CN102424375B - Preparation method for vertical carbon nanotube array - Google Patents
Preparation method for vertical carbon nanotube array Download PDFInfo
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- CN102424375B CN102424375B CN201110263453XA CN201110263453A CN102424375B CN 102424375 B CN102424375 B CN 102424375B CN 201110263453X A CN201110263453X A CN 201110263453XA CN 201110263453 A CN201110263453 A CN 201110263453A CN 102424375 B CN102424375 B CN 102424375B
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Abstract
The invention provides a preparation method for a vertical single wall carbon nanotube array. The method comprises the following steps: (1) depositing an aluminum film with a thickness of 3 to 20 nanometers on the surface of a substrate; (2) oxidizing the aluminum film at room temperature or at a temperature lower than 200 DEG C as needed; (3) depositing a catalyst layer with a thickness of 0.2 to 1.0 nanometer on the aluminum film or on the oxidized aluminum film; (4) depositing an aluminum film with a thickness of no more than 0.5 nanometer on the catalyst layer; (5) preheating or pretreating a product obtained in step (4) in the presence of 0.1 to 100 millibar low pressure reducing atmosphere; (6) introducing carbon source gas with a concentration of 0.1% to 50% at a growth temperature of 550 to 850 DEG C for growth of the single walled vertical carbon nanotube array. According to the invention, the disadvantages of preparation of single walled carbon nanotubes in the prior art are overcome or at least alleviated; preparation of the single walled vertical carbon nanotube array is realized by using as-simple-as-possible technology and process, and very effective control of the diameter, density and length of the single walled vertical carbon nanotube array can be achieved.
Description
Technical field
The present invention relates to field of nanometer technology, relate more specifically to the nano-tube array technology of preparing, furthermore, relate to a kind of method for preparing vertical carbon nanotube array (including but not limited to the Single Walled Carbon Nanotube orthogonal array).
Background technology
Single Walled Carbon Nanotube can be regarded the seamless tube of diameter below several nanometers (for example 5 nanometers) that is rolled into by certain orientation by the graphite flake of individual layer (being that graphite is rare) visually as.According to the difference of curl direction (chirality), Single Walled Carbon Nanotube may show as metallicity or semiconductive.Except Single Walled Carbon Nanotube, also has multi-walled carbon nano-tubes.Multi-walled carbon nano-tubes can be regarded as by many diameters different Single Walled Carbon Nanotube and mutually be nested and form, and wherein the interlamellar spacing of Single Walled Carbon Nanotube and graphite is close.Multi-walled carbon nano-tubes shows as metal properties.
Carbon nanotube is a kind of desirable monodimension nanometer material, and its length-to-diameter ratio can reach 132,000,000:1, higher than other conventional material, and has the special physicals that significantly is different from blocky graphite, diamond and zero dimension rich happy rare (carbon 60, carbon 70 etc.).For example, the bandwidth of Single Walled Carbon Nanotube is generally between 0-2eV; Maximum current density can reach 10
13A/m
2, be 1000 times of copper; Thermal conductivity reaches ~ 2000W/ (mK), is 5 times of copper; Young's modulus is 1TPa approximately, and the maximum tensile strength is 100GPa approximately, and the strength ratio steel is high 100 times, and weight only has the sixth of steel.This makes carbon nanotube have application prospect very widely at optics, electronics and mechanical field.For example, carbon nanotube can be used for Carbon Nanotubes Reinforced Composites, transparent conducting thin film, feds, nano-transistor, nano-sensor, super capacitor, management device and super large-scale integration interconnection line etc.Due to the existing metal properties of Single Walled Carbon Nanotube, semiconductor properties is arranged again, so its application prospect is more extensive than multi-walled carbon nano-tubes.Current, the application of carbon nanotube has been subject to the serious restriction of its technology of preparing, main restricting factor is and can't effectively controls in process of production the activity of catalyzer, also is difficult to effectively control in process of production the characteristic of carbon nanotube: as orientation, density, quality, purity, diameter and chirality etc.
Preparation method of carbon nano-tube commonly used mainly contains at present: arc discharge method, laser ablation method, chemical Vapor deposition process, solid-phase pyrolysis, electric glow discharge method and gas combustion method and polyreaction synthesis method etc.But most methods can only prepare foreign matter content, and (being mainly the carbon material of metal catalyst and other form) is very high, is orientated mixed and disorderly carbon nanotube powder.Chemical Vapor deposition process is present topmost method for carbon nano-tube oriented growth, the aspects such as its quality at carbon nanotube, purity, orientation, length, density and area, especially selective ensemble growth have the incomparable superiority of other method.
