CN101150088A - Method for adjusting and controlling single-wall carbon nano tube axial energy belt - Google Patents
Method for adjusting and controlling single-wall carbon nano tube axial energy belt Download PDFInfo
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- CN101150088A CN101150088A CNA2006101132126A CN200610113212A CN101150088A CN 101150088 A CN101150088 A CN 101150088A CN A2006101132126 A CNA2006101132126 A CN A2006101132126A CN 200610113212 A CN200610113212 A CN 200610113212A CN 101150088 A CN101150088 A CN 101150088A
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Abstract
This invention provides a method for realizing adjusting and controlling energy-bands of single-wall carbon nm tubes axially including: 1, setting up multiple convex and/or concave micro-nanometer structures on a Si02/Si substrate, 2, applying a micro-contact printing method to deposit catalyst at one end of the substrate to grow a super-long single-wall carbon nm tube array by a chemical gas-phase deposition method, 3, the carbon nm tube array is set on the micro-nanometer structures to control the energy band structure axially.
Description
Technical field
The invention belongs to the nanometer electronic device technical field, especially a kind of Single Walled Carbon Nanotube axially can be with the implementation method of regulation and control.
Background technology
Single Walled Carbon Nanotube has particular structure and excellent electricity, mechanical performance, and it is synthetic, character and application are that recent two decades comes scientific circles and the common problem of paying close attention to of industrial circle.Single Walled Carbon Nanotube shows wide application prospect in the nanometer electronic device field, is hopeful the core material that substituted for silicon becomes large scale integrated circuit.
Its band structure of the structures shape of Single Walled Carbon Nanotube, band structure determines character such as its electricity, mechanics again, character is again and then determine its application.The Single Walled Carbon Nanotube of controlled acquisition special properties is the key of carbon nano tube device practicability, but does not also find the effective way by growth control single wall nano tubular construction so far.In this case, the Single Walled Carbon Nanotube that growth is obtained carries out being with regulation and control to realize the controlled research focus that becomes of its character.At present, carry out to be with the method for modifying to comprise to Single Walled Carbon Nanotube: to realize chemical doping or utilize scanning probe microscopy to make Single Walled Carbon Nanotube generation deformation by gas absorption.These two kinds of methods are with the Single Walled Carbon Nanotube growth and can be with two processes of regulation and control separately, the poor stability of chemical doping, utilize low, the DeGrain of scanning probe microscopy driving efficiency, these two kinds of technology are all incompatible with existing semiconductor technology, can't realize the controllable adjustment that Single Walled Carbon Nanotube can be with efficiently, fast.
Summary of the invention
At above-mentioned existing in prior technology problem and shortage, the purpose of this invention is to provide the implementation method that a kind of Single Walled Carbon Nanotube axially can be with regulation and control.
Above-mentioned purpose of the present invention is achieved by the following technical solutions:
A kind of Single Walled Carbon Nanotube axially can be with the implementation method of regulation and control, and its step comprises:
(1) at SiO
2Make up the micro-nano structure of a plurality of projectioies and/or depression on/the Si substrate, form heterogeneous substrate;
(2) end at substrate adopts the micro-contact-printing deposited catalyst, utilizes chemical gaseous phase depositing process growth overlength single-wall carbon nanotube array;
(3) carbon nano pipe array rides on the micro-nano structure on the substrate, makes that the band structure of carbon nano-tube is regulated and control vertically.
In the step 1, at SiO
2One or more of evaporation metal, semiconductor or insulator on/the Si substrate, or, form protruding micro-nano structure by micro-contact printing deposition techniques molecular layer.
In the step 1, at SiO
2The groove that adopts electron beam lithography, reactive ion etching to obtain on/Si the substrate forms the micro-nano structure that caves in.
After the step 1, at SiO
2Can fill metal, semiconductor or insulating material in the groove that etching obtains on/the Si substrate.
