CN101948105A - Method for preparing vertical array of high-purity single-walled carbon nanotubes - Google Patents
Method for preparing vertical array of high-purity single-walled carbon nanotubes Download PDFInfo
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Abstract
The invention discloses a method for preparing the vertical array of high-purity single-walled carbon nanotubes, and in particular relates to a moisture-assisted chemical vapor deposition method under normal pressure. In the method, aluminum oxide-supported transitional metal Fe is taken as a catalyst, inert gas and hydrogen are taken as carrier gas, 50 to 1000ppm moisture is added into chemical vapor deposition atmosphere to improve the efficiency and prolong the service life of the catalyst, and high-purity single-walled carbon nanotubes which are vertical to a substrate are prepared. By the method, the relatively high carbon nanotube array can be grown within ten minutes, and the carbon purity of the single-walled nanotubes can reach 99 weight percent.
Description
Technical field
The present invention is a kind of method for preparing the arranged vertical single-wall carbon nanotube array, and the moisture auxiliary chemical vapor deposition method prepares the method for high purity Single Walled Carbon Nanotube orthogonal array under a kind of normal pressure, belongs to field of nanometer technology.
Background technology
Carbon nanotube is the one dimension hollow nano material of being curled and being formed by the graphite flake layer that carbon atom forms.Structural singularity has determined carbon nanotube to have the performance of a series of excellences, as high physical strength, unique electroconductibility, good heat transfer ability, high specific surface area, chemical stability and good field emission property or the like.Therefore, since the nineties in last century, carbon nanotube is once the extensive concern of finding just to have caused international academic community and industrial community.
In the various macroscopic body materials that carbon nanotube constituted, as carbon nano-tube fibre, carbon nanotube yarn, carbon nano-tube sheets etc., the carbon nano pipe array of arranged vertical is owing to have good directivity, therefore the excellent properties of single-root carbon nano-tube can be farthest kept, aspects such as filed emission cathode material, heat interfacial material, integrated circuit interconnection, transmitter, support of the catalyst can be widely used in.
According to the number of plies of the graphite flake that constitutes carbon nanotube, carbon nanotube is divided into two kinds of Single Walled Carbon Nanotube and multi-walled carbon nano-tubes usually.Therefore the single-wall carbon nanotube array of arranged vertical all has important application prospects at aspects such as catalysis, absorption, filtration, energy storage and nano electron devices owing to have outstanding electroconductibility, crystallinity and high specific surface area.
Since the nineties in last century, people have carried out extensive studies for the preparation of array of multi-walled carbon nanotubes.Successively adopt hot CVD and plasma enhanced chemical vapor deposition (PECVD) method, prepare the array of multi-walled carbon nanotubes of arranged vertical.Through research in recent years, the technology of preparing of multi-walled carbon nano-tubes is gradually attained maturation, can realize the fairly large preparation of sample at present.Yet for single-wall carbon nanotube array, because technique controlling difficulty is big, therefore great majority research up to the present also is only limited to laboratory scale, and the purity of the sample that obtains and preparation efficiency are all very low.Ethanol chemical Vapor deposition process (Alcohol CVD) is
By people such as S. Muruyama in 2002 (S. Maruyama, R. Kojima, Y. Miyauchi, S. Chiashi, M. Kohno. Chem. Phys. Lett. 2002 360:229-234) proposes.This technology is introduced alcohol vapour as carbon source, though the single-wall carbon nanotube array of can growth of vertical arranging, growth efficiency is but very low, can only obtain tens microns high Single Walled Carbon Nanotube in ten minutes.
Summary of the invention
The objective of the invention is to overcome the drawback of prior art for preparing Single Walled Carbon Nanotube, big as conventional CVD method growing single-wall carbon nano tube array difficulty, the not high shortcoming of the carbon nano pipe purity that obtains, the technology of the moisture assistant chemical vapor deposition under a kind of normal pressure is provided.
The method for preparing the arranged vertical single-wall carbon nanotube array of the present invention, based on the aumospheric pressure cvd technology, transition-metal Fe with alumina load is a catalyzer, rare gas element and hydrogen are carrier gas, moisture by adding 50-1000ppm concentration in growth atmosphere makes the high purity Single Walled Carbon Nanotube of arranging perpendicular to substrate to improve catalyst efficiency and life-span.