Aspect the Single Walled Carbon Nanotube orthogonal array prepares, the technical scheme that the people such as the most representative is MaruyamaShigeo proposed in 2004.Described technical scheme is utilized normal pressure thermal chemical vapor deposition method, and the alcohol of using has been prepared the Single Walled Carbon Nanotube orthogonal array first as raw material.Its shortcoming is that productive rate is extremely low, and carbon nanotube can only grow into several micron thickness.The people such as the people such as Hata Kenji and ZhongGuofang has prepared respectively millimetre-sized Single Walled Carbon Nanotube orthogonal array subsequently.The former uses atmospheric steam auxiliary heat chemical gaseous phase depositing process, but use ethene as carbon source, obtain high productive rate by the method for adding ppm ten to several thousand water vapors in growth atmosphere, (for example can prepare fast the carbon nanotube of 1-2 millimeter, preparation speed is approximately 200 microns/minute), but the life-span of catalyzer generally is no more than half an hour, the diameter of single-wall carbon nano tube of growth is bigger than normal (for example, mean diameter reaches the 3-4 nanometer), its length density is controlled very difficult; Latter utilizes remote microwave plasma activated chemical vapour deposition method, although the productive rate of unit time is not high, but the life-span of catalyzer reached more than tens hours, its moderate growth velocity (for example, preparation speed is approximately 20 microns/minute) makes the length of carbon nanotube control in addition becomes possibility.
Summary of the invention
The object of the invention is to overcome or alleviate at least prior art and prepare the drawback of Single Walled Carbon Nanotube, realize the preparation of Single Walled Carbon Nanotube by simple as far as possible technology and technique.
For achieving the above object, the invention provides a kind of method for preparing the Single Walled Carbon Nanotube orthogonal array, described method comprises the steps:
(1) deposit thickness is the aluminium film of 3-20 nanometer on substrate surface;
(2) as required, at room temperature oxidation or at the temperature lower than 200 degrees centigrade the described aluminium film of oxidation;
(3) catalyst layer of deposition 0.2-1.0 nanometer on described aluminium film or pellumina;
(4) deposit the aluminium film that is not thicker than 0.5 nanometer on described catalyst layer;
(5) substrate that the product of step (4) has namely been deposited catalyzer/support membrane is put on the sample warm table or well heater of vacuum chamber of low-pressure chemical vapor deposition system, vacuum chamber is evacuated to and is better than more than 0.01 millibar, then described substrate was heated in 1-10 minute the growth temperature of 550-850 degree centigrade under 0.1-100 millibar hydrogen atmosphere from room temperature; Perhaps described substrate is put on the indoor sample transport mechanism of low-pressure chemical vapor deposition system vacuum, vacuum chamber is vacuumized and makes back end vacuum tightness be better than 0.01 millibar, then under 0.1-100 millibar hydrogen atmosphere, the sample warm table is heated to 550-900 degree centigrade from room temperature, with sample transport mechanism, described substrate is sent on well heater again, makes substrate be heated rapidly to the growth temperature of 550-850 degree centigrade.
(6) after reaching described growth temperature, pass into concentration and be set as the carbon-source gas of 0.1-50%, the time of 10 seconds to 100 hours of growing.Wherein said carbon-source gas is that the carbonaceous gass such as acetylene gas or methane, ethene carry out converted acetylene gas after pyroprocessing or Cement Composite Treated by Plasma.Diluent gas is hydrogen.It is invariable that the concentration of growth temperature and carbon-source gas both can keep, also can be as required respectively 0.1-50% and 550-850 degree centigrade of certain adjustment of work.
Use hydrogen as diluent gas.As a kind of interchangeable embodiment, the substrate that also product of step (4) namely can have been deposited catalyzer/support membrane is put on the sample warm table or well heater of vacuum chamber of low-pressure chemical vapor deposition system, vacuum chamber is evacuated to more than 0.01 millibar, then pass into the carbon-source gas (preferred acetylene gas) that concentration is set as 0.1-50%, diluent gas is hydrogen, then under 0.1-100 millibar air pressure with described substrate heating to the growth temperature of 550-850 degree centigrade and keep time of 10 seconds to 100 hours.
Preferably, described method may further include following step: (7) after growth finishes, close carbon-source gas and/or hydrogen supply to vacuum chamber, and stopped heating, simultaneously with the maximum pumping speed vacuum chamber of finding time, and when being cooled to room temperature, the temperature of described substrate takes out goods.
The thickness of the described aluminium film that preferably, deposits on described catalyst layer is between the 0.3-0.5 nanometer; At the thickness of the described aluminium film that deposits on substrate surface between the 5-10 nanometer, and oxidation under room temperature or low temperature in air, oxygen or low-temperature oxygen plasma atmosphere before the described catalyst layer of deposition in advance.
Preferably, the thickness of described catalyst layer is conducive to super-high density (〉 10 between the 0.2-0.4 nanometer
13Root/square centimeter order of magnitude) and the growth of micron order carbon nanotube; The thickness of described catalyst layer is conducive to low density (10 between the 0.7-1.0 nanometer
11Root/square centimeter order of magnitude) and the growth of grade carbon nanotube; The thickness of described catalyst layer is conducive to intermediate density (10 between the 0.4-0.7 nanometer
12Root/square centimeter order of magnitude) growth of carbon nanotube.
Preferably, temperature-rise period described in described step (2) is: take room temperature as starting point, in 10-30 millibar hydrogen reduction atmosphere with the temperature of substrate at 3-5 minute with the interior 550-850 degree centigrade that rises to, and the wall of vacuum chamber keeps water-cooled or air cooling (this is conducive to assurance equipment and staff's safety).Described temperature-rise period can be both persistently overheating, can be also temperature-gradient method.Temperature-gradient method is exactly to comprise at least once temperature be elevated to an intermediate value and keep for some time, then continues to heat up, until reach growth temperature.
