CN102020239A - Patterning growth method of single-walled carbon nanotubes by surface ruling method - Google Patents
Patterning growth method of single-walled carbon nanotubes by surface ruling method Download PDFInfo
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- CN102020239A CN102020239A CN2009101872957A CN200910187295A CN102020239A CN 102020239 A CN102020239 A CN 102020239A CN 2009101872957 A CN2009101872957 A CN 2009101872957A CN 200910187295 A CN200910187295 A CN 200910187295A CN 102020239 A CN102020239 A CN 102020239A
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Abstract
The invention relates to a patterning preparation technology of single-walled carbon nanotubes, in particular to a patterning growth method of single-walled carbon nanotubes through the surface ruling of a silicon substrate with silicon oxide, which is suitable for the height localizability and the patterning growth of high-quality single-walled carbon nanotubes without impurity residue. The method comprises the following steps of: firstly, ruling the surface of the substrate which is a silicon chip with a thermal oxide layer with a sharp object into a certain pattern to generate a plurality of catalytic active sites in substrate surface localization; then, forming nucleating points of the single-walled carbon nanotubes through high-wetting oxidation treatment; and preparing the single-walled carbon nanotubes through the schizolysis of a carbon source at 600-1,100 DEG C. The invention realizes the location and the patterning growth of the high-quality single-walled carbon nanotubes without any metal impurities in a simple silicon substrate ruling mode, has the advantages of simple and convenient operation, low cost, good localizability and easy patterning and lays a foundation for the application of the single-walled carbon nanotubes in the fields of nano electronic devices, sensors, and the like.
Description
Technical field:
The present invention relates to the patterning technology of preparing of CNT, be specially a kind of utilization simple surface delineation, in the method for surface of silicon location and patterned growth SWNT, be applicable to that the preparation of location and patterning does not contain the high-quality SWNT that any metal impurities pollute.
Background technology:
SWNT has excellent electricity, optics, calorifics and mechanical property, makes it all have wide application prospect in fields such as nanometer electronic device, opto-electronic device, sensor, catalyst carrier, composite and drug delivery and biomedicines.Therefore, since CNT was found, it all was the forward position and the hot issue of domestic and international physical chemistry circle and material educational circles that its theoretical research and application are explored all the time.SWNT shows as metal properties and semiconductor properties according to its diameter is different with chirality, so nanometer electronic device is considered to one of most important potential application of SWNT, greatly the process of propulsion information revolution.
Yet, want to realize the application of SWNT in the nanometer electronic device field, just must solve its location and patterned growth on the silicon substrate surface.Through various countries scientist effort for many years, very big progress has been arranged on this direction at present, as utilize magnesium-yttrium-transition metal catalyst such as iron, cobalt, nickel, auxiliary with electron beam lithography, photoetching technique and micro-contact printing technology, substantially, located growth, oriented growth and the patterned growth of SWNT on the surface of silicon be can be implemented in, but still many difficulties and challenge are faced with.As the located growth commonly used at present and the method for patterned growth SWNT, need increase the cost of its suitability for industrialized production and application by means of complicated and expensive electron beam lithography and photoetching technique mostly.In addition, nearly all present method for preparing SWNT all will be used metallic catalyst, and the metal impurities and the conventional semiconductor technology that remain in the SWNT are incompatible, and can greatly influence the intrinsic rerum natura of SWNT, and then hinder its application in the nanometer electronic device field; Also can only partly remove metallic catalyst impurity in the SWNT by the post processing purification process, and these last handling processes can be inevitably damage to the structure of SWNT, reduce its quality.Therefore, develop the method for a kind of simple location and patterned growth SWNT, in this process, can avoid simultaneously the introducing of any metal impurities again, will greatly promote the application study of nanometer electronic device, opto-electronic device and sensor, have huge commercial Application background and vast market prospect based on SWNT.
Summary of the invention:
But the object of the present invention is to provide a kind of simple located growth and patterned growth not to contain the method for the SWNT of any metal impurities, it is the method that has the silicon substrate patterned growth SWNT of silica by surface delineation, and that this method has is simple to operate, cost is low, highly locate and advantage such as patternable growth.
