CN101613099A - The method of preparing patterned carbon nano-structured material by electron beam lithography - Google Patents
The method of preparing patterned carbon nano-structured material by electron beam lithography Download PDFInfo
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- CN101613099A CN101613099A CN200910117348A CN200910117348A CN101613099A CN 101613099 A CN101613099 A CN 101613099A CN 200910117348 A CN200910117348 A CN 200910117348A CN 200910117348 A CN200910117348 A CN 200910117348A CN 101613099 A CN101613099 A CN 101613099A
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Abstract
The invention provides a kind of method that adopts the electron beam exposure polymethyl methacrylate film to prepare the patterned carbon nano material.This method is earlier about 1 * 10
-5Under the vacuum of Pa, adopt the electron beam exposure polymethyl methacrylate film, use the mixing solutions development polymethyl methacrylate film of methyl iso-butyl ketone (MIBK) and Virahol again, clean with pure Virahol then, dry under the high pure nitrogen environment at last.The beam spot size of the dosage of the present invention by the controlling electron beam photoetching, electron beam and the thickness of polymethylmethacrylate are realized the control of the carbon nano-structured material of different pattern, the tolerance range height of pattern.Be mainly used in unicircuit, an emission, nano-electrode, optics, aspects such as biosensor.
Description
Technical field
The invention belongs to technical field of nano material, relate to a kind of patterned carbon preparation of nanomaterials, relate in particular to a kind of method that adopts the beamwriter lithography polymethyl methacrylate film to prepare patterned carbon nano-structured material.
Background technology
The carbon nano-structured material of patterning is because emission on the scene, unicircuit, and nano-electrode, optics, the potential application of aspects such as biological device has caused people's attention.At present, the method for the carbon nano-structured material of preparation patterning has a lot, comprises chemical vapour deposition, sputtering method, and electron beam irradiation individual layer macromolecular material, e-beam induced deposition method or the like, the presoma that the whole bag of tricks uses is all different.
The e-beam induced deposition method is that hydrocarbon gas resolves into amorphous carbon under high-intensity electron beam effect, this method has very high resolving power and step simple, but owing to relate to diffusion, absorption and the decomposition of gas in reaction process, this method efficiency ratio in the relative large size material of preparation is lower.
Electron beam lithography is to utilize electron beam directly to draw on the wafer of electronic corrosion-resistant or the technology of projection copying figure scribbling.Electronic corrosion-resistant is a kind of to electron-sensitive high molecular polymer.Through the electronic corrosion-resistant generation molecular chain reorganization that electron beam scanning is crossed, the resist generation chemical property of exposure figure part is changed.Through developing and photographic fixing, obtain high-resolution resist exposure figure.The main processes of electron beam lithography is gluing, preceding baking, electron beam exposure, development and post bake.Modern beamwriter lithography equipment can have been made the meticulous linear less than 10nm.
Polymethylmethacrylate (PMMA) has good insulation performance performance and optical property, and electron beam is had very strong susceptibility, can be used as electronic corrosion-resistant.Therefore, the present invention utilizes the carbon nano-structured material of beamwriter lithography polymethylmethacrylate (PMMA) film preparation patterning to have should to have actual using value.
Summary of the invention
The purpose of this invention is to provide a kind of method that adopts the electron beam exposure polymethyl methacrylate film to prepare the patterned carbon nano material.
The present invention adopts the electron beam exposure polymethyl methacrylate film to prepare the method for patterned carbon nano material, is earlier 1 * 10
-2～1 * 10
-8Adopt electron beam exposure polymethyl methacrylate film (PMMA) under the vacuum of Pa, obtain with developing liquid developing again.
All electron-beam exposure systems of beamwriter lithography polymethyl methacrylate film (PMMA) all are connected with graphicalphanumeric generator.The carbon nano-structured material for preparing different pattern by the dosage that changes beamwriter lithography.Electron beam exposure bombards electron sensitive resist with high-energy electron exactly, physical-chemical reactions such as resist generation polymerization or division, and the good just positive corrosion-resisting agent of polymethylmethacrylate, but polymethylmethacrylate is transformed into negative resist under the electron beam of high dosage.Under certain dosage, the carbon atom in the polymethylmethacrylate (PMMA) forms covalent linkage, thereby forms patterned carbon nano-structured.