Preferably, described carbon-source gas is acetylene gas.
Preferably, described carbon-source gas can be for carrying out converted acetylene gas after pyroprocessing or Cement Composite Treated by Plasma to methane, ethene.
Preferably, by controlling the thickness of catalyzer, in conjunction with the temperature of substrate in warm and the time of preheating, the concentration of acetylene in process of growth, the temperature of substrate and the time of growth, adjust diameter Distribution, mean diameter, density and the length of prepared Single Walled Carbon Nanotube orthogonal array.
Preferably, the diameter Distribution of the Single Walled Carbon Nanotube in described Single Walled Carbon Nanotube orthogonal array can (for example be regulated in the 0.5-4 nanometer range, 0.5-2 nanometer), mean diameter is regulated in the 0.9-2.0 nanometer range, length can be in 10 nanometers-5 millimeter with interior adjusting, density can be in super-high density 10
13Root/square centimeter is to 10
11Regulate in root/square centimeter order of magnitude scope, carbon nano pipe purity can be up to more than 99wt%.
Particularly, the present invention prepares the method for Single Walled Carbon Nanotube orthogonal array, can comprise two parts: a part relate to a kind of sandwich style nanocatalyst/the support membrane structure (for example: AlO
x/ Fe/AlO
x/ substrate) Design ﹠ preparation, catalyzer be with iron (Fe), and the transition metal such as cobalt (Co) or nickel (Ni) or its alloy are main, and support membrane uses aluminum oxide (Al
2O
3Perhaps AlO
x); Another part relates to the pre-treatment of catalyzer under the low-pressure chemical vapor deposition condition and forming core and the oriented growth of Single Walled Carbon Nanotube.
The method of preparation provided by the present invention single-wall carbon nanotube array arranged vertically, can comprise the steps:
One, the Design ﹠ preparation of the nanocatalyst of sandwich style
(1) utilize the technology such as sputter coating or evaporation coating at substrate surface deposition 3-20 nano aluminum (Al) film, preferred thickness is the 5-10 nanometer, can be in a side surface or the upper deposition of many side surfaces (as three-dimensional substrate) of substrate, wherein substrate is generally monocrystalline silicon piece or metal alloy film.
(2) as required, can specially the described aluminium film of step (1) be exposed in air, pure oxygen or oxygen-enriched atmosphere, or carry out room temperature natural oxidation or low temperature (＜200 degrees centigrade) oxidation in the oxygen enrichment plasma body, thereby form fine and close pellumina AlO
x.
(3) utilize the technology such as sputter coating or evaporation coating to deposit the catalyst layer of 0.2-1 nanometer on above-mentioned aluminium film or pellumina, typical catalyst is iron.
(4) utilize again the deposition techniques such as sputter coating or evaporation coating not to be thicker than the aluminium film of 0.5 nanometer on described catalyst layer.The aluminium film is partially oxidized to I haven't seen you for ages because being exposed to air, thereby forms a kind of AlO
x/ Fe/AlO
xThe catalyzer of sandwich style/support membrane system.Whole catalyst preparation process is seen Fig. 1.
Two, the preparation of Single Walled Carbon Nanotube orthogonal array
(5) substrate that the product of step (4) has namely been deposited catalyzer/support membrane is put on the sample warm table or well heater of vacuum chamber of low-pressure chemical vapor deposition system, as shown in Figure 2, after good seal, vacuum chamber is evacuated to and is better than 0.01 millibar, otherwise for safety, carry out system leak detection and maintenance makes it reach airtight requirement.Then described substrate was heated in 1-10 minute the growth temperature of 550-850 degree centigrade under 0.1-100 millibar hydrogen atmosphere from room temperature; Perhaps described substrate is put on the indoor sample transport mechanism of low-pressure chemical vapor deposition system vacuum, vacuum chamber is vacuumized and makes back end vacuum tightness be better than 0.01 millibar, then under 0.1-100 millibar hydrogen atmosphere, the sample warm table is heated to 550-900 degree centigrade from room temperature, with sample transport mechanism, described substrate directly is sent on high temperature heater (HTH) again, makes substrate be heated rapidly to the growth temperature of 550-850 degree centigrade.
This step is called substrate preheating or substrate pre-treatment.The vacuum chamber wall generally adopts water-cooled or air cooling to guarantee safety.Optimum condition is to use the High Purity Hydrogen of 200-500 standard state ml/min flow in 3-5 minute, substrate to be elevated to and to remain on 650-750 degree centigrade from room temperature under 10-30 millibar condition.
