CN1979768A - Method for adopting positive electronic corrosion-resistant to prepare metal nano electrode - Google Patents
Method for adopting positive electronic corrosion-resistant to prepare metal nano electrode Download PDFInfo
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- CN1979768A CN1979768A CN 200510130438 CN200510130438A CN1979768A CN 1979768 A CN1979768 A CN 1979768A CN 200510130438 CN200510130438 CN 200510130438 CN 200510130438 A CN200510130438 A CN 200510130438A CN 1979768 A CN1979768 A CN 1979768A
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Abstract
A method uses the positive electron anticorrosion agent to prepare metal nano electrode. The main features of the invention is to use the neighboring effect of electron band, use the EBL to gain a pair or a group of the positive electron anticorrosion agent groove figures that have line, hole and other various shapes at the space that is measured by nano on various underlay, and then use secondly the metal deposition and peel off technology to prepare various metal material nano electrode. The main procedures of which include coating the positive electron anticorrosion agent on the interlay; baking frontally; expose by direct electron band; develop; to fix; vaporize or sputtering metal; to peel off in the acetone. The distance between the metal nano electrode that is prepared by such method can be 30~100mm, is suitable to make various quanta component, nano line, nano tube component, single electronic component and various components or circuit. The method has many advantages, such as: less technology procedure, simple, stable and reliable, multiple uses and can be compatible with the traditional CMOS technology.
Description
Technical field
The invention belongs to technical field of nano-processing, particularly a kind of preparation method of metal nano electrode.
Background technology
Since over half a century, be that the semiconductor integrated circuit of mainstream technology is being followed " Moore's Law " always and developed rapidly with CMOS, its characteristic size has entered into nanoscale, but also be faced with simultaneously more and more serious challenge, therefore become the focus of research based on the nano electron device of new material, new principle such as various quantum dot device, nano wire, nanometer tube device, single-electron device etc.In the making of these nano electron devices, size is little, good conductivity, making with the nano-electrode in nanometer scale gap are keys, also is a difficult point.
Application number is that 200410095163.9 Chinese invention patent mainly adopts chemical method to prepare electrode in conjunction with the utilization of macromolecular material, but kind electrode does not reach nanoscale.Application number is that 200410010181.2 Chinese invention patent prepares silver-colored nano-electrode with atomic force microscope (AFM) etching nanowire-junction combination method, has low, the shortcoming that can not large-scale production of efficient.Application number is that 99116576.4 Chinese invention patent adopts flame fusion and etching method to prepare class carbon fibre electrode, and electrode material is single, and only is used for biological field.Optical lithography is because its high efficiency is the mainstream technology of making electrode at present, but the resolution of optical lithography is subjected to the restriction of exposure wavelength to be difficult to reach nanometer resolution.Electron beam lithography is because the electron beam wavelength is very short, and diffraction effect can be ignored substantially, has very high resolution, and the resolution of high performance electronic bundle mask aligner can reach several nanometers.Therefore, adopt the electronic corrosion-resistant of electron beam lithography, and be aided with the deposit and the stripping technology of metallic film material, can prepare the metal nano electrode of various spacings less than 100nm in conjunction with the height explanation.This method has that processing step is few, simple, reliable and stable, purposes is many, can with the advantage of traditional cmos process compatibility.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing spacing less than the metal nano electrode of 100nm.
To achieve these goals, the present invention adopts electron beam lithography, and it is a kind of effective nanoprocessing means, has nano level resolution.The present invention mainly utilizes the proximity effect in the electron beam exposure, be that high-power electron beam can produce low-angle preceding scattering in the incident process in resist, on substrate, can produce the back scattering of wide-angle, make on the adjacent domain of exposure region, to produce additional exposure that the developed width of the back figure that develops is greater than the original design width of figure.Therefore, when design exposure domain, be provided with nearerly a pair of or a block graphics (100-400nm), just be easy to obtain spacing less than a pair of of 100nm or one group of positive electronic corrosion-resistant groove pattern in exposure, after developing, can prepare metal nano electrode with peeling off by follow-up metal deposit with different shapes such as lines, holes.
A kind of employing positive electronic corrosion-resistant utilizes electron beam lithography (EBL), metal deposit and stripping technology to prepare the method for metal nano electrode, and the concrete processing step of preparation metal nano electrode is as follows:
(1) identifying and correcting property of coating high score electronic corrosion-resistant on substrate;
(2) electronic corrosion-resistant is carried out preceding baking;
(3) electronic corrosion-resistant is carried out e-beam direct-writing exposure;
(4) develop, remove the electronic corrosion-resistant of exposure area;
(5) photographic fixing;
(6) deposition of electrode material;
(7) in acetone, peel off, remove electronic corrosion-resistant and on electrode material.
