CN111056526A - Method for preparing semiconductor carbon nano tube array film - Google Patents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
- B81B7/00—Microstructural systems; Auxiliary parts of microstructural devices or systems
- B81B7/04—Networks or arrays of similar microstructural devices
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
- B81C1/00023—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems without movable or flexible elements
- B81C1/00031—Regular or irregular arrays of nanoscale structures, e.g. etch mask layer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
Abstract
The invention relates to a method for preparing a semiconductor carbon nano tube array film, belonging to the field of carbon nano tube electronics. The method comprises the following steps: dissolving a semiconducting carbon nano tube in a volatile organic solvent to obtain a semiconducting carbon nano tube solution; adding a first solvent which is immiscible with the volatile organic solvent into the semiconductive carbon nanotube solution, uniformly mixing, standing, and defoaming after the first solvent forms a clear two-phase interface on the carbon nanotube solution to obtain a two-phase solution; taking a substrate, cleaning and drying the substrate, vertically immersing the substrate into the two-phase solution, and vertically pulling the substrate out of the two-phase solution; and cleaning and drying the substrate to obtain the semiconductor carbon nanotube array film. The semiconductor carbon nanotube array film prepared by the invention has the advantages of consistent orientation, uniform arrangement, good repeatability and array density as high as 100 plus 200 pieces/mu m, can improve the properties of driving current and the like of a carbon nanotube device, and promotes the industrial application of the carbon nanotube array.
Description
Technical Field
The invention relates to a method for preparing a semiconductor carbon nano tube array film, belonging to the field of carbon nano tube electronics.
Background
The semiconducting carbon nanotubes (SWNTs) have excellent electrical, thermal and mechanical properties, are compatible with the traditional semiconductor process and the novel printing electronic process, and have wide application prospects in the future electronic field.
The semiconductor carbon nanotube array film can be used as a channel material of an electronic component, not only eliminates the adverse effect of a metallic carbon tube on the on-off ratio, but also eliminates the adverse effect of a carbon tube-carbon tube junction in the carbon tube network film on the carrier mobility, and has great application value in the aspects of high-performance logic electronics, radio frequency electronics and the like.
At present, two methods are mainly adopted for preparing the carbon nanotube array. One is a carbon nanotube array directly synthesized by a vapor deposition method (CVD), but the content of the metallic carbon nanotubes in the carbon nanotube array prepared by the method is more than 1 percent, which is not beneficial to the on-off ratio of devices; secondly, the carbon nanotube array is prepared by a suspension evaporation self-assembly method (FESA), but the arrangement of the carbon nanotube array obtained by the method is easily influenced by air and water surface fluctuation, and the density of the carbon tubes is generally 30-60 pieces/mum, so that the driving current of the device is limited.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for preparing a semiconducting carbon nanotube array film. Compared with the prior art, the semiconductor carbon nanotube array film prepared by the invention has the advantages of consistent orientation, uniform arrangement, good repeatability and high array density (100 plus 200 pieces/mum), can improve the properties of driving current and the like of a carbon nanotube device, and promotes the industrial application of the carbon nanotube array.
The technical scheme for solving the technical problems is as follows: a method of making a semiconducting carbon nanotube array film, comprising:
1) taking a semiconducting carbon nano tube, and dissolving the semiconducting carbon nano tube in a volatile organic solvent through ultrasonic crushing to obtain a semiconducting carbon nano tube solution;
2) taking a first solvent which is immiscible with the volatile organic solvent, slowly adding the first solvent into the semiconducting carbon nanotube solution prepared in the step 1), uniformly mixing, standing, and defoaming after the first solvent forms a clear two-phase interface on the semiconducting carbon nanotube solution to obtain a two-phase solution;
3) taking a substrate, cleaning the substrate by acetone and isopropanol, drying the substrate at a high temperature, vertically immersing the substrate into the two-phase solution obtained in the step 2), and vertically pulling the substrate out of the two-phase solution until the substrate is completely pulled out of the liquid level;
4) and cleaning the substrate by using an organic solvent, and drying by using high-purity gas to obtain the semiconductor carbon nanotube array film.
The method for preparing the semiconductor carbon nanotube array film has the beneficial effects that:
the method for preparing the semiconductor carbon nanotube array film has the advantages of simple conditions, convenient operation, good controllability and high repeatability, and can be used for continuous preparation. By controlling the concentration of the semiconductive carbon nanotube solution, the proportion of the two-phase solvent, the pulling speed of the substrate and other parameters, the density of the carbon tubes in the carbon tube array film can be effectively controlled, and the performance of the device can be further regulated and controlled.