(6) directly introduce certain density acetylene (for example, 0.1-50%C2H2, use hydrogen as diluent gas) after the substrate pre-treatment finishes, thereby start forming core and the growth of Single Walled Carbon Nanotube.Acetylene can be also other carbonaceous gas as the process Cement Composite Treated by Plasma such as methane, ethene or heat and produce.In this process, the air pressure of the total flux of gas and vacuum chamber and preprocessing process generally are consistent, but also can be inconsistent.Concentration and the growth time of acetylene are determined according to real needs, concentration does not wait from some thousandths of to percent tens, time remaining did not wait by tens hours in tens seconds, for example continue 10 seconds to 100 hours (such as 10 seconds, 1 minute kind, 10 minutes, 1 hour, 5 hours, 20 hours, 50 hours, 100 hours etc. particularly); The Single Walled Carbon Nanotube of growth is perpendicular to the surface of substrate.
In addition, a kind of replaceable embodiment as step (5) and (6), the substrate that also product of step (4) namely can have been deposited catalyzer/support membrane is put on the sample warm table or well heater of vacuum chamber of low-pressure chemical vapor deposition system, vacuum chamber is evacuated to more than 0.01 millibar, then pass into the carbon-source gas (preferred acetylene gas) that concentration is set as 0.1-50%, diluent gas is hydrogen, then under 0.1-100 millibar air pressure with described substrate heating to the growth temperature of 550-850 degree centigrade and keep time of 10 seconds to 100 hours.This embodiment omits pre-treatment step, but the quality of Single Walled Carbon Nanotube upper space is slightly poor, and the quality of the following carbon nanotube in surface is all fine.
(7) after growth finishes, stop supplies carbon-source gas and/or hydrogen immediately, cut off the power supply of well heater,, simultaneously with the gas in the emptying vacuum chamber of maximum pumping speed, then system cools taken out sample to lesser temps.
In said process, prepared surface A lO
xCan the partial coverage catalyzer, aggregate into larger nano particle by surface diffusion thereby effectively suppress catalyzer in pre-treatment and carbon nano tube growth process.Prepared bottom AlO
xFine and close support membrane can promote counter the invade profit of catalyzer in preprocessing process on the one hand, thereby forms as far as possible little nano particle, can effectively stop on the other hand catalyzer to pass through bulk diffusion and the substrate reaction.The test confirmation, by the catalyzer with the upper type preparation, its activity can continue at least tens hours in the low-pressure chemical vapor deposition process.
In said process,, to large area substrates, can improve the homogeneity of Single Walled Carbon Nanotube growth with gas distributor or the current equalizer of shower hair style, as shown in Figure 2.According to the size of area and the vacuum chamber of substrate, the flow of gas can also further increase or reduce, but air pressure generally remains in 0.1-100 millibar scope.
In said process, by the thickness of regulating catalyst layer, the temperature and time of substrate preheating, can effectively control size and the density of nano particle, in conjunction with suitable concentration of acetylene, control, the diameter Distribution of Single Walled Carbon Nanotube and density just can be effectively controlled.Can realize again the length control of Single Walled Carbon Nanotube by the length of growth time.Particularly point out, by using present method, the contriver has realized super-high density (〉 10 first in world wide
13The preparation of Single Walled Carbon Nanotube orthogonal array root/square centimeter), for laying a good foundation with the carbon nanotube instead of copper in nano chips interconnection applications of future generation.
In the single-wall carbon nanotube array arranged vertically that the present invention obtains, the diameter Distribution of Single Walled Carbon Nanotube is different because of thickness and the pretreated condition of catalyzer, and mean diameter can be regulated between the 1.0-2.5 nanometer, and density can be 5 * 10
11-5 * 10
13Regulate low density (≤10 between root/square centimeter
12Root/square centimeter) the longest the reaching more than 5 millimeters of Single Walled Carbon Nanotube length, but super-high density (〉=10
13Root/square centimeter) Single Walled Carbon Nanotube length is no more than tens microns.Reason is that the growth of carbon nanotube is subject to carbon-source gas spreads in carbon nano pipe array restriction.The prepared single wall carbon nano pipe purity of the present invention can be up to more than 99wt%.
The Single Walled Carbon Nanotube preparation method that the present invention proposes, have the growth controllability high, the high characteristics of the carbon nano pipe purity that obtains, the diameter Distribution of Single Walled Carbon Nanotube, the controllability of density and length significantly is better than the preparation method of other aumospheric pressure cvd single-wall carbon nanotube array.
As do not have clear and definite opposite statement, the term in literary composition " maximum pumping speed " to refer to the exhaust velocity that reaches connecting when valve between CVD vacuum chamber and vacuum pump is opened fully.
As do not have clear and definite opposite statement, the carbon-source gas concentration in literary composition to refer to the standard volume flow ratio of carbon-source gas and total gas (comprising carbon-source gas and diluent gas).For example, carbon-source gas concentration 50% refers to that a carbon-source gas mixes with a diluent gas and the concentration that obtains.
Description of drawings
Fig. 1 is the schematic diagram for preparing of catalyzer.
Fig. 2 is single-wall carbon nanotube array low-pressure chemical vapor deposition schematic diagram.It comprises low-pressure chemical vapor deposition vacuum chamber 1, inlet mouth 2, vacuum pumping opening 3, gas distributor or current equalizer 4 and well heater and sample table 5.
Fig. 3 is Single Walled Carbon Nanotube orthogonal array scanning electron photomicrograph prepared in embodiment 1.
