CN103935956A - Graphene nanoribbon boundary trimming method based on tip-enhanced Raman spectroscopy - Google Patents
Graphene nanoribbon boundary trimming method based on tip-enhanced Raman spectroscopy Download PDFInfo
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Abstract
The invention discloses a graphene nanoribbon boundary trimming method based on the tip-enhanced Raman spectroscopy. The graphene nanoribbon boundary trimming method based on the tip-enhanced Raman spectroscopy comprises the steps that firstly, a graphene nanoribbon with a boundary to be trimmed is transferred onto a substrate, a silicon nitride cantilever conducting probe is made to be in contact with the graphene nanoribbon, and an electrified probe is directly pressed to the top end of the graphene nanoribbon; the silicon nitride cantilever conducting probe is powered on, the silicon nitride cantilever conducting probe is connected to the electrified probe and bias voltage is exerted so that a loop can be formed, and current is made to pass through the graphene nanoribbon; the boundary of the graphene nanoribbon is scanned with the silicon nitride cantilever conducting probe, the scanning speed is controlled to range from 10 micron/s to 30 micron/s, carbon atoms on the boundary are stimulated through energy and then atom reconstruction is conducted automatically, and a crystalline atomic-scale graphene nanoribbon is generated on the graphene boundary; other defects are prevented from being generated on the graphene nanoribbon on the basis that the boundary of the graphene nanoribbon is reconstructed, operation is convenient, and monitoring can be conducted conveniently during operation.
Description
Technical field
The invention belongs to field of nanometer technology, be specifically related to a kind of graphene nanobelt border method of modifying based on Tip-Enhanced Raman Spectroscopy (Tip-enhanced Raman spectroscopy, TERS) system.
Background technology
Graphene is a kind of by the former molecular material of monolayer carbon, has numerous very special physical characteristics, and under room temperature, the migration velocity of electronics in grapheme material is 200 times of silicon conductor.Research is before this verified, and CNT (by the curling cylindrical structure forming of Graphene) has fabulous electric conductivity, but the comparatively complicated CNT of structure is difficult to be arranged on electronic chip inside.Along with deepening continuously that Graphene is studied, Graphene is applied in traditional field-effect transistor and becomes a kind of trend, the microelectronic component preparation based on Graphene and the electrology characteristic of Graphene become study hotspot.Conventionally, the field-effect transistor using in digital circuit need to have higher on-off ratio, to the gate source voltage changing is had to response speed faster, therefore needs to possess less grid and the higher conducting channel of electron mobility.And Graphene is a kind of semi-metallic of zero band gap, therefore only open the band gap of Graphene, could improve the transistorized on-off ratio of Graphene.Research is found, double-layer graphite alkene is added vertical electric field or Graphene is adulterated and can open the band gap of Graphene, and another opens comparatively easily the method for Graphene band gap and prepares exactly graphene nanobelt, and its band gap width and the width of nanobelt and relevant with the shape on border.
Graphene nanobelt has two kinds of border structures: armchair and zigzag.Border structure is very important in the rare nanostructured of graphite, wherein armchair graphene nanobelt shows as semiconductor property, sawtooth pattern graphene nanobelt shows metalline, and the probability that carrier penetrates Schottky barrier does not change with the variation of size and length.The boundary condition of graphene nanobelt and width are most important on the impact of graphene nanobelt field-effect transistor character.Due to the restriction of nanobelt boundary condition and width, the preparation of graphene nanobelt faces huge challenge.The conventional preparation method of the rare nanobelt of graphite, as CNT cutting-out method, nanowire mask etching method and photoetching process etc., do not possess the ability on the rare border of controlled working graphite, what obtain is all unordered border structures, the rare nanobelt structure of graphite on uncontrollable definite border.At present, by the anisotropic etching effect in conjunction with traditional micro-processing technology and Graphene, can accurately prepare smooth sawtooth pattern (atom level) border structure, but, on the graphene nanobelt that ion cutting obtains, to graphene nanobelt (Graphene nanoribbon, GNR), preparation has proposed higher requirement to the removal problem of residual high oxide and surface impurity.Carbon atom during graphite is rare is SP
2configuration, if carried out cutting, will inevitably destroyedly there are dangling bonds in its border atomic structure, introduced defect in Graphene, reduced the mobility of carrier in Graphene raceway groove.Therefore the rare nanobelt of graphite of, preparing for conventional method can carry out border modification by prior art.Different borders is modified, and the Electronic Transport Properties of the rare nanobelt of graphite is had to different impacts.