Wherein the substrate described in the step (1) is the insulation or the high resistant substrate of surfacing, cleaning, and substrate uses SiO
2, Si
3N
4, Al
2O
3, MgO, CaO, high-impedance state Si, Ge, GaAs, GaN, InP, InAs, ZnO, ZnS, CdS etc., described positive electronic corrosion-resistant can adopt PMMA, ZEP520, KRS, UV-III, P single or multiple lift resists such as (SI-CMS), also needs to take between (3) step and (4) step baking step in back when adopting these two kinds chemistry of KRS, UV-III to amplify resist.
Wherein the e-beam direct-writing exposure described in the step (3) can adopt the JBX-5000LS electron-beam lithography system that JEOL company produces, and its accelerating voltage is 50KeV, and electronic beam current is less than 100pA.Electrode pattern is spaced apart 100-400nm during design exposure domain.
Wherein the groove pattern of the positive electronic corrosion-resistant that forms after the photographic fixing described in development described in the electron beam exposure described in the step (3), the step (4) and the step (5) must have " undercutting " section structure, top is wider than in the bottom that is groove, so that follow-up peeling off.
Wherein the deposit described in the step (6) is the method for growing film materials such as evaporation, sputter, described electrode material is Al, Pt, Au, Ag, W, Ti, Cr, ITO single or multiple lift electrode materials such as (transparent), and the gross thickness of electrode material must be less than the thickness of electronic corrosion-resistant.
Wherein peeling off described in the step (7) needs to soak in acetone earlier, then sonic oscillation in acetone.
Description of drawings
Fig. 1-Fig. 5 is the process chart of the present invention and specific embodiment thereof;
Fig. 6 and Fig. 7 are respectively according to the ZEP520 positive electronic corrosion-resistant mask of the specific embodiment flow preparation of Fig. 1-shown in Figure 5 and scanning electron microscopy (SEM) photo of the Cr/Au metal nano electrode that corresponding spacing is 60nm.
Embodiment
In order to illustrate further content of the present invention, by description, further describe concrete grammar of the present invention below in conjunction with accompanying drawing to specific embodiment, wherein:
As shown in Figure 1, at surfacing, clean SiO
2, Si
3N
4, Al
2O
3, dielectric substrate such as MgO, CaO, high-impedance state Semiconductor substrate 1 such as Si, Ge, GaAs, GaN, InP, InAs, ZnO, ZnS, CdS on sol evenning machine coating single or multiple lift high-resolution positive electronic corrosion-resistant 2, as PMMA, ZEP520, KRS, UV-III, P (SI-CMS) etc.Adopt baking oven or hot plate to carry out the preceding baking of certain hour and uniform temperature to the good electronic corrosion-resistant 2 of above-mentioned coating then.
As shown in Figure 2, e-beam direct-writing exposure being carried out in the zone 3 and the zone 4 of positive corrosion-resisting agent 2, does not expose in zone 5,6.The interval in zone 3 and zone 4 is that unexposed regional 5 width is 100-400nm.The JBX-5000LS electron-beam lithography system that electron beam exposure can adopt JEOL company to produce, its accelerating voltage is 50KeV, electronic beam current is less than 100pA.
As shown in Figure 3, the positive corrosion-resisting agent that exposed is developed and photographic fixing, remove the electronic corrosion-resistant of exposure area, be formed for the Etching mask 9,10 of deposition of electrode material film.Because electron beam proximity effect, on the adjacent domain of exposure area 3,4, can produce additional exposure, the width of the actual groove figure 7,8 that obtains after the development is greater than the width of design exposure area 3,4, and the width of the resist 9 that the centre stays is also corresponding to designing the not width of exposure area 5.By technology controlling and process, the interval of groove pattern 7,8 is that the width of resist 9 can reach below the 100nm.
As shown in Figure 4, adopt the electrode material membrane 11,12,13 of evaporation or sputtering method depositing Al, Pt, Au, Ag, W, Ti, Cr, ITO single or multiple lifts such as (transparent) conduction, the thickness of electrode film 11,12,13 is lower than the thickness of electronic corrosion-resistant mask 9,10, electrode film is discontinuous, a part (16) is deposited on the electronic corrosion-resistant mask 9,10, another part is deposited on the substrate 1, forms required nano-electrode 11,12.
As shown in Figure 5, adopt acetone immersion, the ultrasonic metal electrode film 13 of peeling off Etching mask 9,10 and top thereof, the interval of finishing on substrate 1 only is the preparation of the nano-electrode 11,12 of 30-100nm.
Specific embodiment
To use ZEP520 positive electronic corrosion-resistant, evaporation Cr/Au double-level-metal electrode film to be example, further specify detailed process method of the present invention and step in conjunction with the accompanying drawings below, wherein:
As shown in Figure 1, in surfacing, clean length SiO is arranged
2With sol evenning machine coating individual layer ZEP520 positive electronic corrosion-resistant 2, the coating rotating speed is 2000rpm on the Si substrate 1 of dielectric film, and the coating time is 60 seconds, and resist thickness is 485nm.Then with baking before baking oven is under 180 ℃ 20 minutes.