The method for preparing the arranged vertical single-wall carbon nanotube array provided by the present invention can comprise the steps:
(1) substrate that will have a catalyzer is put into the silica tube of chemical gas-phase deposition system, heat up behind the good seal, in the temperature-rise period with the mixed gas of rare gas element and hydrogen as shielding gas, reaction system is heated to growth temperature from room temperature;
(2) reach growth temperature after, feed earlier the rare gas element that has moisture, be incubated 1-10 minute; Feed carbon-source gas then, grew 5-30 minute;
(3) behind the growth ending, except that rare gas element, close all reactant gasess (water vapor, hydrogen, carbon-source gas), and strengthen inert gas flow purging tail gas, reaction system begins cooling simultaneously.
In the said process, described temperature-rise period is: 10-15 minute, temperature of reaction system is risen to 750-850 ℃, and intensification is starting point with the room temperature.
In the said process, described rare gas element comprises high-purity argon gas or helium, and the volume ratio of rare gas element and hydrogen can be 1:9~9:1 in the temperature-rise period.
In the said process, required moisture provides by leading up to the rare gas element of bubbler in the carbon nano tube growth, and the volumetric concentration of moisture in growth atmosphere can be 50-1000ppm.
In the said process, in the step (1), the total flux of described rare gas element and hydrogen can be 500-10000sccm.
In the said process, identical in the total flux of step (2) gas that whole process feeds and the step (1), total gas flow rate is constant when guaranteeing that step (1) stage to step (2) stage switches.
In the said process, described carbon-source gas is a high-purity ethylene, and the flow of carbon-source gas can be 10-500sccm, preferred 50-100sccm.
In the said process, described substrate is monocrystalline silicon piece or metal alloy film; Described catalyzer is the Fe film that is deposited on on-chip alumina load.And aluminum oxide film film thickness 10-30nm, iron thin film thickness are 1-2nm.
In the said process, the flow direction of described gas can with substrate parallel or vertical.
In the said process, the moisture that is added plays and improves the catalyst efficiency and the vital role in life-span in the Single Walled Carbon Nanotube process of growth.
In the said process, can distribute, prepare difform carbon nano tube array structure by control catalyst.
In the arranged vertical single-wall carbon nanotube array that the present invention obtains, the diameter Distribution scope of Single Walled Carbon Nanotube is 1.5-4nm, and the array height is 100-5000um, and the array height that example is specifically enumerated is 200-800um, the mitron purity that carbon is received〉99wt%.
The Single Walled Carbon Nanotube preparation method that the present invention proposes has growth efficiency height, institute's high characteristics of the carbon nano pipe purity that obtains, and significantly is better than the method that the chemical vapor deposition method of ethanol is equipped with single-wall carbon nanotube array.
Description of drawings
The low power scanning electron microscope diagram of Fig. 1 Single Walled Carbon Nanotube orthogonal array;
The scanning electron microscope diagram of gained carbon nano pipe array among Fig. 2 embodiment 1;
The scanning electron microscope diagram of gained carbon nano pipe array among Fig. 3 embodiment 1;
The projection electron microscope figure of gained carbon nanotube among Fig. 4 embodiment 1;
The laser Raman spectroscopy figure of gained carbon nanotube among Fig. 5 embodiment 1;
The thermogravimetric analysis result of gained carbon nanotube among Fig. 6 embodiment 1.
Embodiment
Below in conjunction with specific examples the technology of the present invention content is described further, but present embodiment does not limit protection scope of the present invention, every employing similarity method of the present invention and similar variation thereof all should be listed protection scope of the present invention in.
Embodiment 1
1, the preparation of Single Walled Carbon Nanotube orthogonal array
(1) cleaning of substrate: the monocrystalline silicon piece of selecting (100) crystal orientation for use is cut into the small pieces of 1 * 1cm size as growth substrate, ultrasonic cleaning 5 minutes in acetone, alcohol, ultrapure water successively; At last, substrate is dried up with high pure nitrogen.
(2) substrate is packed into the vacuum chamber of electron beam evaporation equipment is evacuated to 1 * 10
-4Behind the Pa, at first deposit the Al of 30nm
2O
3Film under the condition of not destroying vacuum, deposits the Fe film of 1.5nm then; Plated film finishes the back and takes out sample, with its catalyzer as carbon nano tube growth.