Compared with the carbon nanotube array film prepared by the prior art, the carbon nanotube array film prepared by the method provided by the invention has no metallic carbon nanotubes, is uniform in arrangement and high in array density, can obviously increase the on-off ratio of a carbon tube device, improves the carrier mobility and improves the driving current of the device. Meanwhile, the method can be suitable for preparing large-area and uniform carbon nanotube arrays, and is helpful for promoting the application development of the carbon nanotube arrays.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, in 1), the purity of the semiconducting carbon nanotube is not less than 99.99%.
The further scheme has the beneficial effects that the purity of the semiconductor carbon nano tube is limited to be more than or equal to 99.99%, and the performance of subsequent devices can be more excellent.
The semiconducting carbon nanotube or the semiconducting carbon nanotube with the purity of more than or equal to 99.99 percent adopted by the invention can be prepared by the existing method, such as the carbon nanotube material separated by a conjugated polymer coating method, and the excessive conjugated polymer in the separation process is removed, wherein the conjugated polymer comprises any one or more of polyfluorene and derivatives thereof, and polycarbazole and derivatives thereof.
Further, in 1), the power of the ultrasonic crushing is 30-60W, and the time is 1-10 min.
The further scheme has the advantages that the carbon nano tubes are uniformly dispersed in the volatile organic solvent, and the agglomeration phenomenon of the carbon tubes during the subsequent preparation of the array is reduced; the time and power are effectively controlled to prevent the intrinsic properties of the carbon nanotubes from being damaged.
Further, in 1), the volatile organic solvent includes any one or a mixture of two of chloroform and trichloroethane.
The beneficial effect of adopting the further scheme is that the polarity of chloroform or trichloroethane is beneficial to the uniform dispersion of the carbon nano-tubes, and the low boiling point is beneficial to the formation of the array of the subsequent carbon nano-tubes at the interface of two phases.
Further, in 1), the concentration of the semiconducting carbon nanotube solution is 1 to 20.0 μ g/mL.
The method provided by the invention enriches the semiconductive carbon nano tube at the interface of two phases by utilizing the interfacial tension of two immiscible solvents to form the carbon nano tube layer. Researches find that when the concentration of the semiconductive carbon nanotube solution is too low, the density of the carbon nanotubes at the two-phase liquid level is low, and the formed carbon nanotube array is dispersed and discontinuous and is not suitable for preparing devices; when the concentration of the semiconducting carbon nanotube solution is too high, the formed carbon nanotube array is arranged in a double-layer manner, which reduces the gate control performance of the carbon tube device. Therefore, it is preferable to control the concentration of the semiconducting carbon nanotube solution in the appropriate range of 1-20.0 μ g/mL to facilitate the formation of a monolayer, uniform, continuous, high density array.
Further, in 2), the first solvent comprises any one or a mixture of several mutual solvents of cis, trans and cis-trans isomeric mixtures of 2-butene-1, 4-diol, an aqueous solution of 2-butyne-1, 4-diol, ethylene glycol and high-purity water.
The further scheme has the advantages that the solvent is not mutually soluble with chloroform or trichloroethane, and a clear two-phase interface can be formed; and the molecular structure contains hydroxyl, which is beneficial to the enrichment of carbon tubes; in addition, the cleaning agent can be dissolved in isopropanol, acetone and the like, and is easy to clean.
Further, in 2), the mixing method includes any one of mechanical stirring, magnetic stirring and ultrasonic dispersion, and the mixing time is more than 1min until the mixture is uniform.
Further, in 2), the standing time is 1-30min until a clear two-phase interface is formed.
The further scheme has the advantages that the clear interface formed after standing is beneficial to the uniform distribution of the carbon tubes at the interface, and the preparation of the carbon tube array with uniform orientation and uniform distribution is facilitated.
Further, in 2), the defoaming method includes any one of an ultrasonic vibration defoaming method, a centrifugal defoaming method and a vacuum defoaming method.
The further scheme has the advantages that the influence of bubbles generated when the two-phase solution is mixed on the interface can be eliminated through defoaming, and the uniformity of the prepared carbon nanotube array is improved.
Further, in 2), the volume ratio of the volatile organic solvent to the first solvent is more than 1: 1, the volatile organic solvent is excessive, and the first solvent at least covers the liquid surface of the semiconductive carbon nanotube solution.
The beneficial effect of adopting the above further scheme is that the clear two-phase interface is ensured to be formed, and meanwhile, the stability of the film drawing can be ensured more as the liquid level of the upper layer is smaller, thereby being beneficial to the uniformity of the array preparation.