Technical scheme of the present invention is:
A kind of method of surperficial delineation method patterned growth SWNT, this method is with the silicon chip that the has thermal oxide layer substrate as the growing single-wall CNT, by using sharp objects to depict certain pattern at substrate surface, form the SWNT nucleating point by high temperature oxidation process then, and then at high temperature feed carbon source and carrier gas, carbon source is decomposed the carbon active specy that discharges and is adsorbed on these nucleating points, and at its auxiliary SWNT of finally preparing patterning down.
Among the present invention, the thickness of the thermal oxide layer of employed silicon substrate is 1-100nm, and preferable range is 2-50nm.
Among the present invention, the sharp objects of use is silicon chip, quartz plate, potsherd, glass cutter or the atomic-force microscope needle-tip etc. that have wedge angle.
Among the present invention, the oxygen gas flow rate of the silicon substrate high temperature oxidation process after the delineation is the 50-500 ml/min, and preferable range is the 100-200 ml/min; Heat treated temperature is 200-1100 ℃, and preferable range is 500-850 ℃.
Among the present invention, employed carbon source is one or more of hydrocarbons such as methane, ethane, ethene, acetylene, benzene, toluene, cyclohexane and ethanol, methyl alcohol, acetone, carbon monoxide etc., the carbon source flow velocity is the 1-500 ml/min in the course of reaction, and preferable range is the 5-200 ml/min.
Among the present invention, the carrier gas in the CNT growth course is a hydrogen; Perhaps, carrier gas is the gaseous mixture (wherein hydrogen volume is than 〉=1/10) of hydrogen and inert gases such as argon gas or helium, and the carrier gas overall flow rate is the 1-2000 ml/min, and preferable range is the 20-500 ml/min;
The growth temperature of SWNT is 600-1100 ℃ among the present invention, and preferable range is 650-950 ℃.
Adopt the diameter 0.8-1.8nm of the SWNT of the present invention's acquisition.
The invention has the beneficial effects as follows:
1, the present invention proposes a kind of simple surperficial delineation method to realize the located growth and the patterned growth of SWNT on the silicon base.
2, do not use any metallic catalyst in the method for the located growth that proposes of the present invention and patterned growth SWNT, thus in the product without any metal pollutant exist.
3, the inventive method is simple to operate, efficient, cost is low.
Description of drawings:
Fig. 1 is the experimental provision schematic diagram of surperficial delineation method patterned growth SWNT.Among the figure, 1 gas access; 2 have the silicon chip of thermal oxide layer; 3 thermocouples; 4 gas vents.
Fig. 2 has the sign of the silicon substrate patterned growth SWNT of silica for the surface delineation.Wherein, (a) being the low power electron scanning micrograph, be the high power electron scanning micrograph (b) and (c), (d) is the laser Raman spectroscopy that resonates.
Fig. 3 has the electron scanning micrograph of the SWNT of location and patterned growth on the silicon substrate of silica for surface delineation.Wherein, (a) being the cross type pattern, is the linearity pattern (b) and (c), (d) is the end of a linearity pattern.
Fig. 4 is the electron scanning micrograph that utilizes surperficial delineation method SWNT with " CNT " printed words of patterned growth on surface of silicon.
Fig. 5 is for using the contrast of the SWNT of growing after the different sharp objects delineation surface of silicon.Wherein, (a) for using diamond tool to delineate operation, (b) for using the silicon chip that has wedge angle to delineate operation.Lower left corner illustration is corresponding low power electron scanning micrograph.
The specific embodiment:
Be described in further detail the present invention below by embodiment and accompanying drawing.
As shown in Figure 1, apparatus of the present invention adopt the horizontal reacting furnace, and horizontal reacting furnace two ends are respectively equipped with gas access 1 and gas vent 4, and the silicon chip 2 that has thermal oxide layer places horizontal reacting furnace high-temperature region, thermocouple 3 stretches into horizontal reacting furnace high-temperature region, with real-time monitoring reaction temperature.