In the step 2, apply an air-flow in the carbon nano tube growth process, the direction of air-flow is vertical with micro-nano structure.Be floating aloft after carbon nano-tube grows from catalyst, the effect of air-flow makes its direction of growth vertical with micro-nano structure, and carbon nano-tube dropped in the heterogeneous substrate and also vertically rides on the micro-nano structure after air-flow stopped.The single-wall carbon nanotube array length of utilizing the growth of air-flow orientation to obtain can reach Centimeter Level.
The basic principle of regulating and control the Single Walled Carbon Nanotube band structure along tube axial direction by heterogeneous substrate is: have effects such as Van der Waals force, chemical bond and electric charge transfer between heterogeneous micro-nano structure and the carbon nano-tube, the chemical doping effect that can cause carbon nano-tube radially deformation to take place and cause by the Partial charge transfer, thus make that the local band structure of carbon nano-tube is modulated.Different micro-nano structures is different with the interaction of carbon nano-tube, also can be different to the modulating action that carbon nano-tube can be with.Wherein, have more intense electric charge transferance between metal and the carbon nano-tube, the metal of high work function can make it to become the p type to carbon nano electronic, and the metal of low work function can be accepted electronics from carbon nano-tube and make it to become the n type; A little less than the electric charge transferance between semi-conducting material and the carbon nano-tube, and main active force is chemical bond and Van der Waals force between the carbon nano-tube; There is not the electric charge transferance between insulating material and the carbon nano-tube, mainly has chemical bond and Van der Waals force.Suitably design controlled material and stick position can be carried out the regulation and control of different amplitudes along tube axial direction to the band structure of carbon nano-tube.
Advantage of the present invention:
By the Single Walled Carbon Nanotube of growth superlong directional in heterogeneous substrate, realize to be with regulation and control to what Single Walled Carbon Nanotube was carried out segmentation along tube axial direction.This regulate and control method is integrated the growth of Single Walled Carbon Nanotube with being with regulation and control, can realize the design that a large amount of carbon nano-tube axially can be with by rational heterogeneous substrate regulation and control.Because what obtain is the overlength single-wall carbon nanotube array in growth, can obtain a plurality of pipeline sections along individual tubes with different band structures.This control methods are efficient, controlled, designability is strong, and also the semiconductor technology with existing is compatible mutually simultaneously, is applicable to the large scale integrated circuit manufacturing industry.This invention provides important basis for carbon nano-tube in nanometer electronic device field practicability.
Description of drawings
Fig. 1 is that a kind of Single Walled Carbon Nanotube of the present invention axially can be with the schematic diagram of regulate and control method flow process; Wherein, Fig. 1 (a) signal is the heterogeneous substrate for preparing by the micro-nano process technology; What Fig. 1 (b) illustrated is deposited catalyst in the heterogeneous substrate shown in Fig. 1 (a); Fig. 1 (c) signal be that the single-wall carbon nanotube array of the superlong directional that obtains of growth rides in the heterogeneous substrate.
Among the figure: the 1-silicon dioxide substrates; 2,3,4,5 represent different micro-nano structures respectively; The 6-catalyst layer; 7-superlong directional single wall carbon nano pipe array.
Fig. 2 (a) is at Pt-SiO
2The sem photograph of the Single Walled Carbon Nanotube fet array for preparing in the heterogeneous substrate.
Among the figure: 2-is used to regulate and control the Pt bar of carbon nano-tube band structure, and its width is respectively from top to bottom: 1 μ m, 2 μ m, 3 μ m and 4 μ m;
8-is used to measure the Pt electrode of carbon nano-tube electrical properties.
The I that obtains after the Pt bar regulation and control carbon nano-tube band structure of the different in width that Fig. 2 (b) is corresponding with Fig. 2 (a)
Ds-V
gCurve.
