CN101794072B - Method for preparing substrate with nano structure with line width below 20 nanometers - Google Patents
Method for preparing substrate with nano structure with line width below 20 nanometers Download PDFInfo
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- CN101794072B CN101794072B CN201010034315XA CN201010034315A CN101794072B CN 101794072 B CN101794072 B CN 101794072B CN 201010034315X A CN201010034315X A CN 201010034315XA CN 201010034315 A CN201010034315 A CN 201010034315A CN 101794072 B CN101794072 B CN 101794072B
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Abstract
The invention discloses a method for preparing a substrate with a nano structure with the line width below 20 nanometers. The method comprises the following steps: (1) growing a single-layer nano layer in an epitaxial way on the substrate by utilizing a chemical gas-phase deposition method; (2) transferring the single-layer nano layer to an SiO2/Si compound substrate, or growing other substrates with the nano structure on a Si substrate by a sputtering method; (3) preparing a polymethylmethacrylate layer on the single-layer nano layer and drying; (4) exposing the polymethylmethacrylate layer to obtain a patterned polymethylmethacrylate layer; removing the unexposed polymethylmethacrylate to obtain a polymethylmethacrylate negative photoresist pattern used as a mask; (5) etching the mask to decrease the line width of the mask below 20 nanometers; and (6) sequentially etching the mask obtained after finishing the etching in the step (5) and removing the single-layer nano layer which is not protected by the mask to obtain the substrate with the single-layer nano structure with the line width below 20 nanometers. The method is suitable for etching various substrate materials, thereby preparing a corresponding pattern the size of which can reach few nanometers on the substrate.
Description
Technical field
The invention belongs to nanosecond science and technology and advanced material field, relate to the method for the following nano-structured matrix of a kind of preparation 20 nano-scale linewidths.
Background technology
Mono-layer graphite refers to the Graphene of the plane regular hexagon cellular structure that is made up of one deck carbon atom, is prepared first through the method for mechanical cleavage by the A.K.Geim of Britain Man Qiesidun university professor seminar in 2004.
Flawless mono-layer graphite is the semi-metallic of no band gap; Charge carrier has very long free path and very high mobility in the communication process of mono-layer graphite; And high-temperature stability that graphite itself has simultaneously and physical strength make it have good prospect at a high speed and in the high-performance electronic device in preparation.Through width is carried out special selective etch and modification less than the edge of 20 nano-graphite bands; Or the doping through particular solution or atmosphere; Can semimetallic mono-layer graphite be transformed into the semiconductor material of N type or P type, for the application of mono-layer graphite on large scale integrated circuit provides possibility.
Realize the device application of mono-layer graphite, how preparing the mono-layer graphite with given shape and array structure is problem demanding prompt solution; And to realize the preparation and the application of mono-layer graphite quantum device, how to obtain less than the mono-layer graphite structure of 20 nano-scale linewidths important techniques difficult problem especially.
In order to prepare the mono-layer graphite graphic structure that can be used for quantum device on a large scale expeditiously; This method is at first prepared the photoresist mask plate of large ratio of height to width, minimum live width through electron beam overexposure PMMA photoresist on the mono-layer graphite sheet of having prepared; The live width that further controllably reduces mask plate gradually through the oxygen reactive ion etching technology then is below 20 nanometers; Etch away the mono-layer graphite beyond the mask plate restraining barrier through Ar+ ion etching technology more at last, thereby obtain the mono-layer graphite sample of live width, for use in the preparation of mono-layer graphite nano-device less than 20 nanometers.
Summary of the invention
The purpose of this invention is to provide the method that a kind of preparation has the following nano-structured matrix of 20 nano-scale linewidths.
The invention provides two kinds of preparation methods, wherein, preparation has the method for the following mono-layer graphite matrix of 20 nano-scale linewidths, comprises the steps:
1) epitaxial growth mono-layer graphite layer on substrate;
2) the mono-layer graphite layer that said step 1) is obtained is transferred to SiO
2On/Si the compound substrate;
3) in said step 2) preparation polymethyl methacrylate layers and oven dry on the mono-layer graphite layer that obtains;
4) polymethyl methacrylate layers that said step 3) is obtained is made public, and obtains the polymethyl methacrylate layers of patterning; Remove unexposed polymethylmethacrylate, obtain as the negative glue pattern of the polymethylmethacrylate of mask;
5) mask that said step 4) is obtained carries out etching, and the live width of said mask is decreased to below 20 nanometers;
6) the said step 5) etching mask that obtains that finishes is proceeded etching, remove the single-layer nano layer that does not have mask protection, obtain said method with the following mono-layer graphite matrix of 20 nano-scale linewidths.