Fig. 4 is single-wall carbon nanotube array high-resolution transmission electron micrograph prepared in embodiment 1.
Fig. 5 is the laser Raman spectroscopy figure of single-wall carbon nanotube array prepared in embodiment 1.
Fig. 6 is the Single Walled Carbon Nanotube orthogonal array style of the different shape of approximately half cm long prepared in embodiment 2.
Fig. 7 is the laser Raman spectrum of the Single Walled Carbon Nanotube orthogonal array fracture of approximately half cm long prepared in embodiment 2.
Fig. 8 is the thermogravimetric analysis result of grade Single Walled Carbon Nanotube.
Fig. 9 is the scanning electron photomicrograph of super-high density single-wall carbon nanotube array prepared in embodiment 3.
Figure 10 is super-high density single-wall carbon nanotube array high-resolution transmission electron micrograph and carbon nanotube diameter Distribution statistics prepared in embodiment 3.
Figure 11 is the low power electron photomicrograph of super-high density single-wall carbon nanotube array after alcohol-pickled volatilization compression prepared in embodiment 3.
Figure 12 is the chart that shows the Auto-regulating System of Density of Heavy Medium of Single Walled Carbon Nanotube orthogonal array.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further, but the present invention is not limited to the disclosed technical scheme of embodiment in literary composition and concrete technical characterictic,, protection scope of the present invention is defined by the following claims.
One, the preparation of Single Walled Carbon Nanotube orthogonal array
1, the preparation of Single Walled Carbon Nanotube orthogonal array
(1) cleaning of substrate: select the monocrystalline silicon piece in 4 inches (100) crystal orientation of diameter as substrate, use successively acetone, alcohol and deionized water ultrasonic cleaning 5 minutes; Finally substrate is dried up with high pure nitrogen.
(2) substrate is packed in magnetron sputtering vacuum chamber, be evacuated to 1 * 10
-5After millibar, by sputter coating, at substrate surface, deposit 7 nano aluminum films.Take out sample after finishing, and sample is exposed in air, thereby with the oxidation of aluminium film.Again substrate is packed into afterwards in magnetron sputtering vacuum chamber, be evacuated to 1 * 10
-5After millibar, by sputter coating at substrate surface deposition 0.5 nanometer Fe film, then in the situation that not vacuum breaker then deposit 0.5 nano aluminum film.After end, take out sample, and with this substrate be cut to 10 millimeters * 10 millimeters and 6 millimeters * 3 millimeters etc. different big or small little substrates stand-by.
(3) the little substrate of polylith previous step preparation is placed on pyrolitic boron nitride/graphite (PBN/PG) composite heater in the chemical vapour deposition vacuum chamber, after vacuum chamber is evacuated to 0.001 millibar, pass into 200 standard state ml/min high-purity hydrogens, and with air pressure adjustment to 15 millibar, then open heating power supply, sample table was heated to then remain on 650 degrees centigrade in 4 minutes.
(4) preheating after 5 minutes altogether, the flow of hydrogen is adjusted into 195 standard state ml/min, pass into simultaneously 5 standard state ml/min acetylene, start the growth of Single Walled Carbon Nanotube, grow and close all gas and cut off heating power supply after 10 minutes, and the residual gas in the vacuum chamber of finding time fast.In process of growth, air pressure and sample table temperature remain unchanged.Can carefully take out prepared Single Walled Carbon Nanotube when sample table is cooled near room temperature by the time.
2, the sign of Single Walled Carbon Nanotube orthogonal array
Prepared single-wall carbon nanotube array is carried out the signs such as scanning electronic microscope, transmission electron microscope and laser Raman spectroscopy.
The scanning electron photomicrograph that is the single-wall carbon nanotube array that said process obtains shown in Figure 1.The height of carbon nano pipe array is about 200 microns, because average growth rate only has about 20 microns/minute, hang down one more than the order of magnitude than the growth velocity of water at atmospheric pressure steam assistant chemical vapor deposition, so the length of carbon nanotube is easy to by growth time controlled.Can find from figure, the carbon nanotube that obtains is grown perpendicular to substrate, and arranges more neat.
A large amount of macrocracks that sample surfaces occurs are higher signs of carbon nanotube density, and reason is that the effect of the Van der Waals force between adjacent nanotube causes by force top to be shunk.By weighing, measure length, growth area and with the volume density of the prepared single-wall carbon nanotube array of the proofs such as mean diameter of transmission electron microscope observation statistics carbon nanotube, reaching ~ 60 kilograms per cubic meter, area density reaches 10
12Root/more than square centimeter, namely being equivalent to every 100 square nanometers has an above carbon nanotube.Density can be reduced to 10 by the thickness that increases catalyzer
12Root/below square centimeter.