Among the figure:
When the a-source-drain voltage is 0.1V, the I of carbon nano-tube when not having the Pt bar
Ds-V
gCurve
B, c, d, when the e-source-drain voltage was 0.1V, Pt bar width was respectively the I of carbon nano-tube when being 1 μ m, 2 μ m, 3 μ m, 4 μ m
Ds-V
gCurve
Fig. 3 (a) is at TiO
2-SiO
2The sem photograph of the Single Walled Carbon Nanotube fet array for preparing in the heterogeneous substrate.
Among the figure: 3-is used to regulate and control the TiO of carbon nano-tube band structure
2Bar, its width is respectively from top to bottom: 1 μ m, 2 μ m, 3 μ m and 4 μ m;
8-is used to measure the Pt electrode of carbon nano-tube electrical properties.
The TiO of the different length that Fig. 3 (b) is corresponding with Fig. 3 (a)
2The I that obtains after the bar regulation and control carbon nano-tube band structure
Ds-V
gCurve.
Among the figure:
When the f-source-drain voltage is 0.1V, there is not TiO
2The I of carbon nano-tube during bar
Ds-V
gCurve
G, h, i, when the j-source-drain voltage is 0.1V, TiO
2The bar width is respectively the I of carbon nano-tube when being 1 μ m, 2 μ m, 3 μ m, 4 μ m
Ds-V
gCurve
Fig. 4 (a) is at SiO
2Grooved substrate on the sem photograph of the superlong directional single wall carbon nano-tube that obtains of growth.
Among the figure: the groove that the 4-etching obtains.
Fig. 4 (b) is that one section carbon nano-tube among Fig. 4 (a) is at SiO
2The RBM peak of Raman spectrum is with the variation of position in the time of on substrate and the groove.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in detail.
(1) with the thick SiO of surface heat oxidation 300nm
2The silicon chip cleaning-drying after, at its surperficial spin coating PMMA, obtain groove structure by electron beam lithography (EBL), reactive ion etching (RIE) etching, comprise two parts: be used to measure four lines that width is different that embed between six strip electrodes of carbon nano-tube transport property and the four pairs of electrodes.The degree of depth of groove is 80nm, and the width of electrode is 2 μ m, and the width of lines is respectively from top to bottom: 1 μ m, 2 μ m, 3 μ m and 4 μ m; Electron beam deposition (EBD) evaporation 80nm metal platinum (Pt) obtains embedding SiO after peeling off
2The Pt electrode Pt bar different with the electrode intermediate width.
(2) end of the substrate that obtains in step (1) utilizes micro-contact-printing deposition 1 * 10
-2MolL
-1FeCl
3Solution is as catalyst, place the CVD stove, under 950 ℃, with ethanol as carbon source, Ar gas as carrier gas growth overlength single-wall carbon nanotube array, growth time is 20 minutes, applies an air-flow in the growth course, and the direction of air-flow is vertical with the Pt bar, be floating aloft after carbon nano-tube grows from catalyst, the effect of air-flow makes its direction of growth vertical with the Pt bar;
(3) carbon nano-tube dropped in the heterogeneous substrate and also vertically rides on the Pt bar after air-flow stopped;
(4) with probe station and Keithley 4200 semiconductor characterization systems single-wall carbon nanotube array is carried out transport property and measure, obtain the regulation and control result of different in width Pt bar the Single Walled Carbon Nanotube band structure.Fig. 2 is at Pt-SiO
2The sem photograph of the single single-wall carbon nanotube array for preparing in the heterogeneous substrate and corresponding I-V curve.
(1) with the thick SiO of surface heat oxidation 500nm
2The silicon chip cleaning-drying after, at its surperficial spin coating PMMA,, obtain embedding SiO after peeling off by electron beam lithography (EBL), groove, electron beam deposition (EBD) evaporation 100nm metal platinum (Pt) that reactive ion etching (RIE) etching 100nm is thick
2Six Pt electrodes, the width of Pt electrode is 2 μ m.The Pt electrode is used to measure the electrical properties of carbon nano-tube.