In the step 1) of this method, the material of said formation substrate is copper or nickel; Said reaction gas is selected from least a in methane, ethene and the acetylene; Said carrier gas is a hydrogen; The thickness of said substrate is the 700-50000 nanometer, specifically can be 700-40000 nanometer, 700-35000 nanometer, 700-25000 nanometer, 700-10000 nanometer, 700-9000 nanometer, 700-5000 nanometer or 700-4500 nanometer, preferred 700 nanometers; The thickness of said mono-layer graphite layer is the 0.9-1.35 nanometer, specifically can be 0.9-1.2 nanometer or 1.0-0.35 nanometer, preferred 1.35 nanometers; The pressure of deposition is 500-1300mTorr, specifically can be 500-1200mTorr, 600-1300mTorr, 600-1000mTorr, 500-1000mTorr, 500-800mTorr or 550-1000mTorr, preferred 500mTorr; The temperature of deposition is 850-1050 ℃, specifically can be 850-1000 ℃, 850-950 ℃ or 850-900 ℃, preferred 850 ℃; The flow of reaction gas is 2-30SCCM, specifically can be 2-10SCCM, 2-25SCCM, 5-30SCCM, 10-30SCCM, 10-25SCCM or 5-25SCCM, preferred 30SCCM; The time of deposition is 15-60 minute, preferred 30 minutes;
Said step 2) in, said SiO
2/ Si substrate is to be the SiO of 280-320 nanometer by thickness
2Layer and thickness are that the p type Si substrate layer of 500-800 micron is formed; Said mono-layer graphite layer and said SiO
2Layer contact.In this step, said mono-layer graphite layer is transferred to SiO
2Method on the/Si compound substrate is a conventional method, and its concrete steps are:
(1) use speed spin coating one deck PMMA 671.06 of 4000 revolutions per seconds at copper foil surface, hot platform drying glue 4 minutes, natural cooling is designated as sample A;
(2) sample A is put into the FeCl of 0.05g/mL
3Or Fe (NO
3)
3In the solution, reacted 24 hours, dissolve and remove Copper Foil, stay PMMA film and mono-layer graphite membrane suspension, be designated as sample B in solution surface;
(3) with sample B flush away residual Fe Cl in deionized water
3Solution uses to be coated with 300nm thickness SiO
2The Si sheet of layer picks up sample B;
(4) dropwise splash into acetone at sample B edge,, leave standstill up to acetone and volatilize fully, sample B surface PMMA film portion dissolving this moment, lower floor's mono-layer graphite and SiO until submergence sample B
2Combine closely in the surface, this SiO that covers
2Mono-layer graphite film on the/Si compound substrate is designated as sample C;
(5) sample C is put into acetone soln, dissolve and remove remaining PMMA photoresist, use alcohol, deionized water to clean successively, nitrogen dries up;
(6) sample C is put into quartz ampoule, pass through quartz ampoule, annealed 2 hours down, obtain being transferred to SiO at 450 ℃ with 500SCCM argon gas and 500SCCM hydrogen flowing quantity
2High-quality mono-layer graphite layer on the/Si compound substrate.
In the said step 3), the thickness of said polymethyl methacrylate layers is the 50-300 nanometer, preferred 130 nanometers; The said method for preparing polymethyl methacrylate layers is a spin-coating method; In the said spin-coating method, the speed of spin coating is 2000-6000 revolutions per second, preferred 4000 revolutions per seconds; The temperature of oven dry is 170-250 ℃, and preferred 180 ℃, the time of oven dry is 60-300 second, preferred 90 seconds;
In the said step 4), the live width of the polymethyl methacrylate layers of said patterning is the 20-500 nanometer, specifically can be 20-450 nanometer, 20-400 nanometer, 20-300 nanometer, 20-250 nanometer or 20-100 nanometer, preferred 20 nanometers; The dosage of exposure is 7500-45000uAs/cm
2Specifically can be 7500-9000uAs/cm, 8000-45000uAs/cm, 8500-45000uAs/cm, 8500-35000uAs/cm, 8500-9000uAs/cm, 10000-45000uAs/cm, 20000-45000uAs/cm or 30000-45000uAs/cm, preferred 8500uAs/cm
2Step pitch is the 1.6-25.6 nanometer, specifically can be 1.6-20 nanometer, 1.6-15 nanometer, 1.6-10 nanometer or 1.6-15 nanometer, preferred 1.6 nanometers; The accelerating potential of exposure is 5-15kV, preferred 10kV; During the unexposed polymethylmethacrylate of said removal, select for use acetone as solvent;
In the said step 5), the method for etching is the reactive ion etching method, and the gas of etching is selected from oxygen; The flow of the gas of said etching is 20-40SCCM, preferred 30SCCM; The reaction power of etching is 15-40W, preferred 20W; The time of etching is 30-60 second, preferred 30 seconds;
In the said step 6), the method for said etching is the argon ion etching method; In the said etch step, accelerating potential is 400-600eV, specifically can be 400-500eV, 450-550eV, 450-600eV or 500-600eV, preferred 450eV; The electric current of ion beam is 60-100mA, specifically can be 65-95mA, 60-90mA, 65-90mA or 70-80mA, preferred 70mA; The time of etching is 30-300 second, specifically can be 30-90 second, 35-85 second, 40-100 second, 50-70 second, 100-300 second, 50-300 second, 200-300 second, 150-300 second or 150-250 second, preferred 60 seconds.