The silicon chip ruled surface that employing has wedge angle has thermal oxide SiO
2The silicon substrate of layer (10nm) obtains specific pattern.At first, this silicon substrate is positioned over horizontal reacting furnace middle section (reaction zone has thermocouple to monitor furnace temperature in real time in this position); In oxygen atmosphere, be heated to 850 ℃ (oxygen gas flow rate is 100 ml/min in the heating process, and programming rate is 40 ℃/minute), oxidizing thermal treatment 10 minutes; Then, adopt the argon gas exhaust 8 minutes of 1000 ml/min; Continue to heat up, treat that furnace temperature is warming up to 900 ℃ after, feed the mist (gas flow rate is respectively methane 500 ml/min and hydrogen 500 ml/min) of methane and hydrogen, beginning growing single-wall CNT, growth time is 20 minutes.
SEM, AFM and resonance laser Raman spectroscopy are observed and are shown, have only scored area to have SWNT to generate, the SWNT network for random distribution has higher quality, wherein the length of SWNT is at 5-25 μ m, and diameter is at 1.2-1.8nm.
Embodiment 2
Device is as accompanying drawing 1.
The silicon chip ruled surface that employing has wedge angle has thermal oxide SiO
2The silicon substrate of layer (5nm) obtains specific pattern.At first, this silicon substrate is positioned over horizontal reacting furnace middle section (reaction zone has thermocouple to monitor furnace temperature in real time in this position); In oxygen atmosphere, be heated to 850 ℃ (oxygen gas flow rate is 200 ml/min in the heating process, and programming rate is 30 ℃/minute), oxidizing thermal treatment 10 minutes; Then, adopt the argon gas exhaust 8 minutes of 1000 ml/min; Continue to heat up, treat that furnace temperature is warming up to 900 ℃ after, feed the mist (gas flow rate is respectively methane 300 ml/min and hydrogen 500 ml/min) of methane and hydrogen, beginning growing single-wall CNT, growth time is 20 minutes.
SEM, AFM and resonance laser Raman spectroscopy are observed and are shown, have only scored area to have SWNT to generate, the SWNT network for random distribution has higher quality, wherein the length of SWNT is at 4-20 μ m, and diameter is at 0.9-1.6nm.
Embodiment 3
Device is as accompanying drawing 1.
The silicon chip ruled surface that employing has wedge angle has thermal oxide SiO
2The silicon substrate of layer (10nm) obtains specific pattern.At first, this silicon substrate is positioned over horizontal reacting furnace middle section (reaction zone has thermocouple to monitor furnace temperature in real time in this position); In oxygen atmosphere, be heated to 850 ℃ (oxygen gas flow rate is 100 ml/min in the heating process, and programming rate is 40 ℃/minute), oxidizing thermal treatment 10 minutes; Then, adopt the argon gas exhaust 8 minutes of 1000 ml/min; Continue to heat up, after treating that furnace temperature is warming up to 900 ℃, bring ethanol into (wherein by the mode of argon gas bubbling, the flow velocity of argon gas is 200 ml/min, ethanol is positioned over constant temperature in 0 ℃ Meng Shi wash bottle), feed hydrogen simultaneously as buffer gas (gas flow rate is 500 ml/min), beginning growing single-wall CNT, growth time is 20 minutes.
SEM, AFM and resonance laser Raman spectroscopy are observed and are shown, have only scored area to have SWNT to generate, SWNT network for random distribution, the sample surfaces cleaning, has higher quality, wherein the length of SWNT is at 5-22 μ m, and diameter is at 1.2-1.7nm.
Embodiment 4
Device is as accompanying drawing 1.