(3) substrate that will have a catalyzer is put into the silica tube of chemical gas-phase deposition system, feeds helium and the hydrogen (He/H of 2000sccm behind the good seal
2=4/1), and setting program be heated to 850 ℃ with 50 ℃/minute speed.
(4) reach growth temperature after, feed the helium that 100sccm has moisture, the volumetric concentration of moisture in growth atmosphere is 200ppm, and is incubated 5 minutes, makes the Reaktionsofen temperature field reach stable status; Adjust the flow of helium simultaneously, the total gas couette of the feasible silica tube of flowing through is 2000sccm.
(5) ethylene gas of feeding 100sccm begins carbon nano tube growth, and growth time is 10 minutes; Adjust the flow of helium simultaneously, making the total gas couette in the process of growth is 2000sccm.
(6) after reaction finishes, close ethylene gas, and helium gas flow is increased to 5000sccm purging reaction end gas.After treating that furnace temperature is reduced to room temperature, can take out sample.
Experiment repeats 3 times, and the height of the sample different sites that obtained is measured, and the center line average of trying to achieve carbon nano pipe array is about 800 microns.The low power stereoscan photograph that is the single-wall carbon nanotube array that obtains shown in Figure 1.
2, the detection of arranged vertical single-wall carbon nanotube array
The arranged vertical Single Walled Carbon Nanotube that obtains is carried out scanning electronic microscope, transmission electron microscope, laser Raman spectroscopy and thermogravimetric analysis to be characterized.
(1) the sem observation result is shown in Fig. 2,3.Can find that from figure the carbon nanotube that is obtained is grown perpendicular to substrate, arrange comparatively neatly, fine and close that integral body presents the form that a kind of bending makes progress.
(2) the transmission electron microscope observation result as shown in Figure 4.The tube wall of most carbon nanotubes is made up of individual layer in the product, proves that what grown is Single Walled Carbon Nanotube; Through measuring, the diameter Distribution scope of Single Walled Carbon Nanotube is between 1.5-4nm.
Transmission electron microscope observing shows, is not mixed with metal catalyst particles in the carbon nanotube, does not also have tangible decolorizing carbon to adhere to vestige on the tube wall, illustrates that the single wall carbon nano pipe purity that is obtained is very high.
(3) laser Raman spectroscopy of gained carbon nanotube sample as shown in Figure 5.1590cm
-1The Raman peaks at place is the G peak, derives from the graphite-like crystalline structure of carbon nanotube; 1340cm
-1The Raman peaks at place is the D peak, derives from defective and decolorizing carbon in the carbon nanotube structure.The G/D peak intensity ratio of gained sample is about 5, shows that the carbon nanotube crystalline quality is better.
In addition, occur tangible RBM peak in the laser Raman spectroscopy, also confirmed the existence of Single Walled Carbon Nanotube in the sample.
(4) the aerial thermogravimetric analysis measuring result of the sample that obtains as shown in Figure 6.Single Walled Carbon Nanotube reaches peak value since 550 ℃ of quick weight loss during to 645 ℃ of left and right sides, the weightless end in the time of 700 ℃; Do not find tangible residue after the burning, show the carbon based on very high purity of the Single Walled Carbon Nanotube that obtains, greater than 99wt%.
Embodiment 2
One, the preparation of Single Walled Carbon Nanotube orthogonal array
(1) cleaning of substrate: the monocrystalline silicon piece of selecting (100) crystal orientation for use is cut into the small pieces of 1 * 1cm size as growth substrate, ultrasonic cleaning 5 minutes in acetone, alcohol, ultrapure water successively; At last, substrate is dried up with high pure nitrogen.
(2) substrate is packed into the vacuum chamber of magnetron sputtering equipment is evacuated to 2 * 10
-4Behind the Pa, at first deposit the Al of 30nm
2O
3Film under the condition of not destroying vacuum, deposits the Fe film of 1.2nm then; Plated film finishes the back and takes out sample, with its catalyzer as carbon nano tube growth.
(3) substrate that will have a catalyzer is put into the silica tube of chemical gas-phase deposition system, feeds helium and the hydrogen (He/H of 2000sccm behind the good seal
2=4/1), and setting program be heated to 850 ℃ with 50 ℃/minute speed.