Have an application in preparation mono-layer graphite nano-device of the following mono-layer graphite matrix of 20 nano-scale linewidths and this mono-layer graphite matrix according to what above-mentioned preparation method obtained, also belong to protection scope of the present invention.
Preparation provided by the invention has the method for the nano-structured matrix below 20 nano-scale linewidths, comprises the steps:
1) preparation metal film layer nano-structured matrix on substrate;
2) preparation polymethyl methacrylate layers and oven dry on the metal film layer that said step 1) obtains;
3) with said step 2) polymethyl methacrylate layers that obtains makes public, and obtains the polymethyl methacrylate layers of patterning; Remove unexposed polymethylmethacrylate, obtain as the negative glue pattern of the polymethylmethacrylate of mask;
4) mask that said step 3) is obtained carries out etching, and the live width of said mask is decreased to below 20 nanometers;
5) the mask continuation etching that said step 4) etching is finished and obtains is removed the single-layer nano layer that does not have mask protection, obtains the said nano-structured matrix that has below 20 nano-scale linewidths.
In the step 1) of this method, various substrates commonly used all are applicable to this method, like silicon substrate; The method for preparing said metal film layer nano-structured matrix is ion beam sputtering or thermal evaporation; In the said ion beam sputtering, the ion energy that sputter is used is 400-600eV, specifically can be 400-500eV, 450-550eV, 450-600eV or 500-600eV; Preferred 450eV, line is 60-80mA, specifically can be 65-75mA, 60-70mA, 65-70mA or 70-80mA; Preferred 70mA; Sputtering time is 1～60 minute, specifically can be 5-40 minute, 5-50 minute, 8-12 minute, 10-50 minute, 15-45 minute or 5-10 minute, preferred 8 minutes; In the said thermal evaporation; Heating current is 50A-80A; Preferred 60A; Sedimentation velocity is
preferred
sedimentation time 20 minutes-120 minutes; Specifically can be 20-50 minute, 25-120 minute, 25-35 minute, 25-110 minute, 25-100 minute, 50-110 minute, 50-120 minute, 30-100 minute or 20-40 minute, preferred 30 minutes.
Said step 2) in, the thickness of said polymethyl methacrylate layers is the 50-300 nanometer, preferred 130 nanometers; The said method for preparing polymethyl methacrylate layers is a spin-coating method; In the said spin-coating method, the speed of spin coating is 2000-6000 revolutions per second, preferred 4000 revolutions per seconds; The temperature of oven dry is 170-250 ℃, and preferred 180 ℃, the time of oven dry is 60-300 second, preferred 90 seconds;
In the said step 3), the live width of the polymethyl methacrylate layers of said patterning is the 20-500 nanometer, preferred 20 nanometers; In the step of exposure, dosage is 7500-45000uAs/cm
2Specifically can be 7500-9000uAs/cm, 8000-45000uAs/cm, 8500-45000uAs/cm, 8500-35000uAs/cm, 8500-9000uAs/cm, 10000-45000uAs/cm, 20000-45000uAs/cm or 30000-45000uAs/cm, preferred 8500uAs/cm
2, step pitch is the 1.6-25.6 nanometer, specifically can be 1.6-20 nanometer, 1.6-15 nanometer, 1.6-10 nanometer or 1.6-15 nanometer; Preferred 1.6 nanometers, accelerating potential are 5-15kV, preferred 10kV; During the unexposed polymethylmethacrylate of said removal, select for use acetone as solvent;
In the said step 4), the method for said etching is the reactive ion etching method, and the gas of etching is selected from oxygen; The flow of the gas of said etching is 20-40SCCM, preferred 30SCCM; The reaction power of etching is 15-40W, preferred 20W; The time of etching is 30-60 second, preferred 30 seconds;
In the said step 5), the method for said etching is the argon ion etching method; In the said etch step, accelerating potential is 400-600eV, preferred 450eV; The electric current of reactive ion beam is 60-100mA, preferred 70mA; The time of etching is 30-300 second, preferred 60 seconds.