Above-mentioned prepared sample is carried out the observation of high-resolution and the clear transmission electron microscope of superelevation, result shows, prepared carbon nanotube is Single Walled Carbon Nanotube, do not observe metal catalyst particles, double-walled or multi-walled carbon nano-tubes, do not observe obvious decolorizing carbon on tube wall yet and adhere to vestige, illustrate that the Single Walled Carbon Nanotube quality and the purity that obtain are all very high.Fig. 4 a is depicted as Single Walled Carbon Nanotube (the i:0.9 nanometer of two different diameters, the photo of the atomic resolution ii:2.6 nanometer), Fig. 4 b are the diameter Distribution figure of Single Walled Carbon Nanotube, can find out, the diameter Distribution of carbon nanotube is between the 0.5-4 nanometer, and mean diameter is 1.3 nanometers.Mean diameter is starkly lower than the 2.8-3.0 nanometer of water at atmospheric pressure steam assistant chemical vapor deposition.
The laser Raman spectroscopy of the Single Walled Carbon Nanotube sample that said process is prepared as shown in Figure 5.0-400cm
-1Between peak and 1591cm
-1Acromion or the detached peaks at peak (are positioned at 1555cm
-1Place) be the laser Raman spectrum fingerprint of Single Walled Carbon Nanotube.0-400cm
-1Between peak come from the breathing mould (RBM) of Single Walled Carbon Nanotube, the diameter that different peaks are corresponding different.The appearance at these peaks, and the intensity at RBM peak is also higher, proves that also prepared carbon nanotube is Single Walled Carbon Nanotube.1591cm
-1The Raman peaks at place is the G peak, derives from the graphite flake layer structure of carbon nanotube; 1340cm
-1The Raman peaks at place is the D peak, derives from defect and decolorizing carbon in carbon nanotube structure.The G/D peak intensity ratio of gained sample reaches 8 left and right, shows that the quality of Single Walled Carbon Nanotube is fine.
One, half cm long Single Walled Carbon Nanotube orthogonal array style (patterning) growth
1, half cm length Single Walled Carbon Nanotube orthogonal array style growth
(1) cleaning of substrate: select the monocrystalline silicon piece in 4 inches (100) crystal orientation of diameter as substrate, use successively acetone, alcohol and deionized water ultrasonic cleaning 5 minutes; Finally substrate is dried up with high pure nitrogen.
(2) substrate is packed in magnetron sputtering vacuum chamber, one of surface coverage has the mask of 400 microns * 4 millimeters style arrays, is evacuated to 1 * 10
-5After millibar, deposit the Al style array of 400 microns * 4 millimeters of 10 nanometer thickness at substrate surface by sputter coating.Take out sample after finishing, and sample is exposed in air, thus this aluminium film of oxidation.Again substrate is packed into afterwards in magnetron sputtering vacuum chamber, do not re-use mask, be evacuated to 1x10
-5After millibar, by sputter coating at substrate surface deposition 0.5-0.7 nanometer Fe film, then in the situation that not vacuum breaker then deposit 0.5 nano aluminum film.After end, take out sample, and this substrate is cut to the little substrate of 6 millimeters * 3 millimeters, all have 400 microns * 4 millimeters silver color of a visible rectangular on each little substrate.
Utilize the method same with step (2), use the catalyst array of other other different pattern of Mask Fabrication, as round dot, honeycomb array etc.
(3) the little substrate of the above step of polylith preparation is placed on induction heating molybdenum (Mo) sample table in remote microwave plasma activated chemical vapour deposition vacuum chamber, treats that vacuum chamber is evacuated to 1x10
-6After holder, pass into 5 standard state ml/min high-purity methanes and 45 standard state ml/min high-purity hydrogens, and, with air pressure adjustment to 20 holder, then open induction heating power, sample table was heated to then remain on 700 ° of C in 3 minutes.
(4) preheating after 5 minutes altogether, open the remote microwave plasma body of 60W, methane will be converted into acetylene by certain ratio, thereby start the growth of Single Walled Carbon Nanotube, difference according to catalyzer style array, grow after 5-40 hour and close all gas supply and cut off induction heating power, and the residual gas in the vacuum chamber of finding time fast.Can carefully take out prepared Single Walled Carbon Nanotube goods when sample table is cooled near room temperature by the time.
Length to the Single Walled Carbon Nanotube of the sample that obtains is measured, and the length of carbon nanotube can reach more than 5 millimeters.Be approximately half centimetre high that obtains shown in Fig. 6 a-c, the low power stereoscan photograph of the single-wall carbon nanotube array of various different shapes.Fig. 6 d is depicted as the growth length of corresponding carbon nanotube and the graph of a relation of time.Test confirms, carbon nanotube is higher because of density, even catalyzer has been carried out the style design, if mean density is still higher, its growth still is subject to the impact of carbon source diffusion mass transfer, so length and time present parabolical relation.But for the very large tiny rectangular catalyzer of spacing, the length of carbon nanotube and time are almost linear, see Fig. 6 d.This also shows, the prepared catalyzer of the present invention is under the low-pressure chemical vapor deposition condition, and its activity/life-span can keep more than tens hours.