(4) reach growth temperature after, feed the helium that 100sccm has moisture, the volumetric concentration of moisture in growth atmosphere is 100ppm, and is incubated 5 minutes, makes the Reaktionsofen temperature field reach stable status; Adjust the flow of helium simultaneously, making the total gas couette in the process of growth is 2000sccm.
(5) ethylene gas of feeding 50sccm begins carbon nano tube growth, and growth time is 10 minutes; Adjust the flow of helium simultaneously, making the total gas couette in the process of growth is 2000sccm.
(6) after reaction finishes, close ethylene gas, and helium gas flow is increased to 5000sccm purging reaction end gas.After treating that furnace temperature is reduced to room temperature, can take out sample.
Experiment repeats 3 times, and the height of acquisition sample different sites is measured, and the center line average of trying to achieve carbon nano pipe array is about 500 microns.
Transmission electron microscope observation is the result show, the carbon nanotube that obtains is a Single Walled Carbon Nanotube.Find tangible RBM peak during laser Raman spectroscopy is analyzed, confirmed the existence of Single Walled Carbon Nanotube; Raman spectrum G/D peak intensity ratio is about 8, shows that the crystalline quality of Single Walled Carbon Nanotube is good.
The preparation of embodiment 3 Single Walled Carbon Nanotube orthogonal array
(1) cleaning of substrate: the monocrystalline silicon piece of selecting (100) crystal orientation for use is cut into the small pieces of 1cm * 1cm as growth substrate, ultrasonic cleaning 5 minutes in acetone, alcohol, ultrapure water successively; At last, substrate is dried up with high pure nitrogen.
(2) substrate is packed into the vacuum chamber of electron beam evaporation equipment is evacuated to 1 * 10
-4Behind the Pa, at first deposit the Al of 10nm
2O
3Film under the condition of not destroying vacuum, deposits the Fe film of 1.0nm then; Plated film finishes the back and takes out sample, with its catalyzer as carbon nano tube growth.
(3) substrate that will have a catalyzer is put into the silica tube of chemical gas-phase deposition system, feeds argon gas and the hydrogen (Ar/H of 2000sccm behind the good seal
2=6/4), and setting program be heated to 850 ℃ with 50 ℃/minute speed.
(4) reach growth temperature after, feed the argon gas that 25sccm has moisture, the volumetric concentration of moisture in growth atmosphere is 50ppm, and is incubated 5 minutes, makes the Reaktionsofen temperature field reach stable status; Adjust the flow of argon gas simultaneously, making the total gas couette in the process of growth is 2000sccm.
(5) ethylene gas of feeding 50sccm begins carbon nano tube growth, and growth time is 10 minutes; Adjust the flow of argon gas simultaneously, making the total gas couette in the process of growth is 2000sccm.
(6) after reaction finishes, close all gas except that argon gas, and argon flow amount is increased to 5000sccm purging reaction end gas.After treating that furnace temperature is reduced to room temperature, can take out sample.
Experiment repeats 3 times, and the height of acquisition sample different sites is measured, and the center line average of trying to achieve carbon nano pipe array is about 200 microns.
Transmission electron microscope observation is the result show, the carbon nanotube that obtains is a Single Walled Carbon Nanotube.Find tangible RBM peak during laser Raman spectroscopy is analyzed, confirmed the existence of Single Walled Carbon Nanotube; Raman spectrum G/D peak intensity ratio is about 7, shows that the crystalline quality of Single Walled Carbon Nanotube is good.
The preparation of embodiment 4 Single Walled Carbon Nanotube orthogonal array
(1) cleaning of substrate: select for use YEF426 alloy-steel sheet (Fe-42%Ni-6%Cr) as growth substrate, be cut into the small pieces of 1cm * 1cm behind the sanding and polishing, ultrasonic cleaning 5 minutes in acetone, alcohol, ultrapure water successively; At last, substrate is dried up with high pure nitrogen.
(2) substrate is packed into the vacuum chamber of electron beam evaporation equipment is evacuated to 1 * 10
-4Behind the Pa, at first deposit the Al of 10nm
2O
3Film under the condition of not destroying vacuum, deposits the Fe film of 1.0nm then; Plated film finishes the back and takes out sample, with its catalyzer as carbon nano tube growth.