What prepare according to the method described above has nano-structured matrix and the application of this nano-structured matrix in the preparation nano-device below 20 nano-scale linewidths, also belongs to protection scope of the present invention.
In each step of above-mentioned two methods, be to guarantee the cleanliness factor of sample, all experimental implementation remain in the ultra-clean chamber of 100 cleanliness factors and accomplish; All equipment that contact with sample are the ultrasonic cleaning through acetone, absolute ethyl alcohol, deionization ultra-clean water all; In preparation, beamwriter lithography, oxygen reactive ion etching, the Ar+ ion etching of sample are operated, all remain in the corresponding high vacuum of instrument; In the characterization of sample, sample is kept in the confined space of electrostatic isolation all the time.
The present invention uses the negative glue pattern of PMMA as mask plate; Mainly based on following some: (1) PMMA is during as the positive glue of electron beam exposure; In the preparation live width during less than the figure of 50 nanometer rice; Not only need very high electron accelerating voltage, and the adhesion of figure for preparing and substrate is very poor, comes off easily.And under the situation of high dose; Bonding can take place in PMMA molecule once more after chain rupture; Improved the resolution of photoresist greatly; Even obtain the fine pattern about 20 nanometers also can making public under the very low electron accelerating voltage, have good bonding force between figure and the substrate simultaneously, obscission can not take place.(2) the negative glue of PMMA not only can directly be prepared the mask plate figure near 20 nano-scale linewidths through electron beam exposure, and can react with oxonium ion because of it as mask plate, thereby can be so that this mask plate can further be thinned.(3) the negative glue pattern of PMMA has good insulation performance property and stability; The negative glue mask plate of PMMA that after argon ion etching, is retained in the mono-layer graphite sample surfaces not only can not influence the transport property of graphite itself; And can be used as the insulation course of top grid, for further various nano-devices of preparation bring great convenience.
Negative glue reversal effect when the present invention utilizes the PMMA overexposure is at first prepared the photoresist figure near 20 nano-scale linewidths; Utilize the negative glue pattern of PMMA to react with oxonium ion again, further attenuate obtains littler live width, keeps etching power 20W this moment; Mono-layer graphite is the chemically stable state; Can do not obtained less than after the negative glue mask plate of the PMMA of 20 nanometers, in the process of using argon ion etching by the oxonium ion reactive ion etching; Because the negative glue mask plate of the PMMA for preparing has very big depth-width ratio; Thickness is much larger than mono-layer graphite, thereby can guarantee after mono-layer graphite is etched, still to exist as mask, so that as the insulation course on the sample on the mono-layer graphite.Method provided by the invention not only can be used to the etching mono-layer graphite, also can be used to any backing material of etching, thereby on substrate, prepares the respective graphical that size can reach several nanometers.
This method of reducing photoresist through the oxonium ion reactive ion etching not only can be used for reducing the negative glue mask plate of PMMA, also can be used for reducing the mask plate (etch rate of substrate is much smaller than the etch rate of mask plate) that other can react with oxonium ion; Also can be through changing the kind of reactive ion, reduce the mask plate that other can not reduce with oxonium ion.
After negative glue etches the mono-layer graphite sample with special pattern as mask plate through PMMA; Can also use the negative glue of the PMMA that remains as insulation course, prepare the top gate electrode easily and efficiently or prepare quantum device through multiple spin coating with space framework.
The invention provides the method for a kind of efficient, simple and quick preparation live width that controllability is strong less than the individual layer figure matrix of 20 nanometers.When glue is born in the PMMA conduct; Not only (10keV) can obtain very high resolution (20 nanometer) under lower electron accelerating voltage; The PMMA of unexposed area then can remove through the cleaning of acetone; Very long time shutter when having avoided the positive glue of PMMA, improved the efficient of figure preparation greatly as mask plate; And this mask plate can also be controllably under the oxygen reactive ion etching further attenuate with dwindle, thereby obtain the negative glue pattern mask plate of PMMA below 20 nanometers.The mask plate that produces through the PMMA overexposure simultaneously can also solve the difficulty of graphite quantum device top grid preparation as insulation course dexterously after etching.
Description of drawings
Fig. 1 uses PMMA to prepare the mono-layer graphite band process synoptic diagram of the following live width of 20 nanometers as negative glue mask plate.
The large ratio of height to width fine pattern SEM image of Fig. 2 for using PMMA 495K under the situation of overexposure, to obtain.
Fig. 3 for (a1) before using the oxygen reactive ion to the negative glue mask plate etching of PMMA (b1) with etching after (a2) (b2) graphic width change.