The thickness of the dosage that the present invention exposes by controlling electron beam, the beam spot size of electron beam and polymethylmethacrylate is realized the control of the carbon nano-structured material of different pattern.
Fig. 1 is for adopting the electron beam exposure PMMA film of various dose, the carbon nano-structured material of the different pattern that obtains.As seen from Figure 1, the electron beam exposure PMMA film of various dose obtains the dot pattern of different diameter.
Fig. 2 is the carbon nano-structured size of dosage control by the control Points And lines.A1, a2, a3, a4 carbon nano-structured size among Fig. 2 for obtaining by reference mark dosage.Fig. 2 b1, b2, b3, b4 are line dosage carbon nano-structured of corresponding a1, a2, a3, a4.As seen from Figure 2, the size of nano dot and nano wire can strictly be controlled by dose point and line dosage.
By a large amount of studies show that, when the dose point of electron beam is controlled in 0.01～10pC scope, the diameter of point can be controlled between 5 nanometers to 10 micron.When the line dosage control of electron beam was between 0.01～10 μ C/cm, the width of line can be controlled between 5 nanometers to 10 micron.
The regional dosage control of electron beam is at 1～100mC/cm
2Between.
The beam spot size of electron beam of the present invention is between 2～10nm.
The polymethyl methacrylate film that the present invention adopts adopts spin-coating method to make; The thickness of polymethyl methacrylate film should be controlled within 10～1000nm scope.
Pattern of the present invention can be by programdesign, thereby and makes the carbon pattern of random procedure design by the deflection of figure projector controlling electron beam.
Developing solution of the present invention can adopt at least a in acetone, Virahol, methyl iso-butyl ketone (MIBK), the chlorobenzene.Preferable methyl isobutyl ketone and Virahol were with 1: 1～1: 3 volume ratio blended mixing solutions.
The present invention compared with prior art has the following advantages:
1, efficient height: adopt beamwriter lithography PMMA film to make the PMMA carbonization prepare the carbon nanomaterial of patterning, compare with other method, processing step is few, and principle is simple, has improved preparation efficiency greatly.
2, the tolerance range height of pattern: the dosage by controlling electron beam photoetching threshold value is realized the control of the carbon nano-structured material of different pattern, the tolerance range height of pattern.
3, preparation technology is simple, is easy to control, handled easily.
The carbon nanomaterial that 4, can prepare large-area patterning by industrialized electron beam exposure equipment.
Description of drawings
Fig. 1 is for adopting the beamwriter lithography PMMA film of various dose, the carbon nano-structured material of the different pattern that obtains
(a) dosage of each some 1.5pC; (b) dosage of each some 3pC;
(c) dosage of each some 4.5pC; (d) dosage of each some 6pC;
Fig. 2 is the carbon nano-structured size of dosage control by the control Points And lines
(a1) dosage of each some 3pC; (a2) dosage of each some 6pC;
(a3) dosage of each some 9pC; (a4) dosage of each some 15pC;
(b1) dosage of every line 60nC/cm; (b2) dosage of every line 90nC/cm;
(b3) dosage of every line 150nC/cm; (b4) dosage of every line 600nC/cm;
The 10nm diameter that Fig. 3 obtains by controlling electron beam diameter and graphic designs for embodiment 3, the carbon nano-dot matrix in 50nm cycle
The 12nm live width that Fig. 4 obtains by controlling electron beam diameter and graphic designs for embodiment 4, the carbon nanometer grating in 50nm cycle
The L molded lines in the 24nm cycle that Fig. 5 obtains by controlling electron beam diameter and graphic designs for embodiment 5
Embodiment
The preparation of embodiment one, dot pattern carbon nanomaterial
1, the preparation of PMMA film
Prepare the PMMA film with spin coating method: adopting p (100) Si is substrate, and the PMMA of mass concentration 2% is dissolved in the chlorobenzene, and controls revolution speed is 3000rpm then, obtains the polymethyl methacrylate film that thickness is 128nm.In order to remove the tack of desolvating and improving film and substrate, the PMMA film for preparing is toasted 60s down at 180 ℃.