Adopt the diamond tool ruled surface to have thermal oxide SiO
2The silicon substrate of layer (10nm) obtains specific pattern.At first, this silicon substrate is positioned over horizontal reacting furnace middle section (reaction zone has thermocouple to monitor furnace temperature in real time in this position); In oxygen atmosphere, be heated to 850 ℃ (oxygen gas flow rate is 100 ml/min in the heating process, and programming rate is 40 ℃/minute), oxidizing thermal treatment 10 minutes; Then, adopt the argon gas exhaust 8 minutes of 1000 ml/min; Continue to heat up, after treating that furnace temperature is warming up to 900 ℃, the mixed carbon source of bringing ethanol and methyl alcohol into by the mode of argon gas bubbling (wherein, the flow velocity of argon gas is 200 ml/min, the volume ratio of ethanol and methyl alcohol is 10: 1, is positioned over constant temperature in 0 ℃ Meng Shi wash bottle), feed hydrogen simultaneously as buffer gas (gas flow rate is 500 ml/min), beginning growing single-wall CNT, growth time is 20 minutes.
SEM, AFM and resonance laser Raman spectroscopy are observed and are shown, have only scored area to have SWNT to generate, SWNT network for random distribution, the sample surfaces cleaning, has higher quality, wherein the length of SWNT is at 5-21 μ m, and diameter is at 1.1-1.7nm.
Embodiment 5
Device is as accompanying drawing 1.
Adopt the afm tip ruled surface to have thermal oxide SiO
2The silicon substrate of layer (5nm) obtains specific pattern.At first, this silicon substrate is positioned over horizontal reacting furnace middle section (reaction zone has thermocouple to monitor furnace temperature in real time in this position); In oxygen atmosphere, be heated to 850 ℃ (oxygen gas flow rate is 100 ml/min in the heating process, and programming rate is 40 ℃/minute), oxidation processes 5 minutes; Then, adopt the argon gas exhaust 8 minutes of 1000 ml/min; Continue to heat up, treat that furnace temperature is warming up to 900 ℃ after, feed the mist (gas flow rate is respectively methane 500 ml/min and hydrogen 500 ml/min) of methane and hydrogen, beginning growing single-wall CNT, growth time is 5 minutes.
SEM, AFM and resonance laser Raman spectroscopy are observed and are shown, the SWNT confinement is grown in the very narrow scored area, SWNT network for random distribution, has higher quality, wherein the length of SWNT is at 1-5 μ m, and diameter is at 0.8-1.2nm.
As shown in Figure 1, air inlet one end has four mass flowmenters among the figure, and optionally control feeds gases such as argon gas, helium, hydrogen, methane, ethane, carbon monoxide.Liquid carbon source (as ethanol, methyl alcohol, benzene, toluene, cyclohexane etc.) places 0 ℃ Meng Shi wash bottle, brings into by the gaseous mixture bubbling of argon gas or argon gas and helium.
As shown in Figure 2, have from surface delineation silica silicon substrate patterned growth SWNT sign as can be seen, the SWNT located growth is in chiasma type cut network, the resonance laser Raman spectroscopy shows that SWNT has very high quality (the D mould is 0.05 with the ratio of the intensity of G mould), and the location and the patterned growth that adopt simple delineation method can realize SWNT are described.Among the figure, SiO
2/ Si specifically is meant and has thermal oxide SiO
2The silicon substrate of layer.
As shown in Figure 3, have from surface delineation the silicon substrate location of silica and patterned growth SWNT electron scanning micrograph as can be seen, the SWNT located growth is in cross or linear pattern cut, beyond the cut and the place that stops of cut then do not have the generation of SWNT, illustrate that the simple delineation method of employing can realize the location and the patterned growth of SWNT.
As shown in Figure 4, from the stereoscan photograph that utilizes surperficial delineation method SWNT with " CNT " printed words of patterned growth on surface of silicon as can be seen, the SWNT patterned growth has proved that this method can realize the SWNT patterned growth of arbitrary shape on the cut with " CNT " printed words.(annotate: CNT is carbon nanotube, i.e. the abbreviation of CNT English).
As shown in Figure 5, from the contrast of using the SWNT of growing after the different sharp objects delineation surface of silicon as can be seen, use diamond tool and sharp-pointed silicon chip delineation can realize the location and the patterned growth of SWNT, but the density difference of the SWNT of the substrate surface of two kinds of rose methods preparation illustrate that variation by the delineation condition and selection (during as the kind of stroke cutter, tip size, delineation the size of dynamics etc.) can realize the control to SWNT density to a certain extent.