Fig. 4 is the comparison of mono-layer graphite (a1) back (a2) before the oxygen reactive ion etching of same area.
Fig. 5 is the comparison of the negative glue mask plate figure of the PMMA of same area and mono-layer graphite (a) back (b) before argon ion etching.
Fig. 6 is for using the Au nano wire SEM image of same process preparation less than 20 nanometers.
The SEM image of the Cu nano wire that Fig. 7 prepares for embodiment 3; Wherein, Fig. 7 a is for having afterwards the SEM image of the Cu figure of the negative glue mask plate of PMMA through Ar ion etching, Fig. 7 b is the SEM image of the Cu nanometer lines about the high wide 20nm of being that obtains after the etching.
Embodiment
Below in conjunction with specific embodiment the present invention is described further, but the present invention is not limited to following examples.
Through the method for thermal oxide, the SiO of growth one deck 300 nanometer thickness on the boron doped Si sheet of (111) orientation p type
2Layer.Subsequently, silicon chip is cut into the fritter of 1cm * 1cm, through acetone, absolute ethyl alcohol, deionized water ultrasonic five minutes respectively, nitrogen dried up subsequent use, and above-mentioned fritter silicon chip is designated as substrate A.
1) in quartz ampoule, pack into the Copper Foil (available from Alfa Aesar company, goods number is No.13382) of 1cm * 1cm passes to hydrogen with 2SCCM earlier under the pressure of 40mTorr; And be warming up to 850 ℃ gradually; Keep temperature and hydrogen flowing quantity constant, under 500mTorr pressure, passed to methane 30 minutes, be cooled to room temperature then rapidly with 30SCCM; Preparing thickness is the mono-layer graphite sample of 1.35 nanometers, shown in Fig. 1 a;
2) at the mono-layer graphite sample surfaces with 671.06,180 ℃ of hot platform drying glues of 4000 revolutions per seconds of spin coating PMMA 5 minutes, behind the natural cooling at the Fe of 0.05g/mL (NO
3)
3Soak one day one night in the solution, remove Copper Foil, obtain to float over solution surface adhesion the PMMA film of mono-layer graphite, be designated as film B, with said film B flush away residual Fe (NO in deionized water
3)
3Behind the solution, use substrate A in above-mentioned solution, to pick up film B, dropwise splash into acetone,, leave standstill up to acetone and volatilize fully, film B surface PMMA film portion dissolving this moment, lower floor's mono-layer graphite and SiO until submergence film B at film B edge
2Combine closely in the surface, this SiO that covers
2Mono-layer graphite film on the/Si compound substrate is designated as film C, and C puts into acetone soln with film, dissolves to remove remaining PMMA photoresist; Use alcohol, deionized water to clean successively; Nitrogen dries up, and C puts into quartz ampoule with film, passes through quartz ampoule with 500SCCM argon gas and 500SCCM hydrogen flowing quantity; Annealed 2 hours down at 450 ℃, can obtain being transferred to SiO
2High-quality mono-layer graphite layer on the/Si compound substrate;
3) in step 2) the mono-layer graphite laminar surface that obtains is with 4000 revolutions per seconds of spin coating PMMA 495K; Even glue 40 seconds; The drying glue in 90 seconds of 180 ℃ of hot platforms obtains the photoresist that thickness is 130 nanometers, puts into electron beam lithography machine (Raith e Line) behind the natural cooling and carries out etching.
4) under the 10kV accelerating potential, use 7500uAs/cm
2Exposure dose, the step pitch of 1.6 nanometers, the negative glue mask plate pattern of the exposure PMMA that obtains designing is shown in Fig. 1 c and d.The large ratio of height to width fine pattern SEM image of Fig. 2 for using PMMA 495K under the situation of overexposure, to obtain.
5) under the oxygen flow of 30SCCM, with the etching power of 20W, used oxonium ion reactive ion etching machine engraving erosion sample 30 seconds, further below negative glue mask plate to 20 nano-scale linewidth of attenuate PMMA, shown in Fig. 1 e.Fig. 3 is that (a2) after (a1) before using the oxygen reactive ion to the negative glue mask plate etching of PMMA, (b1) and the etching, (b2) graphic width change.Wherein, Fig. 3 (a1), (b1) are on the mono-layer graphite that the method through chemical vapor deposition prepares; Through the figure that the PMMA overexposure obtains, Fig. 3 (a2), (b2) are in the oxygen reactive ion etching machine, with the etching power of 20W; Pass under the oxygen flow condition of 30SCCM the contrast of the attenuate of etching PMMA mask plate after 30 seconds.Fig. 4 is the comparison of mono-layer graphite (a1) back (a2) before the oxygen reactive ion etching of same area.Among the figure in the frame of broken lines the negative glue mask plate lines of PMMA can find out that under this etching power, even etch away the negative glue mask plate of PMMA fully, mono-layer graphite still has good stability, attenuate is not etched.