The transmission electron microscope observation result shows, the carbon nanotube that obtains is Single Walled Carbon Nanotube.The Laser Roman spectroscopic analysis of composition (see figure 7) has also confirmed the existence of Single Walled Carbon Nanotube; Raman spectrum G/D peak intensity, than be increased to 25 of bottom by 6 of top, shows that the crystalline quality of Single Walled Carbon Nanotube is very good.Because these Single Walled Carbon Nanotube are grown with root growth mechanism, namely from the granules of catalyst that is fixed on carbon nanotube root/substrate surface, start to grow, the carbon nanotube at top its quality after being exposed to for a long time the chemical vapour deposition environment degenerates to some extent and is difficult to avoid.
The preparation of grade Single Walled Carbon Nanotube also makes the thermogravimetric analysis of Single Walled Carbon Nanotube more easily realize.Figure 8 shows that the aerial thermogravimetric analysis measuring result of grade Single Walled Carbon Nanotube.Single Walled Carbon Nanotube, since 600 degrees centigrade of quick weight loss, reaches peak value during to 675 degrees centigrade of left and right, the weightless end in the time of 750 degrees centigrade; Almost do not find residue after burning, show the carbon based on very high purity of acquisition Single Walled Carbon Nanotube, greater than 99.9wt%.
The preparation of embodiment 3 super-high density Single Walled Carbon Nanotube orthogonal array
(1) cleaning of substrate: selecting diameter is 4 inches, the surface heat 200 nanometer SiO that grown
2Si(100) single-chip is as growth substrate, cleaned 5 minutes in acetone, alcohol and deionized water for ultrasonic successively; Finally substrate is dried up with high pure nitrogen.
(2) substrate is packed in magnetron sputtering vacuum chamber, be evacuated to 1 * 10
-5After millibar, by sputter coating, at substrate surface, deposit 5-7 nano aluminum film.Take out sample after finishing, and be exposed to for a long time sample in air, or with low temperature room temperature oxygen plasma treatment substrate even, thereby strengthen this aluminium film in room temperature or the oxidation under lower than 200 degrees centigrade, form the catalyzer support membrane of particularly compact, make ultra-thin catalyzer can not lose because of bulk diffusion.Again substrate is packed into afterwards in magnetron sputtering vacuum chamber, be evacuated to 1x10
-5After millibar, by sputter coating at substrate surface deposition 0.3-0.4 nanometer Fe film, then in the situation that not vacuum breaker then deposit 0.3-0.5 nano aluminum film.After end, take out sample, and with this substrate be cut to 10 millimeters * 10 millimeters and 6 millimeters * 3 millimeters etc. the little substrate that varies in size stand-by.
(3) scales/electronic balance weighing of sensitivity up to 0.01mg numbered and used to the substrate of 10 millimeters * 10 millimeter, the quality that record is corresponding.
(4) the polylith previous step being prepared substrate is placed on pyrolitic boron nitride/graphite (PBN/PG) composite heater/sample table in the chemical vapour deposition vacuum chamber, after vacuum chamber is evacuated to 0.001 millibar, pass into 500 standard state ml/min high-purity hydrogens, and with air pressure adjustment to 15 millibar, then open heating power supply, sample table was heated to then remain on 700 ° of C in 3 minutes.
(5) preheating after 4 minutes altogether, pass into the acetylene of 6-10%, regulate simultaneously the flow of high-purity hydrogen, total flux is remained unchanged, so just started the growth of Single Walled Carbon Nanotube, close all gas supply after growth half a minute to tens minute and cut off heating power supply, and the residual gas in the vacuum chamber of finding time fast.In process of growth, air pressure and sample table temperature remain unchanged.By the time sample table cooling near room temperature the time can carefully take out prepared Single Walled Carbon Nanotube.
To prepared Single Walled Carbon Nanotube carry out linear measure with scanning electronic microscope, find that carbon nano tube surface is very smooth, be difficult to observe macrocrack noted earlier; The arrangement of carbon nanotube is extremely fine and close in addition, and length generally is no more than 10 microns, has almost stopped growth in several minutes, as shown in Figure 9.Prepared sample is found with the high-resolution transmission electron microscope observation, and prepared diameter of single-wall carbon nano tube is distributed between the 0.5-2.0 nanometer, and mean diameter only has 1.0 nanometers, is far superior to the Single Walled Carbon Nanotube of aumospheric pressure cvd method preparation.The quality of Single Walled Carbon Nanotube is also very high, does not only observe decolorizing carbon, and double-walled or multi-walled carbon nano-tubes also are difficult to observe metal catalyst particles.Prepared Single Walled Carbon Nanotube orthogonal array is carried out the laser Raman spectrum sign also confirmed this point.
Single Walled Carbon Nanotube sample to 10 millimeters * 10 millimeters is used high-sensitive scales/electronic balance weighing again, by the weightening finish of Single Walled Carbon Nanotube, and the growth area, length and mean diameter can obtain volume density and the area density of Single Walled Carbon Nanotube.Measurement shows, the present invention in worldwide, has prepared the Single Walled Carbon Nanotube orthogonal array of super-high density first, and its density is up to 10
13Root/more than square centimeter, being equivalent to every 10 square nanometers just has 1 above carbon nanotube; Density ~ 4x10 far above the single-wall carbon nanotube array of water vapour assistant chemical vapor deposition preparation
11Root/square centimeter.Following table has been listed the partial density measuring result.
