrifice layer, release polymers flexible electrode.
Embodiment two:
Slightly different on present embodiment and the embodiment one different operating procedures that only are to remove described lower metal sacrifice layer and form metal level, promptly after adopting electrochemical erosion method to remove the upper strata sacrificial metal layer, adopt wet etching to remove described lower metal sacrifice layer earlier, then surface deposition one metal level that is being formed with graphical photoresist layer again, adopt the stripping technology removal to deposit the graphical photoresist layer of metal at last to form corresponding graphical metal level, thereby finish the nonplanar structure surface metal patternization, because concrete operations are familiar with by those skilled in the art, so no longer describe in detail.
In sum, the method of minute graphic representation of metal with non-plane surface of the present invention is thoroughly removed photoresist residual in the nonplanar structure by utilization electrochemistry releasing sacrificial layer technology in stripping technology, effectively finish the graphical of photoresist, and then guaranteed the effective utilization of stripping technology at nonplanar structure, widened the range of application of Lift-Off technology.
Claims (6)
1. the method for a minute graphic representation of metal with non-plane surface is characterized in that comprising step:
1) form two sacrificial metal layer up and down at a substrate surface that contains nonplanar structure, wherein, the lower metal sacrifice layer covers the whole metalized surface for the treatment of of described substrate, and makes its standard electrode EMF be higher than the standard electrode EMF of upper strata sacrificial metal layer;
2) by spin coating photoresist, exposure, development and wet etching forming graphical upper strata sacrificial metal layer, and make that described graphical upper strata sacrificial metal layer only covers described substrate wait to metallize the surface of nonplanar structure;
3) on the sacrificial metal layer of described upper strata, pass through spin on polymers, exposure and development to form polymer layer;
4) spin coating photoresist, exposure and develop on described polymer layer to form the graphical photoresist layer in the stripping technology;
5) adopt the described upper strata of electrochemistry anodic attack sacrificial metal layer to remove residual photoresist attached to it;
6) remove described lower metal sacrifice layer, and at surface deposition one metal level that is formed with graphical photoresist layer, and adopt stripping technology to remove described graphical photoresist layer to form corresponding graphical metal level.
2. the method for minute graphic representation of metal with non-plane surface as claimed in claim 1, it is characterized in that: described step 6) further comprises step:
(1) adopt wet etching to remove described lower metal sacrifice layer;
(2) surface deposition one metal level that is being formed with graphical photoresist layer:
(3) adopt stripping technology to remove the graphical photoresist layer that has deposited metal.
3. the method for minute graphic representation of metal with non-plane surface as claimed in claim 1, it is characterized in that: described step 6) further comprises step:
(1) surface deposition one metal level that is being formed with graphical photoresist layer:
(2) adopt stripping technology to remove the graphical photoresist layer that has deposited metal;
(3) be that mould is being removed the surface casting polymer of described graphical photoresist layer with described substrate, and make its curing;
(4) adopt wet method or electrochemical erosion method to remove described lower metal sacrifice layer to form the nonplanar structure surface metal patternization of counter-rotating.
4. the method for minute graphic representation of metal with non-plane surface as claimed in claim 1 is characterized in that: a kind of in gold, copper, nickel, chromium and the titanium of described lower metal sacrificial layer material.
5. the method for minute graphic representation of metal with non-plane surface as claimed in claim 4, it is characterized in that: described upper strata metallic sacrificial layer material can be selected in copper, nickel, chromium, titanium and aluminium according to the material of described lower metal sacrifice layer.
6. the method for minute graphic representation of metal with non-plane surface as claimed in claim 1 is characterized in that: described polymer is a kind of in polyimides, Parylene and the dimethyl silicone polymer.
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| CNB2007100451078A CN100505159C (en) | 2007-08-21 | 2007-08-21 | Method for minute graphic representation of metal with non-plane surface |
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| CNB2007100451078A CN100505159C (en) | 2007-08-21 | 2007-08-21 | Method for minute graphic representation of metal with non-plane surface |
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| CN101110355A true CN101110355A (en) | 2008-01-23 |
| CN100505159C CN100505159C (en) | 2009-06-24 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058126A (en) * | 2012-11-30 | 2013-04-24 | 北京遥测技术研究所 | Processing method for surface electrodes of three-dimensional quartz micro-mechanical structure |
| CN105084301A (en) * | 2014-05-16 | 2015-11-25 | 上海蓝沛新材料科技股份有限公司 | Method for preparing embedded micro-nano level metal line on base material surface of special type product |
| CN108553755A (en) * | 2018-05-03 | 2018-09-21 | 国家纳米科学中心 | A kind of flexible 3 D nerve electrode and preparation method thereof |
| CN110143569A (en) * | 2019-05-29 | 2019-08-20 | 京东方科技集团股份有限公司 | The preparation method of microelectrode diaphragm |
| CN111641249A (en) * | 2020-06-04 | 2020-09-08 | 清华大学 | Flexible wearable power supply device and manufacturing method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5854126A (en) * | 1997-03-31 | 1998-12-29 | Siemens Aktiengesellschaft | Method for forming metallization in semiconductor devices with a self-planarizing material |
| US6965189B2 (en) * | 2002-09-20 | 2005-11-15 | Monodrive Inc. | Bending actuators and sensors constructed from shaped active materials and methods for making the same |
| CN100466323C (en) * | 2005-12-28 | 2009-03-04 | 中国科学院化学研究所 | A non plane channel organic field effect transistor |
-
2007
- 2007-08-21 CN CNB2007100451078A patent/CN100505159C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058126A (en) * | 2012-11-30 | 2013-04-24 | 北京遥测技术研究所 | Processing method for surface electrodes of three-dimensional quartz micro-mechanical structure |
| CN103058126B (en) * | 2012-11-30 | 2015-11-25 | 北京遥测技术研究所 | A kind of processing method of three-dimensional quartz micro mechanical structure surface electrode |
| CN105084301A (en) * | 2014-05-16 | 2015-11-25 | 上海蓝沛新材料科技股份有限公司 | Method for preparing embedded micro-nano level metal line on base material surface of special type product |
| CN108553755A (en) * | 2018-05-03 | 2018-09-21 | 国家纳米科学中心 | A kind of flexible 3 D nerve electrode and preparation method thereof |
| CN110143569A (en) * | 2019-05-29 | 2019-08-20 | 京东方科技集团股份有限公司 | The preparation method of microelectrode diaphragm |
| CN111641249A (en) * | 2020-06-04 | 2020-09-08 | 清华大学 | Flexible wearable power supply device and manufacturing method |
| CN111641249B (en) * | 2020-06-04 | 2021-03-09 | 清华大学 | Flexible wearable power supply device and manufacturing method |
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| CN100505159C (en) | 2009-06-24 |
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