6) argon ion of use 450eV, under the 70mA line, etching sample 30 seconds obtains the mono-layer graphite pattern below live width 20 nanometers, and the negative glue mask plate width of PMMA does not have significant change, shown in Fig. 1 f.Fig. 5 is the comparison of the negative glue mask plate figure of the PMMA of same area and mono-layer graphite (a) back (b) before argon ion etching.Wherein, Fig. 5 (a1) and (a2) be in the argon ion etching machine, with the beam current density of 70mA, under the 450eV ion energy, the comparison diagram before and after the etching 60 seconds.Can find out that the mono-layer graphite that obtains through the CVD growth is etched fully, the zone of multilayer also obviously is thinned, and the width of PMMA mask plate does not have obvious variation; Fig. 5 (b) is the SEM figure after the argon ion etching, can find out, does not have the regional mono-layer graphite of the negative glue mask plate protection of PMMA to be etched totally.
Embodiment 2
Silicon chip is cut into the fritter of 1cm * 1cm, and through acetone, absolute ethyl alcohol, deionized water ultrasonic five minutes respectively, nitrogen dried up subsequent use.
1) on silicon chip, obtain the Au film that thickness is 280 nanometers through ion beam sputtering, sputter uses ion energy to be 450eV, and line is 70mA, and sputtering time is 40min.
2) at sample surfaces with 3000 revolutions per seconds of spin coating PMMA 495K, even glue 60 seconds, the drying glue in 90 seconds of 180 ℃ of hot platforms obtains the photoresist that thickness is 140 nanometers, puts into electron beam lithography machine (Raith e Line) behind the natural cooling and carries out etching.
3) under the 10kV accelerating potential, use 8500uAs/cm
2Exposure dose, the step pitch of 1.6 nanometers, the negative glue mask plate pattern of the exposure PMMA that obtains designing
4) under the oxygen flow of 30SCCM, with the etching power of 15W, used oxonium ion reactive ion etching machine engraving erosion sample 60 seconds, further below negative glue mask plate to 20 nano-scale linewidth of attenuate PMMA
5) argon ion of use 450eV; Under the 70mA line; Etching sample 5-10 minute obtains the Au line image that has the negative glue mask plate remnants of part PMMA below live width 20 nanometers, uses the oxygen reactive ion etching long enough time; Remove the negative glue mask plate pattern of remaining PMMA, promptly obtain the figure of various live widths less than the Au of 20 nanometers.
Fig. 6 is for prepare the SEM image of gained live width less than the Au nano wire of 20 nanometers according to the method described above.Wherein, Fig. 6 (a1) and (a2) shown the thinning process of the negative glue mask plate of PMMA before and after the oxygen reactive ion etching 30s; (a1) the negative glue pattern that obtains for overexposure PMMA on the Au substrate; (a2) be through the negative glue of the PMMA as mask plate of peroxide reactive ion attenuate.Fig. 6 (b1) and (b2) to be respectively with the negative glue of PMMA be the large ratio of height to width Au lines less than 20 nanometers that mask plate obtains through argon ion etching.
Embodiment 3,
Silicon chip is cut into the fritter of 1cm * 1cm, and through acetone, absolute ethyl alcohol, deionized water ultrasonic five minutes respectively, nitrogen dried up subsequent use.
1) on silicon chip, obtain the Cu film that thickness is 20 nanometers through ion beam sputtering, sputter uses ion energy to be 450eV, and line is 70mA, and sputtering time is 8min.
2) at sample surfaces with 6000 revolutions per seconds of spin coating PMMA 495K, even glue 60 seconds, the drying glue in 90 seconds of 180 ℃ of hot platforms obtains the photoresist that thickness is 80 nanometers, puts into electron beam lithography machine (Raith e Line) behind the natural cooling and carries out etching.
3) under the 10kV accelerating potential, use 7500uAs/cm
2Exposure dose, the step pitch of 1.6 nanometers, the negative glue mask plate pattern of the exposure PMMA that obtains designing
4) under the oxygen flow of 30SCCM, with the etching power of 15W, used oxonium ion reactive ion etching machine engraving erosion sample 30 seconds, further below negative glue mask plate to 20 nano-scale linewidth of attenuate PMMA
5) argon ion of use 450eV, under the 70mA line, etching sample 1 minute uses the oxygen reactive ion etching long enough time, removes the negative glue mask plate pattern of remaining PMMA, promptly obtains the figure of live width less than the Cu of 20 nanometers.What a figure showed among Fig. 7 is through having the Cu figure of the negative glue mask plate of PMMA after the Ar ion etching; In oxonium ion reactive ion etching machine with the 30SCCM oxygen flow; 35W power etching 10 minutes promptly obtains the nanometer lines (Fig. 7 b) of the Cu about the high wide 20nm of being.