Further, in 3), the base includes any one of a hydrophobic or hydrophilic silicon/silica substrate, a ST-tangential or Z-tangential quartz substrate, and a polymer thin film flexible substrate.
Further, in 3), the temperature for high-temperature drying is 60-120 ℃ and the time is 10-60 min.
Further, in 3), the substrate is vertically drawn out from the two-phase solution at a rate of 1 to 20 mm/min.
The further scheme has the advantages that the phenomenon that the uniformity of the arrangement direction of the carbon nano tubes is influenced by the disturbance of the substrate to the two-phase interface when the pulling speed is too high is avoided, and the carbon tubes are arranged densely and are easy to stack and enrich when the pulling speed is too low.
Further, in 4), the organic solvent includes any one of toluene, xylene, and tetrahydrofuran.
The further scheme has the beneficial effects that polar solvents such as toluene, xylene and tetrahydrofuran can dissolve impurities attached to the carbon nanotube film during film drawing, so that the cleanness of the film is ensured, and the subsequent use is facilitated.
Further, in 4), the high-purity gas includes high-purity nitrogen gas or high-purity air. According to the national standard, high-purity gas, high-purity nitrogen or high-purity air refers to gas, nitrogen or air with the purity of not less than 99.999%.
The invention also provides a semiconducting carbon nanotube array film prepared by the method.
The invention also provides a logic device and/or a radio frequency device, which comprises the semiconductive carbon nanotube array film. In the semiconductor carbon nanotube array prepared by the invention, all the carbon nanotubes are uniformly arranged in an oriented manner, the linearity is high, the array density is high, the influence of carbon tube-carbon tube junctions can be eliminated, the carrier mobility is improved, and the driving current is increased. The logic device and/or the radio frequency device prepared by the semiconductor carbon nanotube array have wide application prospect.
Drawings
FIG. 1 is a scanning electron microscope image of a semiconducting carbon nanotube array film prepared in example 1;
FIG. 2 is a scanning electron microscope photograph of the semiconducting carbon nanotube array film prepared in example 3;
FIG. 3 is a scanning electron microscope photograph of the semiconducting carbon nanotube array film prepared in example 5;
fig. 4 is a scanning electron microscope image of the semiconducting carbon nanotube array film prepared in comparative example 1.
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.
Example 1
1) A semiconducting carbon nanotube with the purity of 99.99 percent separated by using a polyfluorene derivative PFO-BPy is taken and dispersed in a chloroform solution by using an ultrasonication instrument to form a semiconducting carbon nanotube solution with the concentration of 2 mug/mL. The power of the ultrasonic crusher is 45W, and the time is 2 min. Wherein the polyfluorene derivative is PFO-BPy (CAS: 1423043-97-3), ADS153UV, American dye Source, Inc.
2) Mixing 20mL of the semiconducting carbon nanotube solution prepared in the step 1) with 2mL of a 2-butene-1, 4-diol cis-trans-isomeric mixture, ultrasonically oscillating for 2min, standing for 10min to form a clear two-phase interface, and ultrasonically defoaming for 2min for later use to obtain a two-phase solution.
3) Cleaning a hydrophobic or hydrophilic silicon/silicon dioxide substrate by using acetone and isopropanol, drying the substrate for 30min at the temperature of 80 ℃, vertically immersing the substrate into the two-phase solution in the step 2), and vertically pulling the substrate out of the two-phase solution at the pulling speed of 2mm/min until the substrate is completely pulled out of the liquid level.
4) And cleaning the substrate with a toluene solution, and drying the substrate with high-purity nitrogen to obtain the semiconductor carbon nanotube array film.
The surface topography of the prepared semiconducting carbon nanotube array was characterized using a scanning electron microscope, as shown in fig. 1. As can be seen from FIG. 1, the carbon nanotubes are uniformly oriented and arranged, and the array density is as high as 100/μm, i.e., the semiconductor carbon nanotube array film is successfully prepared.
Example 2
1) Taking a semiconducting carbon nanotube with the purity of 99.99 percent separated by polycarbazole PCz, and dispersing the semiconducting carbon nanotube in a chloroform solution by using an ultrasonicator to form a semiconducting carbon nanotube solution with the concentration of 2 mug/mL. The power of the ultrasonic crusher is 45W, and the time is 3 min.
2) Mixing 10mL of the semiconducting carbon nanotube solution prepared in the step 1) with 10mL of a cis-trans isomeric mixture of 2-butene-1, 4-diol, ultrasonically oscillating for 5min, standing for 10min to form a clear two-phase interface, and ultrasonically defoaming for 5min for later use to obtain a two-phase solution.