(3) substrate that will have a catalyzer is put into the silica tube of chemical gas-phase deposition system, feeds helium and the hydrogen (Ar/H of 1000sccm behind the good seal
2=1/9), and setting program be heated to 850 ℃ with 50 ℃/minute speed.
(4) reach growth temperature after, feed the argon gas that 250sccm has moisture, the volumetric concentration of moisture in growth atmosphere is 1000ppm, and is incubated 3 minutes, makes the Reaktionsofen temperature field reach stable status; Adjust the flow of argon gas simultaneously, making the total gas couette in the process of growth is 1000sccm.
(5) ethylene gas of feeding 100sccm begins carbon nano tube growth, and growth time is 10 minutes; Adjust the flow of argon gas simultaneously, making the total gas couette in the process of growth is 1000sccm.
(6) behind the growth ending, close all gas except that argon gas, and argon flow amount is increased to 5000sccm purging reaction end gas.After treating that furnace temperature is reduced to room temperature, can take out sample.
Experiment repeats 3 times, and the height of acquisition sample different sites is measured, and the center line average of trying to achieve carbon nano pipe array is about 300 microns.
Transmission electron microscope observation is the result show, the carbon nanotube that obtains is a Single Walled Carbon Nanotube.Find tangible RBM peak during laser Raman spectroscopy is analyzed, confirmed the existence of Single Walled Carbon Nanotube; Raman spectrum G/D peak intensity ratio is about 5, shows that the crystalline quality of Single Walled Carbon Nanotube is better.
Claims (9)
1. method for preparing the arranged vertical single-wall carbon nanotube array, for based on the aumospheric pressure cvd technology, Fe with alumina load is a catalyzer, rare gas element and hydrogen are carrier gas, by in growth atmosphere, adding the moisture of 50-1000ppm concentration, make the Single Walled Carbon Nanotube of arranging perpendicular to substrate.
2. prepare the method for arranged vertical single-wall carbon nanotube array according to claim 1, it is characterized in that, comprise the steps:
(1) substrate that will have a catalyzer is put into the silica tube of chemical gas-phase deposition system, heat up behind the good seal, in the temperature-rise period with rare gas element and hydrogen as shielding gas, reaction system is heated to growth temperature from room temperature;
(2) reach growth temperature after, feed earlier the rare gas element that has moisture, be incubated 1-10 minute; Feed carbon-source gas then, grew 5-30 minute;
(3) behind the growth ending, except that rare gas element, close all reactant gasess, and strengthen inert gas flow purging tail gas, reaction system begins to be cooled to room temperature acquisition arranged vertical single-wall carbon nanotube array simultaneously.
3. as preparing the method for arranged vertical single-wall carbon nanotube array as described in the claim 2, it is characterized in that the temperature-rise period described in the step 1 is: be starting point with the room temperature, temperature of reaction system was risen to 750-850 ℃ in 10-15 minute.
4. as preparing the method for arranged vertical single-wall carbon nanotube array as described in the claim 2, it is characterized in that described rare gas element is selected from argon gas or helium.
5. as preparing the method for arranged vertical single-wall carbon nanotube array as described in the claim 2, it is characterized in that, in the step 2, the described rare gas element that has moisture is for obtaining one road rare gas element after by bubbler, and the concentration of moisture in growth atmosphere is 50-1000ppm.
6. as preparing the method for arranged vertical single-wall carbon nanotube array as described in the claim 2, it is characterized in that described carbon-source gas is an ethene.
7. as preparing the method for arranged vertical single-wall carbon nanotube array as described in the claim 2, it is characterized in that described substrate is monocrystalline silicon piece or metal alloy film; Described catalyzer is for being deposited on on-chip aluminum oxide/iron thin film, and aluminum oxide film film thickness 10-30nm, and iron thin film thickness is 1-2nm.
8. as preparing the method for arranged vertical single-wall carbon nanotube array as described in the claim 2, it is characterized in that, distribute, prepare difform carbon nano tube array structure by control catalyst.
9. prepare the method for arranged vertical single-wall carbon nanotube array as claim 1-8 as described in arbitrary, it is characterized in that in the described array, the diameter Distribution scope of Single Walled Carbon Nanotube is 1.5-4nm, the array height is 100-5000um, carbon nano pipe purity〉99wt%.
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