(2) substrate that step (1) is obtained spin coating PMMA once more, by electron beam lithography (EBL), reactive ion etching (RIE) etching, lines, electron beam deposition (EBD) evaporation 100nm Titanium (Ti) that four width that etching 100nm is thick between four pairs of Pt electrodes are different obtain embedding SiO after peeling off
2The different Ti bar of width, the width of lines is respectively from top to bottom: 1 μ m, 2 μ m, 3 μ m and 4 μ m; Heated 1 hour under 300 ℃ under the oxygen atmosphere in Muffle furnace, the Ti bar is oxidized to TiO
2
(3) end in heterogeneous substrate utilizes micro-contact-printing deposition 2 * 10
-2MolL
-1FeCl
3Solution places the CVD stove as catalyst, under 940 ℃, with ethanol as carbon source, Ar gas as carrier gas growth overlength single-wall carbon nanotube array, growth time is 30 minutes, applies an air-flow in the growth course, the direction of air-flow and TiO
2Bar is vertical, and promptly carbon nano-tube is floating aloft after growing from catalyst, and the effect of air-flow makes its direction of growth and TiO
2Bar is vertical;
(4) carbon nano-tube dropped on and also vertically rides over TiO in the heterogeneous substrate after air-flow stopped
2On the bar;
(5) with probe station and Keithley 4200 semiconductor characterization systems step (3) is obtained the Single Walled Carbon Nanotube fet array and carry out the transport property measurement.Obtain the TiO of different in width
2Bar is to the regulation and control result of Single Walled Carbon Nanotube band structure.Fig. 3 is at TiO
2-SiO
2The sem photograph of the single Single Walled Carbon Nanotube fet array for preparing in the heterogeneous substrate and corresponding I-V curve.
(1) with the thick SiO of surface heat oxidation 1000nm
2The silicon chip cleaning-drying after, at its surperficial spin coating PMMA, by electron beam lithography (EBL), the thick SiO of reactive ion etching (RIE) etching 500nm
2, obtain SiO
2The groove structure of suprabasil different in width.
(2) end of the heterogeneous substrate that obtains in step (1) utilizes micro-contact-printing deposition 5 * 10
-3MolL
-1FeCl
3Solution is as catalyst, place the CVD stove, under 960 ℃, with ethanol as carbon source, Ar gas as carrier gas growth overlength single-wall carbon nanotube array, growth time is 45 minutes, applies an air-flow in the growth course, and the direction of air-flow is vertical with the micro-nano groove structure, be floating aloft after carbon nano-tube grows from catalyst, the effect of air-flow makes its direction of growth vertical with the micro-nano groove structure;
(3) carbon nano-tube dropped in the heterogeneous substrate and also vertically rides on the micro-nano groove structure after air-flow stopped;
(4) carbon nano pipe array is carried out Raman spectrum along individual tubes and characterize, more same carbon nano-tube be the variation of Raman shift when unsettled in substrate, obtains the regulation and control result of groove to the carbon nano-tube band structure.Fig. 4 is at SiO
2Groove structure on the sem photograph and the Raman spectrum of the single single-wall carbon nanotube array for preparing.
The efficient controllable pair Single Walled Carbon Nanotube of the present invention carries out being with regulation and control, is to obtain a large amount of carbon nano tube devices unit and realize the basis that element height is integrated, and also be the key of carbon nano tube device practicability.
In sum, the invention discloses the implementation method that a kind of Single Walled Carbon Nanotube axially can be with regulation and control.Above-described application scenarios and embodiment are not to be used to limit the present invention, and any those skilled in the art without departing from the spirit and scope of the present invention, can do various changes and retouching, so protection scope of the present invention is looked the claim scope and defined.
Claims (8)
1. a Single Walled Carbon Nanotube axially can be with the implementation method of regulation and control, and its step comprises:
(1) at SiO
2Make up the micro-nano structure of a plurality of projectioies and/or depression on/the Si substrate;
(2) end at substrate adopts the micro-contact-printing deposited catalyst, utilizes chemical gaseous phase depositing process growth overlength single-wall carbon nanotube array;
(3) carbon nano pipe array rides on the micro-nano structure on the substrate, makes that the band structure of carbon nano-tube is regulated and control vertically.