The impact of the electric property of the boundary condition of Graphene on device also can not be ignored, therefore the restructuring of the inner carbon atom of the selection to GNR border and defect seems particularly important.Existing researcher is by the integrated system (TEM-STM) based on transmission electron microscope and PSTM, utilize Joule heat that the carbon atom of graphene edge is at high temperature evaporated, nanobelt border re-constructs, and has effectively formed the continuously specific border of crystalline state.
Tip-Enhanced Raman Spectroscopy technology based near field optic principle and SPM technology is a kind of new technology that developed recently gets up.Tip-Enhanced Raman Spectroscopy technology combines SPM scanning technique and needle point strengthens optical detector technology.Needle point enhancing optical technology can strengthen the raman spectral signal of nanometer local greatly, further improve signal to noise ratio, when beam of laser is radiated at apart from sample surfaces nanometer spacing with suitable method, radius of curvature is (atomic force microscope or PSTM STM needle point) on the needle point of the gold-plated or platinum plating of the SPM of tens nanometers time, due to optical antenna resonance enhancement, near needle point, electromagnetic field is greatly strengthened, thereby strengthen near the Raman signal of the nanometer local of needle point, the SPM technology with nano-space resolution ratio is combined with Tip-Enhanced Raman Spectroscopy technology, can apply bias voltage so that sample surfaces is modified at conducting probe and sample.This technology has been applied to the sign of semi-conducting material, DNA molecular and biomolecule etc.
Summary of the invention
The object of the invention is for overcome above-mentioned conventional graphite alkene nanobelt border comparatively coarse, had a strong impact on its electric conductivity, be the problem that hinders a large obstacle of graphene nanobelt electric transmission, a kind of completely newly graphene nanobelt border method of modifying based on Tip-Enhanced Raman Spectroscopy (TERS) system is provided, can have processed consistent, the rare nanobelt structure of graphite periodically.
The present invention realizes foregoing invention object by following means: Tip-Enhanced Raman Spectroscopy system is made up of FT-Raman and confocal Raman system and atomic force microscopy system, atomic force microscopy system adopts silicon nitride cantilevers conducting probe, first graphene nanobelt to be finished border is transferred on substrate, silicon nitride cantilevers conducting probe is contacted with limit graphene nanobelt, will add electric probe and be directly pressed in the top of border graphene nanobelt to be finished; Silicon nitride cantilevers conducting probe is connected with the mains, connect with adding electric probe and on graphene nanobelt, apply bias voltage to form loop by silicon nitride cantilevers conducting probe, allow electric current pass graphene nanobelt; The border of graphene nanobelt is scanned with silicon nitride cantilevers conducting probe, gated sweep speed is 10-30 μ m/s, and the carbon atom on border is subject to energy excitation and spontaneously carries out atom reconstruct, and graphene edge generates the graphene nanobelt of the atom level of crystalline state.
The present invention adopts the beneficial effect having after technique scheme to be: the present invention can carry out border restructuring modification to the unordered graphene nanobelt in the border of being prepared by conventional method, on the basis that the border of graphene nanobelt is reconstructed, can not introduce other defect to graphene nanobelt, in the Raman spectrum system that the boundary types reconstruct of graphene nanobelt and modifying process use needle point to strengthen, realize, the Raman spectroscopy that needle point strengthens can carry out monitoring constantly to the situation of carrying out of reconstruct when the border of graphene nanobelt is reconstructed, whether monitoring reaches expection requirement.The present invention is easy to operate, and in operating process, is convenient to monitoring, and the preparation to graphene nanobelt field-effect transistor and popularization have huge progradation.
Brief description of the drawings
Fig. 1 is the armchair border schematic diagram of graphene nanobelt;
Fig. 2 is the sawtooth pattern border schematic diagram of graphene nanobelt;
Fig. 3 is that the graphene nanobelt border that utilizes Tip-Enhanced Raman Spectroscopy (TERS) system to prepare conventional method processes the enforcement schematic diagram of reconstruct;
Fig. 4 is Raman spectrogram irregular and the sawtooth pattern graphene nanobelt border that process is modified, first figure is the Raman spectrogram on irregular sawtooth pattern graphene nanobelt border, second figure is the Raman spectrogram on the sawtooth pattern graphene nanobelt border through modifying, and illustration is wherein Lorentz lorentz's fitted figure picture of each G characteristic peak.