The above results shows, the present invention is in a kind of mode of simple delineation silicon substrate, the location and the patterned growth of the high-quality SWNT of any metal impurities have been realized not containing, have easy and simple to handle, cost is low, polarization good and be easy to the characteristics of patterning, for SWNT is laid a good foundation in the application in fields such as nanometer electronic device and sensor.
Claims (7)
1. the method for a surperficial delineation method patterned growth SWNT, it is characterized in that: this method is with the silicon chip that the has thermal oxide layer substrate as the growing single-wall CNT, by using sharp objects to depict pattern at substrate surface, form the SWNT nucleating point by high temperature oxidation process under 200-1100 ℃ condition then, and then under 600-1100 ℃ of high temperature, feed carbon source and carrier gas, the SWNT of the cracking reaction growth patternsization by carbon source.
2. according to the method for the described surperficial delineation method patterned growth SWNT of claim 1, it is characterized in that: employed sharp objects is silicon chip, quartz plate, potsherd, glass cutter or the atomic-force microscope needle-tip that has wedge angle.
3. according to the method for the described surperficial delineation method patterned growth SWNT of claim 1, it is characterized in that: in the course of reaction, carbon source is one or more of hydrocarbon methane, ethane, ethene, acetylene, benzene, toluene, cyclohexane and ethanol, methyl alcohol, acetone, carbon monoxide, and the carbon source flow velocity is the 1-500 ml/min.
4. according to the method for the described surperficial delineation method patterned growth SWNT of claim 1, it is characterized in that: in the course of reaction, carrier gas is a hydrogen; Perhaps, carrier gas is the gaseous mixture of hydrogen and inert gas, and wherein hydrogen volume is than 〉=1/10, and the carrier gas overall flow rate is the 1-2000 ml/min.
5. according to the method for the described surperficial delineation method patterned growth SWNT of claim 1, it is characterized in that: the oxygen gas flow rate of the silicon substrate high temperature oxidation process after the delineation is the 50-500 ml/min, and heat treated temperature is 500-850 ℃.
6. according to the method for the described surperficial delineation method patterned growth SWNT of claim 1, it is characterized in that: the growth temperature of SWNT is 650-950 ℃.
7. according to the method for the described surperficial delineation method patterned growth SWNT of claim 1, it is characterized in that: the thickness of the thermal oxide layer of employed silicon substrate is 1-100nm.
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Cited By (3)
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| CN103738912A (en) * | 2013-12-27 | 2014-04-23 | 西南交通大学 | Monocrystalline silicon non-destructive surface nanometer machining method based on tribo-chemistry induction etching |
| WO2014071693A1 (en) * | 2012-11-08 | 2014-05-15 | 北京大学 | Single-walled carbon nanotube positioning and growing method |
| CN109672080A (en) * | 2019-01-18 | 2019-04-23 | 华东师范大学 | A kind of Low threshold optical pumping accidental laser based on patterned substrate |
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- 2009-09-09 CN CN2009101872957A patent/CN102020239A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014071693A1 (en) * | 2012-11-08 | 2014-05-15 | 北京大学 | Single-walled carbon nanotube positioning and growing method |
| CN103738912A (en) * | 2013-12-27 | 2014-04-23 | 西南交通大学 | Monocrystalline silicon non-destructive surface nanometer machining method based on tribo-chemistry induction etching |
| CN103738912B (en) * | 2013-12-27 | 2016-02-03 | 西南交通大学 | Based on the monocrystalline silicon surface non-destructive nano processing method of tribochemistry induction etching |
| CN109672080A (en) * | 2019-01-18 | 2019-04-23 | 华东师范大学 | A kind of Low threshold optical pumping accidental laser based on patterned substrate |
| CN109672080B (en) * | 2019-01-18 | 2020-07-14 | 华东师范大学 | Low-threshold optically pumped random laser based on patterned substrate |
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Application publication date: 20110420 |