2, the preparation of patterned carbon nano material
With electron-beam lithography system exposure PMMA film, the voltage of electron beam exposure, the electric current of beam spot size and electron beam is controlled at 30kV respectively, 10nm and 49pA, and the vacuum of working spaces is lower than 1 * 10
-5Pa.After the exposure, mixing solutions (volume ratio of methyl iso-butyl ketone (MIBK) and Virahol is 1: 3) with methyl iso-butyl ketone (MIBK) and Virahol soaks development PMMA film 60s under 20 ℃ envrionment temperature earlier, clean 60s with pure Virahol then, dry up with the high pure nitrogen rifle at last.
Thereby prepare the different pattern carbon nano-structured material by the dosage that changes the change exposure of the electron beam residence time; By the deflection of figure projector controlling electron beam, and the direction and the distance of control deflection, the dot matrix of different cycles obtained.The dot pattern of the different diameter that Fig. 1 obtains for the beamwriter lithography PMMA film of various dose and the dot matrix of same period.
The preparation of embodiment two, line pattern carbon nanomaterial
1, the preparation of PMMA film
The preparation method is with embodiment 1.
2, the preparation of line pattern carbon nanomaterial
With electron-beam lithography system exposure PMMA film.The voltage of photoetching, the electric current of spot size and electron beam is controlled at 30kV respectively, 10nm and 49pA, the vacuum of working spaces is lower than 1 * 10
-5Pa.After the exposure, mixing solutions (volume ratio of methyl iso-butyl ketone (MIBK) and Virahol is 1: 3) with methyl iso-butyl ketone (MIBK) and Virahol soaks development PMMA film 60s under 20 ℃ envrionment temperature earlier, and then, dry up with the high pure nitrogen rifle at last with pure Virahol cleaning 60s.
Thereby prepare different pattern carbon nano-structured material (seeing Fig. 2 a1, a2, a3, a4) by the dosage that changes the change exposure of the electron beam residence time; Thereby move the line pattern of preparing random length by figure projector controlling electron beam and (see Fig. 2 b1～b4).
Embodiment three: the carbon nano-dot matrix in 10nm diameter 50nm cycle is made
1, the preparation of PMMA film
The preparation method is with embodiment one
2, the carbon nano-dot matrix in 10nm diameter 50nm cycle is made
The figure of design is the hexagonal structure of cycle 50nm.With electron-beam lithography system exposure PMMA film.The voltage of beamwriter lithography, the electric current of spot size and electron beam is controlled at 30kV respectively, 2nm and 20pA, the vacuum of working spaces is lower than 1 * 10
-5Pa.After the exposure, earlier under 20 ℃ envrionment temperature with mixing solutions (volume ratio of methyl iso-butyl ketone (MIBK) and Virahol is 1: 3) the development PMMA film 60s of methyl iso-butyl ketone (MIBK) and Virahol, and then, dry up with the high pure nitrogen rifle at last with pure IPA cleaning 60s.
Prepare patterned carbon nano-structured material by the graphic designs that changes beamwriter lithography.The pattern of the carbon nano-structured material of preparation is seen Fig. 3.
Embodiment four: the carbon nanometer grating in 50 nanometer cycles of 12nm live width is made
1, the preparation of PMMA film
The preparation method is with embodiment one
2, the carbon nanometer grating in 12nm diameter 50nm cycle is made
The figure of design is the optical grating construction in 50nm cycle.With electron-beam lithography system exposure PMMA film.The voltage of beamwriter lithography, the electric current of spot size and electron beam is controlled at 30kV respectively, 2nm and 20pA, the vacuum of working spaces is lower than 1 * 10
-5Pa.After the exposure, the mixing solutions (volume ratio of methyl iso-butyl ketone (MIBK) and Virahol is 1: 3) with methyl iso-butyl ketone (MIBK) and Virahol soaks PMMA film 60s under 20 ℃ envrionment temperature earlier, and then cleans 60s with pure IPA, dries up with the high pure nitrogen rifle at last.
We prepare patterned carbon nano-structured material by the graphic designs that changes beamwriter lithography.The pattern of the carbon nano-structured material of preparation is seen Fig. 4.