3) Cleaning a hydrophobic or hydrophilic silicon/silicon dioxide substrate by using acetone and isopropanol, drying the substrate for 30min at the temperature of 80 ℃, vertically immersing the substrate into the two-phase solution prepared in the step 2), and vertically pulling the substrate out of the two-phase solution at the pulling speed of 5mm/min until the substrate is completely pulled out of the two-phase interface.
4) And cleaning the substrate with a toluene solution, and drying the substrate with high-purity nitrogen to obtain the semiconductor carbon nanotube array film.
Example 3
1) Taking a semiconducting carbon nanotube with the purity of 99.99 percent separated by polycarbazole PCz, and dispersing the semiconducting carbon nanotube in a chloroform solution by using an ultrasonicator to form a semiconducting carbon nanotube solution with the concentration of 5 mu g/mL. The power of the ultrasonic crusher is 40W, and the time is 5 min.
2) Mixing 20mL of the semiconducting carbon nanotube solution prepared in the step 1) with 5mL of a cis-trans isomeric mixture of 2-butene-1, 4-diol, ultrasonically oscillating for 2min, standing for 2min to form a clear two-phase interface, and ultrasonically defoaming for 2min for later use to obtain a two-phase solution.
3) Cleaning a hydrophobic or hydrophilic silicon/silicon dioxide substrate by using acetone and isopropanol, drying the substrate for 20min at 100 ℃, vertically immersing the substrate into the two-phase solution prepared in the step 2), and vertically pulling the substrate out of the two-phase solution at a pulling speed of 5mm/min until the substrate is completely pulled out of a two-phase interface.
4) And cleaning the substrate with a toluene solution, and drying the substrate with high-purity nitrogen to obtain the semiconductor carbon nanotube array film.
The surface topography of the prepared semiconducting carbon nanotube array was characterized using a scanning electron microscope, as shown in fig. 2. As can be seen from FIG. 2, the carbon nanotubes are uniformly oriented and arranged, and the array density reaches 150/μm, i.e., the semi-conductive carbon nanotube quasi-array film is successfully prepared.
Example 4
1) A semiconducting carbon nanotube with the purity of 99.99 percent separated by using a polyfluorene derivative PFO-BPy is taken and dispersed in a chloroform solution by using an ultrasonication instrument to form a semiconducting carbon nanotube solution with the concentration of 10 mu g/mL. The power of the ultrasonic crusher is 45W, and the time is 5 min. Wherein the polyfluorene derivative is PFO-BPy (CAS: 1423043-97-3), ADS153UV, American dye Source, Inc.
2) Mixing 20mL of the semiconducting carbon nanotube solution prepared in the step 1) with 5mL of glycol, magnetically stirring for 2min, standing for 5min to form a clear two-phase interface, and performing vacuum defoaming for 2min to obtain a two-phase solution.
3) Cleaning a hydrophobic or hydrophilic silicon/silicon dioxide substrate by using acetone and isopropanol, drying the substrate for 20min at 100 ℃, vertically immersing the substrate into the two-phase solution prepared in the step 2), and vertically pulling the substrate out of the two-phase solution at a pulling speed of 10mm/min until the substrate is completely pulled out of a two-phase interface.
4) And cleaning the substrate with a toluene solution, and drying the substrate with high-purity nitrogen to obtain the semiconductor carbon nanotube array film.
Example 5
1) Taking a semiconducting carbon nanotube with the purity of 99.99 percent separated by polycarbazole PCz, and dispersing the semiconducting carbon nanotube in a chloroform solution by using an ultrasonicator to form a semiconducting carbon nanotube solution with the concentration of 10 mug/mL. The power of the ultrasonic crusher is 40W, and the time is 10 min.
2) Mixing 20mL of the semiconducting carbon nanotube solution prepared in the step 1) with 2mL of a 2-butyne-1, 4-diol cis-trans-isomeric mixture aqueous solution, magnetically stirring for 2min, standing for 5min to form a clear two-phase interface, and performing ultrasonic defoaming for 2min for later use.
3) Cleaning the silicon/silicon dioxide substrate with acetone and isopropanol, drying at 100 ℃ for 20min, vertically immersing into the solution prepared in the step 2), vertically pulling the substrate out of the two-phase solution at the pulling speed of 6mm/min, and stopping pulling until the substrate is completely pulled out of the two-phase liquid level.
4) And cleaning the substrate with a toluene solution, and drying the substrate with high-purity nitrogen to obtain the semiconductor carbon nanotube array film.
The surface topography of the prepared semiconducting carbon nanotube array was characterized using a scanning electron microscope, as shown in fig. 3. As can be seen from FIG. 3, the carbon nanotubes are uniformly arranged, and the array density is as high as 200/μm, i.e., the semiconductor carbon nanotube array film is successfully prepared.