As shown in Figure 2, e-beam direct-writing exposure being carried out in the zone 3 and the zone 4 of ZEP520 resist 2, does not expose in zone 5,6.The width in zone 3 and zone 4 is 350nm, and the interval in zone 3 and zone 4 is that unexposed regional 5 width is 250nm.Electron beam exposure can adopt the JEOLJBX-5000LS electron-beam lithography system, and accelerating voltage is 50KeV, and electronic beam current is 100pA, and exposure dose is 170 μ C/cm
2
As shown in Figure 3, use pentyl acetate developing liquid developing 2 minutes, use methyl iso-butyl ketone (MIBK) (MIBK) fixing solution photographic fixing 15 seconds immediately, form the Etching mask 9,10 of electrode material membrane deposit.The width of the actual groove figure 7,8 that obtains after development, the photographic fixing is greater than the width of design exposure area 3,4, and the width of the ZEP520 resist 9 that the centre stays is also corresponding to designing the not width of exposure area 5.The interval of groove pattern 7,8 is that the width of resist 9 can reach below the 100nm.In the SEM section photo shown in Figure 6, the top spacing of ZEP520 resist groove pattern is 90nm, and the bottom spacing is 60nm.
As shown in Figure 4, evaporation 50nm thick Cr/Au metal electrode material film 11,12,13, wherein the Au layer after, mainly utilize its good electrical conductivity; The Cr layer is thinner, rises to strengthen Au and SiO
2The adhering effect of substrate.The Cr/Au gross thickness is lower than the thickness of ZEP520 Etching mask 9,10, and the Cr/Au film is discontinuous, and a part of Cr/Au film (16) is deposited on the ZEP520 Etching mask 9,10, and another part is deposited on Si/SiO
2On the substrate 1, form required Cr/Au nano-electrode 11,12.
As shown in Figure 5, adopt acetone soak, ultrasonic peel off ZEP520 Etching mask 9,10 and on Cr/Au metal electrode film 13, finish the preparation that is spaced apart the Cr/Au nano-electrode 11,12 below the 100nm on substrate 1.In the SEM surface picture shown in Figure 7, the spacing of the Cr/Au metal nano electrode for preparing is 60nm, and white portion is the Cr/Au electrode among the figure.
Claims (6)
1, a kind of employing positive electronic corrosion-resistant utilizes electron beam lithography, metal deposit and stripping technology to prepare the method for metal nano electrode, it is characterized in that, comprises the steps:
(1) on substrate, applies positive electronic corrosion-resistant;
(2) preceding baking;
(3) e-beam direct-writing exposure;
(4) develop;
(5) photographic fixing;
(6) deposition of electrode material;
(7) peel off.
2, the method for preparing metal nano electrode according to claim 1 is characterized in that, wherein the substrate described in the step (1) is smooth dielectric substrate or high-resistance semi-conductor substrate, and substrate uses SiO
2, Si
3N
4, Al
2O
3, MgO, CaO, Si, the Ge of high-impedance state, GaAs, GaN, InP, InAs, ZnO, ZnS, CdS, described positive electronic corrosion-resistant adopts PMMA, ZEP520, KRS, UV-III, P single or multiple lift resist.
3, the method for preparing metal nano electrode according to claim 1, it is characterized in that, wherein the e-beam direct-writing exposure described in the step (3) adopts JEOL JBX-5000LS electron-beam lithography system, its accelerating voltage is 50KeV, electronic beam current is less than 100pA, and electrode pattern is spaced apart 100-400nm in the exposure layout design.
4, the method for preparing metal nano electrode according to claim 1, it is characterized in that, wherein the groove pattern of the positive electronic corrosion-resistant that forms after the photographic fixing described in development described in the electron beam exposure described in the step (3), the step (4) and the step (5) must have " undercutting " section structure, top is wider than in the bottom that is groove, so that follow-up peeling off.
5, the method for preparing metal nano electrode according to claim 1, it is characterized in that, wherein the electrode material described in the step (6) is Al, Pt, Au, Ag, W, Ti, Cr, ITO single or multiple lift electrode material, the gross thickness of electrode material must be less than the thickness of electronic corrosion-resistant, and electrode material can adopt method deposits such as evaporation, sputter.
6, the method for preparing metal nano electrode according to claim 1 is characterized in that, wherein peeling off described in the step (7) needs to soak in acetone earlier, sonic oscillation in acetone then, thereby peel off electronic corrosion-resistant and on electrode material.