Embodiment five: the making of the L molded lines in 24nm cycle
1, the preparation of PMMA film
The preparation method is with embodiment one
2, the making of the L molded lines in 24nm cycle
The figure of design is the L molded lines in 24nm cycle.With electron-beam lithography system exposure PMMA film.The voltage of photoetching, the electric current of spot size and electron beam is controlled at 30kV respectively, 2nm and 20pA, the vacuum of working spaces is lower than 1 * 10
-5Pa.After the exposure, mixing solutions (volume ratio of methyl iso-butyl ketone (MIBK) and Virahol is 1: 3) with methyl iso-butyl ketone (MIBK) and Virahol soaks PMMA film 60s under 20 ℃ envrionment temperature earlier, and then with pure IPA cleaning 60s, dry down with the high pure nitrogen environment at last.
Prepare patterned carbon nano-structured material by the graphic designs that changes beamwriter lithography.The pattern of the carbon nano-structured material of preparation is seen Fig. 5.
Claims (8)
1, a kind of preparation method of patterned carbon nano-structured material is first under the vacuum of 1 * 10-2～1 * 10-8Pa, adopts the electron beam exposure polymethyl methacrylate film, obtains with developing liquid developing again.
2, the preparation method of patterned carbon nano-structured material according to claim 1, it is characterized in that: the dose point of described electron beam is between 0.01～10pC.
3, the preparation method of patterned carbon nano-structured material according to claim 1, it is characterized in that: the line dosage of described electron beam is between 0.01～10 μ C/cm.
4, the preparation method of patterned carbon nano-structured material according to claim 1, it is characterized in that: the regional dosage of described electron beam is at 1～100mC/cm
2Between.
5, the preparation method of patterned carbon nano-structured material according to claim 1, it is characterized in that: the beam spot size of described electron beam is 2～10nm.
6, the preparation method of patterned carbon nano-structured material according to claim 1 is characterized in that: the thickness of described polymethyl methacrylate film is for being 1 nanometer to 10 micron.
7, the preparation method of patterned carbon nano-structured material according to claim 1 is characterized in that: described developing solution is at least a in acetone, Virahol, methyl iso-butyl ketone (MIBK), the chlorobenzene.
8, as the preparation method of patterned carbon nano-structured material as described in the claim 7, it is characterized in that: described developing solution is methyl iso-butyl ketone (MIBK) and Virahol with 1: 1～1: 3 volume ratio blended mixing solutions.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798058A (en) * | 2010-03-12 | 2010-08-11 | 厦门大学 | Method for modifying surface heterogeneous medium of silica-based nanowire |
| CN103072984A (en) * | 2013-01-10 | 2013-05-01 | 海博瑞恩电子科技无锡有限公司 | Preparation method of trans-scale porous carbon material based on photoresist |
| CN110737171A (en) * | 2019-05-07 | 2020-01-31 | 南方科技大学 | Nano graph and preparation method thereof, and preparation method of nano structure |
| CN110980704A (en) * | 2019-12-30 | 2020-04-10 | 中国科学院合肥物质科学研究院 | Electron beam induced patterned graphene and preparation method thereof |
-
2009
- 2009-06-27 CN CN200910117348A patent/CN101613099A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798058A (en) * | 2010-03-12 | 2010-08-11 | 厦门大学 | Method for modifying surface heterogeneous medium of silica-based nanowire |
| CN103072984A (en) * | 2013-01-10 | 2013-05-01 | 海博瑞恩电子科技无锡有限公司 | Preparation method of trans-scale porous carbon material based on photoresist |
| CN103072984B (en) * | 2013-01-10 | 2014-11-12 | 海博瑞恩电子科技无锡有限公司 | Preparation method of trans-scale porous carbon material based on photoresist |
| CN110737171A (en) * | 2019-05-07 | 2020-01-31 | 南方科技大学 | Nano graph and preparation method thereof, and preparation method of nano structure |
| CN110737171B (en) * | 2019-05-07 | 2023-12-01 | 南方科技大学 | Nano pattern and preparation method thereof, and preparation method of nano structure |
| CN110980704A (en) * | 2019-12-30 | 2020-04-10 | 中国科学院合肥物质科学研究院 | Electron beam induced patterned graphene and preparation method thereof |
| CN110980704B (en) * | 2019-12-30 | 2023-01-24 | 中国科学院合肥物质科学研究院 | Electron beam induced patterned graphene and preparation method thereof |
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Open date: 20091230 |