Claims (12)
1. one kind prepares the method with the following mono-layer graphite matrix of 20 nano-scale linewidths, comprises the steps:
1) epitaxial growth mono-layer graphite layer on substrate; Wherein, the material that constitutes said substrate is copper or nickel;
2) the mono-layer graphite layer that said step 1) is obtained is transferred to SiO
2On/Si the compound substrate;
3) in said step 2) preparation polymethyl methacrylate layers and oven dry on the mono-layer graphite layer that obtains;
4) polymethyl methacrylate layers that said step 3) is obtained is made public, and obtains the polymethyl methacrylate layers of patterning; Remove unexposed polymethylmethacrylate, obtain as the negative glue pattern of the polymethylmethacrylate of mask;
5) mask that said step 4) is obtained carries out etching, and the live width of said mask is decreased to below 20 nanometers;
In the step 5), the method for said etching is the reactive ion etching method, and the gas of etching is selected from oxygen; The flow of the gas of said etching is 20-40SCCM; The reaction power of etching is 15-40W; The time of etching is 30-60 second;
6) the said step 5) etching mask that obtains that finishes is proceeded etching, remove the mono-layer graphite layer that does not have mask protection, obtain the said following mono-layer graphite matrix of 20 nano-scale linewidths that has;
In the step 6), the method for said etching is the reactive ion etching method; Reactive ion is selected from argon ion; In the said etch step, accelerating potential is 400-600eV; The electric current of reactive ion beam is 60-100mA; The time of etching is 30-300 second.
2. method according to claim 1 is characterized in that: in the said step 1), the method for epitaxial growth mono-layer graphite layer is the method for chemical vapor deposition on substrate; Reaction gas in the method for said chemical vapor deposition is selected from least a in methane, ethene and the acetylene, and carrier gas is a hydrogen; The thickness of said substrate is the 700-50000 nanometer; The thickness of said mono-layer graphite layer is the 0.9-1.35 nanometer;
Said step 2) in, said SiO
2/ Si substrate is to be the SiO of 280-320 nanometer by thickness
2Layer and thickness are that the p type Si substrate layer of 500-800 micron is formed; Said mono-layer graphite layer and said SiO
2Layer contact;
In the said step 3), the thickness of said polymethyl methacrylate layers is the 50-300 nanometer;
In the said step 4), the live width of the polymethyl methacrylate layers of said patterning is the 20-500 nanometer.
3. method according to claim 2 is characterized in that: in the said step 1), the thickness of said substrate is 700 nanometers; The thickness of said mono-layer graphite layer is 1.35 nanometers;
In the said step 3), the thickness of said polymethyl methacrylate layers is 130 nanometers;
In the said step 4), the live width of the polymethyl methacrylate layers of said patterning is 20 nanometers.
4. according to each described method among the claim 1-3, it is characterized in that: in the said step 1), the method for epitaxial growth mono-layer graphite layer is the method for chemical vapor deposition on substrate; The pressure that deposits in the method for said chemical vapor deposition is 500-1300mTorr; The temperature of deposition is 850-1050 ℃; The time of deposition is 15-60 minute; The flow of the reaction gas that is adopted is 2-30SCCM;
In the said step 3), the said method for preparing polymethyl methacrylate layers is a spin-coating method; In the said spin-coating method, the speed of spin coating is 2000-6000 revolutions per second; The temperature of oven dry is 170-250 ℃, and the time of oven dry is 60-300 second;
In the said step 4), the dosage of exposure is 7500-45000uAs/cm
2Step pitch is the 1.6-25.6 nanometer; The accelerating potential of exposure is 5-15kV; During the unexposed polymethylmethacrylate of said removal, select for use acetone as solvent;
In the said step 5), the flow of the gas of said etching is 30SCCM; The reaction power of etching is 20W; The time of etching is 30 seconds;
In the said step 6), in the said etch step, accelerating potential is 450eV; The electric current of reactive ion beam is 70mA; The time of etching is 60 seconds.