Description of reference numerals is as follows:
1-armchair graphene nanobelt; 2-sawtooth pattern graphene nanobelt; 3-substrate; The graphene nanobelt that 4-border is to be finished; 5-Raman spectrum system; 6-silicon nitride cantilevers conducting probe; 7-add electric probe.
Detailed description of the invention
Below in conjunction with accompanying drawing, the present invention is described further, but protection scope of the present invention is not limited to this.
Fig. 1 and two kinds of border structure types that Figure 2 shows that Graphene of the present invention: armchair graphene nanobelt 1 and sawtooth pattern graphene nanobelt 2.
Figure 3 shows that the enforcement schematic diagram of the graphene nanobelt border reconstruct based on Tip-Enhanced Raman Spectroscopy (TERS) system.The unordered border graphene nanobelt 4 to be finished in border prepared by conventional method is transferred in the target substrate 3 with traditional cmos process compatibility, transfer to the border graphene nanobelt 4 to be finished on substrate 3, before carrying out border modification, first with drying up with nitrogen after acetone, absolute ethyl alcohol, the each ultrasonic 3-5 of deionized water minute.
Tip-Enhanced Raman Spectroscopy system is made up of FT-Raman and confocal Raman system 5 and atomic force microscopy (AFM) system.Atomic force microscopy system adopts silicon nitride cantilevers conducting probe 6, and silicon nitride cantilevers conducting probe 6 is coated with 10-50nm platinum, to meet probe electric conductivity.The elastic constant of silicon nitride cantilevers conducting probe 6 is 0.06-0.58 N/m, and resonant frequency is 18-65 KHz.Silicon nitride cantilevers conducting probe 6 uses carbon nano-tube point or all-metal silk needle point, and its radius of curvature is 5-20nm.
In TERS system, silicon nitride cantilevers conducting probe 6 is connected with the mains, and will add electric probe 7 and be directly pressed in a top of border graphene nanobelt to be finished 4.When AFM adopts contact mode, the silicon nitride cantilevers conducting probe 6 also graphene nanobelt 4 to be finished with border contacts, by silicon nitride cantilevers conducting probe 6 is applied to bias voltage to form loop with adding electric probe 7 on the graphene nanobelt 4 to be finished of border, allow electric current pass border graphene nanobelt to be finished 4.
Under AFM system contact mode, utilize silicon nitride cantilevers conducting probe 6 to scan graphene nanobelt 4 borders to be finished, border, gated sweep speed is 10-30 μ m/s.The joule heating effect causing due to electric current, energy will be dissipated in the Nodes on graphene nanobelt to be finished 4 borders, border, the carbon atom that causes border is subject to energy excitation and spontaneously carries out atom reconstruct, thereby impels graphene nanobelt to be finished 4 borders in border to obtain atom level structural remodelings.Due to the evaporation of part carbon atom and other foreign ions, defective graphene edge generates the nanobelt of crystalline state simultaneously, forms the perfect graphene nanobelt of atom level.When the AFM system graphene nanobelt 4 to be finished to border carries out modification, the variation of the Raman spectrum strengthening by needle point, sawtooth pattern and handrail type Graphene can be made a distinction, thereby realize the evenly preparation of the graphene nanobelt of specific border (armchair and the sawtooth pattern) structure of rule of border, as shown in Figure 4, the appearance of sawtooth pattern nanobelt can cause and is positioned at 1593cm
-1near the splitting of G feature peak-to-peak.
In the border restructuring procedure of border graphene nanobelt 4 to be finished, under nitrogen or ar gas environment, carry out, utilize the Raman spectrum system 5 in TERS system to detect whether reach expection requirement to the border reconstruct situation of graphene nanobelt to be finished 4, can monitor by the variation constantly of Raman spectrum the restructuring situation on graphene nanobelt border, by regulating the sweep speed of bias voltage and silicon nitride cantilevers conducting probe 6 to realize orthoplasy and the carbon atom restructuring on graphene nanobelt border, Tip-Enhanced Raman Spectroscopy system is used the optical maser wavelength of 532nm, the Raman light of laser energy 2mW is monitored.