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| CNB2005101304382A CN100495647C (en) | 2005-12-08 | 2005-12-08 | Method for adopting positive electronic corrosion-resistant to prepare metal nano electrode |
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| CN100495647C CN100495647C (en) | 2009-06-03 |
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| CN101246817B (en) * | 2008-02-29 | 2010-06-02 | 南京大学 | Method for producing silicon quantum wire on insulating layer |
| CN101872134A (en) * | 2010-06-09 | 2010-10-27 | 中国科学院半导体研究所 | Method for improving electron beam exposure efficiency |
| CN101382733B (en) * | 2008-09-27 | 2011-04-20 | 中国科学院微电子研究所 | Method for making graphics of nanometer dimension |
| CN101510050B (en) * | 2009-03-25 | 2011-09-07 | 中国科学院微电子研究所 | Method for extracting electron-beam exposure scattering parameter |
| CN102211755A (en) * | 2010-04-02 | 2011-10-12 | 中国科学院沈阳自动化研究所 | Nanoscale electrode processing method based on AFM (atomic force microscopy) |
| CN101800242B (en) * | 2009-02-11 | 2013-03-06 | 中国科学院微电子研究所 | Nano electron device using nanocrystal material as Coulomb island and manufacture method thereof |
| CN103077888A (en) * | 2013-01-11 | 2013-05-01 | 西安交通大学 | Method for preparing electrode on single nano wire |
| US8679853B2 (en) | 2003-06-20 | 2014-03-25 | Roche Diagnostics Operations, Inc. | Biosensor with laser-sealed capillary space and method of making |
| CN103868766A (en) * | 2012-12-18 | 2014-06-18 | 中国科学院物理研究所 | Preparation method of length standard sample for length measurement of scanning electron microscopy |
| CN104409597A (en) * | 2014-11-14 | 2015-03-11 | 无锡科思电子科技有限公司 | Electrode manufacturing method in red LED (Light Emitting Diode) chip manufacturing process |
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| US8679853B2 (en) | 2003-06-20 | 2014-03-25 | Roche Diagnostics Operations, Inc. | Biosensor with laser-sealed capillary space and method of making |
| CN101246817B (en) * | 2008-02-29 | 2010-06-02 | 南京大学 | Method for producing silicon quantum wire on insulating layer |
| CN101382733B (en) * | 2008-09-27 | 2011-04-20 | 中国科学院微电子研究所 | Method for making graphics of nanometer dimension |
| CN101800242B (en) * | 2009-02-11 | 2013-03-06 | 中国科学院微电子研究所 | Nano electron device using nanocrystal material as Coulomb island and manufacture method thereof |
| CN101510050B (en) * | 2009-03-25 | 2011-09-07 | 中国科学院微电子研究所 | Method for extracting electron-beam exposure scattering parameter |
| CN102211755A (en) * | 2010-04-02 | 2011-10-12 | 中国科学院沈阳自动化研究所 | Nanoscale electrode processing method based on AFM (atomic force microscopy) |
| CN102211755B (en) * | 2010-04-02 | 2014-02-12 | 中国科学院沈阳自动化研究所 | Nanoscale electrode processing method based on AFM (atomic force microscopy) |
| CN101872134B (en) * | 2010-06-09 | 2012-05-23 | 中国科学院半导体研究所 | Method for improving electron beam exposure efficiency |
| CN101872134A (en) * | 2010-06-09 | 2010-10-27 | 中国科学院半导体研究所 | Method for improving electron beam exposure efficiency |
| CN103868766A (en) * | 2012-12-18 | 2014-06-18 | 中国科学院物理研究所 | Preparation method of length standard sample for length measurement of scanning electron microscopy |
| CN103077888A (en) * | 2013-01-11 | 2013-05-01 | 西安交通大学 | Method for preparing electrode on single nano wire |
| CN103077888B (en) * | 2013-01-11 | 2015-07-01 | 西安交通大学 | Method for preparing electrode on single nano wire |
| CN104409597A (en) * | 2014-11-14 | 2015-03-11 | 无锡科思电子科技有限公司 | Electrode manufacturing method in red LED (Light Emitting Diode) chip manufacturing process |
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| CN100495647C (en) | 2009-06-03 |
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Owner name: SEMICONDUCTOR MANUFACTURING INTERNATIONAL (SHANGHA Free format text: FORMER OWNER: INST OF MICROELECTRONICS, C. A. S Effective date: 20130419 Owner name: INST OF MICROELECTRONICS, C. A. S Effective date: 20130419 |
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Effective date of registration: 20130419 Address after: 201203 Shanghai City, Pudong New Area Zhangjiang Road No. 18 Patentee after: Semiconductor Manufacturing International (Shanghai) Corporation Patentee after: Institute of Microelectronics, Chinese Academy of Sciences Address before: 100029 Beijing city Chaoyang District Beitucheng West Road No. 3 Patentee before: Institute of Microelectronics, Chinese Academy of Sciences |