5. method according to claim 4 is characterized in that: in the said step 1), in the process of epitaxial growth mono-layer graphite layer, the pressure that is adopted is 500mTorr on substrate; The temperature that is adopted is 850 ℃; The time of being adopted is 30 minutes; The flow of the reaction gas that is adopted is 30SCCM;
In the said step 3), the said method for preparing polymethyl methacrylate layers is a spin-coating method; In the said spin-coating method, the speed of spin coating is 4000 revolutions per seconds; The temperature of oven dry is 180 ℃, and the time of oven dry is 90 seconds;
In the said step 4), the dosage of exposure is 8500uAs/cm
2Step pitch is 1.6 nanometers; The accelerating potential of exposure is 10kV.
6. the arbitrary said method of claim 1-5 prepares has the following mono-layer graphite matrix of 20 nano-scale linewidths.
7. claim 6 is said has the application of the following mono-layer graphite matrix of 20 nano-scale linewidths in preparation mono-layer graphite nano-device.
8. one kind prepares the method with the nano-structured matrix below 20 nano-scale linewidths, comprises the steps:
1) preparation metal film layer nano-structured matrix on substrate;
2) preparation polymethyl methacrylate layers and oven dry on the metal film layer that said step 1) obtains;
3) with said step 2) polymethyl methacrylate layers that obtains makes public, and obtains the polymethyl methacrylate layers of patterning; Remove unexposed polymethylmethacrylate, obtain as the negative glue pattern of the polymethylmethacrylate of mask;
4) mask that said step 3) is obtained carries out etching, and the live width of said mask is decreased to below 20 nanometers; In the step 4), the method for said etching is the reactive ion etching method, and the gas of etching is selected from oxygen; The flow of the gas of said etching is 20-40SCCM; The reaction power of etching is 15-40W; The time of etching is 30-60 second;
5) the mask continuation etching that said step 4) etching is finished and obtains is removed the single-layer nano layer that does not have mask protection, obtains the said nano-structured matrix that has below 20 nano-scale linewidths;
In the step 5), the method for said etching is the reactive ion etching method; Reactive ion is selected from argon ion; In the said etch step, accelerating potential is 400-600eV; The electric current of reactive ion beam is 60-100mA; The time of etching is 30-300 second.
9. method according to claim 8 is characterized in that: in the said step 1), said substrate is a silicon substrate;
Said step 2) in, the thickness of said polymethyl methacrylate layers is the 50-300 nanometer;
In the said step 3), the live width of the polymethyl methacrylate layers of said patterning is the 20-500 nanometer.
10. method according to claim 9 is characterized in that: said step 2), the thickness of said polymethyl methacrylate layers is 130 nanometers;
In the said step 3), the live width of the polymethyl methacrylate layers of said patterning is 20 nanometers.
11. each described method according to Claim 8-10 is characterized in that: in the said step 1), the method for preparing said metal film layer nano-structured matrix is ion beam sputtering or thermal evaporation; In the said ion beam sputtering, the ion energy that sputter is used is 400-600eV, and line is 60-80mA, and sputtering time is 1-60 minute; In the said thermal evaporation; Heating current is 50A-80A, and sedimentation velocity is 20 minutes-120 minutes for
sedimentation time;
Said step 2) in, the said method for preparing polymethyl methacrylate layers is a spin-coating method; In the said spin-coating method, the speed of spin coating is 2000-6000 revolutions per second; The temperature of oven dry is 170-250 ℃, and the time of oven dry is 60-300 second;
In the said step 3) step of exposure, dosage is 7500-45000uAs/cm
2, step pitch is the 1.6-25.6 nanometer, accelerating potential is 5-15kV, during the unexposed polymethylmethacrylate of said removal, selects for use acetone as solvent;
In the said step 4), the flow of the gas of said etching is 30SCCM; The reaction power of etching is 20W; The time of etching is 30 seconds;
In the said step 5), in the said etch step, accelerating potential is 450eV; The electric current of reactive ion beam is 70mA; The time of etching is 60 seconds.
12. method according to claim 11 is characterized in that: in the said step 1), in the said ion beam sputtering, the ion energy that sputter is used is 450eV, and line is 70mA, and sputtering time is 8 minutes; In the said thermal evaporation; Heating current is 60A, and sedimentation velocity is 30 minutes for
sedimentation time;
Said step 2) in, in the said spin-coating method, the speed of spin coating is 4000 revolutions per seconds; The temperature of oven dry is 180 ℃, and the time of oven dry is 90 seconds;
In the said step 3) step of exposure, dosage is 8500uAs/cm
2, step pitch is 1.6 nanometers, accelerating potential is 10kV.
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| CN104465326B (en) * | 2014-12-03 | 2017-05-31 | 复旦大学 | A kind of use Stencil optical gravings for non-damaging graphene nano-device method |
| CN105668546B (en) * | 2016-01-29 | 2019-03-08 | 中国科学院物理研究所 | A method of preparing the graphene-structured of nanoscale |
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