The density measurement of Single Walled Carbon Nanotube orthogonal array:
Wherein, M0: the weight of substrate before growth, M1: the weight of growth mera, Δ M: weightening finish, S: the area of substrate, L: the length of carbon nanotube, ρ v: volume density, ρ s: area density.
Carbon nano pipe array is after liquid such as alcohol-pickled drying, and its area is often shunk greatly, and its reason is that carbon nanotube is subject to the effect of surface tension of liquid therebetween in the process of drying.The test that above-mentioned prepared super-high density single-wall carbon nanotube array is carried out alcohol-pickled drying shows, after shrinking, the area of Single Walled Carbon Nanotube is still up to 71% of original area, see Figure 11, the single-wall carbon nanotube array for preparing higher than the water vapour assistant chemical vapor deposition far away.Area after latter's compression only has the 3-5% of original area.
Further test is found, the concentration of the acetylene of setting when the density of Single Walled Carbon Nanotube orthogonal array also can be to a certain extent by growth is regulated, as shown in figure 12.
Claims (9)
1. a method for preparing the Single Walled Carbon Nanotube orthogonal array, is characterized in that, comprises the steps:
(1) prepare the nanocatalyst of sandwich style, specifically comprise the steps:
1. deposit thickness is the aluminium film of 3-20 nanometer on a side surface of substrate or many side surfaces;
2. at room temperature or at the aluminium film that step is formed in 1. higher than room temperature but at lower than the temperature of 200 degrees centigrade on described substrate carry out oxidation;
3. deposit the catalyst layer of 0.2-1.0 nanometer thickness on described aluminium film;
4. deposit the aluminium film that is not thicker than 0.5 nanometer on described catalyst layer;
(2) use the resulting nanocatalyst of above-mentioned steps (1) to prepare the Single Walled Carbon Nanotube orthogonal array.
2. the method for preparing the Single Walled Carbon Nanotube orthogonal array as claimed in claim 1, is characterized in that, step (2) comprises the steps:
The product of step (1) is put on the sample warm table of vacuum chamber of low-pressure chemical vapor deposition system, described vacuum chamber is evacuated to 0.01 millibar or lower pressure, then described product was heated in 1-10 minute the 550-850 degree centigrade of growth temperature in scope under 0.1-100 millibar hydrogen atmosphere from room temperature; Perhaps
The product of step (1) is put on the indoor sample transport mechanism of low-pressure chemical vapor deposition system vacuum, vacuum chamber is evacuated to 0.01 millibar or lower pressure, then under 0.1-100 millibar hydrogen atmosphere, described sample warm table is heated to the 550-900 degree centigrade of temperature in scope from room temperature, with sample transport mechanism, described product is sent on described sample warm table again, makes described product be rapidly heated to the growth temperature of 550-850 degree centigrade.
3. the method for preparing the Single Walled Carbon Nanotube orthogonal array as claimed in claim 2, is characterized in that, step (2) comprises the growth step of following carbon nanotube:
After reaching described growth temperature, pass into concentration and be set as the carbon-source gas of 0.1-50%, the time of 10 seconds to 100 hours of growing, wherein said carbon-source gas is used hydrogen as diluent gas.
4. the method for preparing the Single Walled Carbon Nanotube orthogonal array as claimed in claim 1, is characterized in that,
The product of step (1) is put on the sample warm table or well heater of vacuum chamber of low-pressure chemical vapor deposition system, vacuum chamber is evacuated to and makes vacuum tightness be better than 0.01 millibar, then pass into the carbon-source gas that concentration is set as 0.1-50%, diluent gas is hydrogen, then under 0.1-100 millibar air pressure with described substrate heating to the growth temperature of 550-850 degree centigrade and keep time of 10 seconds to 100 hours.
5. the method for preparing the Single Walled Carbon Nanotube orthogonal array as described in claim 3 or 4, is characterized in that, step (2) comprises the steps:
After growth finishes, close carbon-source gas and/or hydrogen supply to vacuum chamber, and stopped heating, simultaneously with the maximum pumping speed vacuum chamber of finding time, and when being cooled to room temperature, the temperature of described substrate takes out goods.
6. the method for preparing the Single Walled Carbon Nanotube orthogonal array as claimed in claim 1, is characterized in that, in described step (1) 2. step carried out in air, oxygen or low-temperature oxygen plasma atmosphere.
7. the method for preparing the Single Walled Carbon Nanotube orthogonal array as described in claim 3 or 4, is characterized in that, described carbon-source gas is acetylene gas.
8. the method for preparing the Single Walled Carbon Nanotube orthogonal array as described in claim 3 or 4, is characterized in that, the acetylene gas of described carbon-source gas for by methane and/or ethene, being converted to through pyroprocessing and/or Cement Composite Treated by Plasma in described vacuum chamber.
9. the method for preparing the Single Walled Carbon Nanotube orthogonal array as described in claim 3 or 4, it is characterized in that, temperature and the rate of heating of substrate in thickness by controlling described catalyzer, heat-processed, the concentration of acetylene in process of growth, adjust diameter Distribution, mean diameter, density and the length of prepared vertical carbon nanotube array.
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