2. Single Walled Carbon Nanotube as claimed in claim 1 axially can be with the implementation method of regulation and control, it is characterized in that: in the step 1, at SiO
2One or more of evaporation metal, semi-conducting material or insulating material on/the Si substrate make up protruding micro-nano structure.
3. Single Walled Carbon Nanotube as claimed in claim 1 axially can be with the implementation method of regulation and control, it is characterized in that: in the step 1, at SiO
2By micro-contact printing deposition techniques molecular layer, make up protruding micro-nano structure on the/Si substrate.
4. axially can be with the implementation method of regulation and control as claim 1,2 or 3 described Single Walled Carbon Nanotube, it is characterized in that: in the step 1, at SiO
2Directly adopt electron beam lithography, reactive ion etching groove on the/Si substrate, make up the depression micro-nano structure.
5. Single Walled Carbon Nanotube as claimed in claim 4 axially can be with the implementation method of regulation and control, it is characterized in that: after the step 1, fill one or more of metal, semi-conducting material or insulating material respectively in groove.
6. Single Walled Carbon Nanotube as claimed in claim 1 axially can be with the implementation method of regulation and control, it is characterized in that: the micro-nano structure that makes up in the step 1 is a width line strip structure inequality.
7. axially can be with the implementation method of regulation and control as claim 1 or 6 described Single Walled Carbon Nanotube, it is characterized in that: in the step 2, apply an air-flow in the carbon nano tube growth process, the direction of air-flow is vertical with micro-nano structure.
8. Single Walled Carbon Nanotube as claimed in claim 1 axially can be with the implementation method of regulation and control, and it is characterized in that: in the step 2, catalyst is FeCl
3Solution, its concentration range are 5 * 10
-3～2 * 10
-2MolL
-1
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786023A (en) * | 2011-05-18 | 2012-11-21 | 中国科学院上海微系统与信息技术研究所 | Cover plate-free carbon nanotube device structure and manufacturing method thereof |
| TWI415789B (en) * | 2009-04-24 | 2013-11-21 | Nat Univ Chung Hsing | Method of forming self-assembled and uniform fullerene array on surface of substrate |
| US8986782B2 (en) | 2009-04-24 | 2015-03-24 | Mon-Shu Ho | Method of forming self-assembly and uniform fullerene array on surface of substrate |
| CN113284970A (en) * | 2021-05-10 | 2021-08-20 | 福州大学 | Carbon nano tube ultra-wideband photoelectric detector and preparation method thereof |
-
2006
- 2006-09-19 CN CNB2006101132126A patent/CN100472753C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI415789B (en) * | 2009-04-24 | 2013-11-21 | Nat Univ Chung Hsing | Method of forming self-assembled and uniform fullerene array on surface of substrate |
| US8986782B2 (en) | 2009-04-24 | 2015-03-24 | Mon-Shu Ho | Method of forming self-assembly and uniform fullerene array on surface of substrate |
| US9109278B2 (en) | 2009-04-24 | 2015-08-18 | Mon-Shu Ho | Method of forming self-assembly and uniform fullerene array on surface of substrate |
| CN102786023A (en) * | 2011-05-18 | 2012-11-21 | 中国科学院上海微系统与信息技术研究所 | Cover plate-free carbon nanotube device structure and manufacturing method thereof |
| CN102786023B (en) * | 2011-05-18 | 2015-01-21 | 中国科学院上海微系统与信息技术研究所 | Cover plate-free carbon nanotube device structure and manufacturing method thereof |
| CN113284970A (en) * | 2021-05-10 | 2021-08-20 | 福州大学 | Carbon nano tube ultra-wideband photoelectric detector and preparation method thereof |
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| CN100472753C (en) | 2009-03-25 |
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Granted publication date: 20090325 Termination date: 20110919 |