Claims (6)
1. the graphene nanobelt border method of modifying based on Tip-Enhanced Raman Spectroscopy, Tip-Enhanced Raman Spectroscopy system is made up of FT-Raman and confocal Raman system and atomic force microscopy system, atomic force microscopy system adopts silicon nitride cantilevers conducting probe, it is characterized in that:
(1) first graphene nanobelt to be finished border is transferred on substrate, described silicon nitride cantilevers conducting probe is contacted with limit graphene nanobelt, will add electric probe and be directly pressed in the top of described graphene nanobelt,
(2) silicon nitride cantilevers conducting probe is connected with the mains, connect with adding electric probe and on graphene nanobelt, apply bias voltage to form loop by silicon nitride cantilevers conducting probe, allow electric current pass graphene nanobelt;
(3) with silicon nitride cantilevers conducting probe, the border of graphene nanobelt is scanned, gated sweep speed is 10-30 μ m/s, the carbon atom on border is subject to energy excitation and spontaneous atom reconstruct, the graphene nanobelt of the atom level of graphene edge generation crystalline state of carrying out.
2. the graphene nanobelt border method of modifying based on Tip-Enhanced Raman Spectroscopy according to claim 1, is characterized in that: step (3) is to carry out under nitrogen or ar gas environment.
3. the graphene nanobelt border method of modifying based on Tip-Enhanced Raman Spectroscopy according to claim 1, is characterized in that:
Silicon nitride cantilevers conducting probe is coated with 10-50nm platinum, and the elastic constant of silicon nitride cantilevers conducting probe is 0.06-0.58 N/m, and resonant frequency is 18-65 kHz.
4. the graphene nanobelt border method of modifying based on Tip-Enhanced Raman Spectroscopy according to claim 1, is characterized in that: the needle point of silicon nitride cantilevers conducting probe is carbon nano-tube point or all-metal silk needle point, and the radius of curvature of needle point is 5-20nm.
5. the graphene nanobelt border method of modifying based on Tip-Enhanced Raman Spectroscopy according to claim 1, is characterized in that: use optical maser wavelength 532nm, the Raman light of laser energy 2mW detects the border reconstruct situation of graphene nanobelt.
6. the graphene nanobelt border method of modifying based on Tip-Enhanced Raman Spectroscopy according to claim 1, it is characterized in that: in step (1), to transferring to graphene nanobelt on substrate first with drying up with nitrogen after acetone, absolute ethyl alcohol, the each ultrasonic 3-5 of deionized water minute.
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| CN106985213A (en) * | 2017-04-28 | 2017-07-28 | 沈阳工业大学 | Utilize the method and apparatus of the accurate controllable cutting graphite alkene band of photocatalytic oxidation |
| CN110117780A (en) * | 2019-03-19 | 2019-08-13 | 中国科学院上海微系统与信息技术研究所 | A kind of two-dimensional material layer and preparation method |
| CN110311010A (en) * | 2019-06-28 | 2019-10-08 | 西安交通大学 | A kind of infrared broad spectrum detector based on graphene nanobelt |
| CN110342504A (en) * | 2019-06-28 | 2019-10-18 | 西安交通大学 | A kind of preparation method of graphene nanobelt |
| CN111505345A (en) * | 2020-05-15 | 2020-08-07 | 大连理工大学 | Atomic force microscope probe modification method based on scanning electron microscope micro-control system |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106985213A (en) * | 2017-04-28 | 2017-07-28 | 沈阳工业大学 | Utilize the method and apparatus of the accurate controllable cutting graphite alkene band of photocatalytic oxidation |
| CN106985213B (en) * | 2017-04-28 | 2019-01-29 | 沈阳工业大学 | Utilize the method and apparatus of the accurate controllable cutting graphite alkene band of photocatalytic oxidation |
| CN110117780A (en) * | 2019-03-19 | 2019-08-13 | 中国科学院上海微系统与信息技术研究所 | A kind of two-dimensional material layer and preparation method |
| CN110311010A (en) * | 2019-06-28 | 2019-10-08 | 西安交通大学 | A kind of infrared broad spectrum detector based on graphene nanobelt |
| CN110342504A (en) * | 2019-06-28 | 2019-10-18 | 西安交通大学 | A kind of preparation method of graphene nanobelt |
| CN110342504B (en) * | 2019-06-28 | 2021-05-28 | 西安交通大学 | Preparation method of graphene nanoribbon |
| CN110311010B (en) * | 2019-06-28 | 2022-06-07 | 西安交通大学 | Infrared wide spectrum detector based on graphene nanoribbons |
| CN111505345A (en) * | 2020-05-15 | 2020-08-07 | 大连理工大学 | Atomic force microscope probe modification method based on scanning electron microscope micro-control system |
| CN111505345B (en) * | 2020-05-15 | 2021-08-10 | 大连理工大学 | Atomic force microscope probe modification method based on scanning electron microscope micro-control system |
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