Comparative example 1
1) Taking a semiconducting carbon nanotube with the purity of 99.99 percent separated by polycarbazole PCz, and dispersing the semiconducting carbon nanotube in a chloroform solution by using an ultrasonicator to form a semiconducting carbon nanotube solution with the concentration of 5 mu g/mL. The power of the ultrasonic crusher is 45W, and the time is 3 min.
2) Cleaning a hydrophobic or hydrophilic silicon/silicon dioxide substrate by using acetone and isopropanol, drying the substrate for 20min at 100 ℃, vertically immersing the substrate into deionized water, and only leaving a part which can clamp the substrate above the water surface, wherein a three-phase interface is formed at the junction of the substrate, the deionized water and air.
3) And (2) putting the semiconductive carbon nanotube solution prepared in the step 1) into a microsyringe, adjusting the distance between the needle point and the three-phase interface to be 2mm, adjusting the inclination angle of the needle point and the horizontal plane to be 45 degrees, and adopting an elbow 25G needle for the microsyringe. Continuously supplying a semiconductive carbon nanotube solution to the three-phase interface, and vertically pulling out the substrate from the deionized water, wherein the supply speed of the semiconductive carbon nanotube solution is 200 mu L/min, the pulling speed of the substrate from the deionized water is 5mm/min, and the process is stopped until the substrate is completely pulled out of the water surface.
4) And cleaning the substrate with a toluene solution, and drying the substrate with high-purity nitrogen to obtain the semi-conductive carbon nano tube quasi-array film.
The surface morphology of the prepared carbon tube array film was characterized using a scanning electron microscope, as shown in fig. 4. As can be seen from fig. 4, the carbon nanotubes are arranged in order, i.e., the semiconducting carbon nanotube array film is prepared; however, the film had some defects and the array density was 40 counts/μm.
In summary, comparing the scanning electron microscope images of the semiconductor carbon nanotube array film prepared by the above examples and comparative examples, it can be seen that the carbon nanotubes prepared by the two-phase method of the present invention are uniformly oriented and arranged, and the array density is much higher than that of the carbon nanotubes prepared by the self-assembly method of comparative example 1, which illustrates that the method solves the technical problem of low density of the carbon nanotubes prepared by the prior art.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A method of making a semiconducting carbon nanotube array film, comprising:
1) taking a semiconducting carbon nano tube, and dissolving the semiconducting carbon nano tube in a volatile organic solvent through ultrasonic crushing to obtain a semiconducting carbon nano tube solution;
2) taking a first solvent which is immiscible with the volatile organic solvent, slowly adding the first solvent into the semiconducting carbon nanotube solution prepared in the step 1), uniformly mixing, standing, and defoaming after the first solvent forms a clear two-phase interface on the semiconducting carbon nanotube solution to obtain a two-phase solution;
3) taking a substrate, cleaning the substrate by acetone and isopropanol, drying the substrate at a high temperature, vertically immersing the substrate into the two-phase solution obtained in the step 2), and vertically pulling the substrate out of the two-phase solution until the substrate is completely pulled out of the liquid level;
4) and cleaning the substrate by using an organic solvent, and drying by using high-purity gas to obtain the semiconductor carbon nanotube array film.
2. The method of claim 1, wherein in 1), the purity of the semiconducting carbon nanotubes is 99.99% or more;
the power of the ultrasonic crushing is 30-60W, and the time is 1-10 min;
the volatile organic solvent comprises one or a mixture of two of chloroform and trichloroethane;
the concentration of the semiconductive carbon nanotube solution is 1-20.0 mug/mL.
3. The method according to claim 1, wherein in 2), the first solvent comprises any one or a mixture of several mutual solvents of cis-, trans-and cis-trans-isomeric mixtures of 2-butene-1, 4-diol, aqueous 2-butyne-1, 4-diol solution, ethylene glycol and high-purity water;
the mixing method comprises any one of mechanical stirring, magnetic stirring and ultrasonic dispersion, and the mixing time is longer than 1min until the mixture is uniformly mixed;
the standing time is 1-30min until a clear two-phase interface is formed;
the defoaming method comprises any one of an ultrasonic oscillation defoaming method, a centrifugal defoaming method and a vacuum defoaming method.
4. The method as claimed in claim 3, wherein in 2), the volume ratio of the volatile organic solvent to the first solvent is greater than 1: 1, and the dosage of the first solvent at least covers the liquid surface of the semiconductive carbon nanotube solution.
5. The method according to any one of claims 1 to 4, wherein in 3), the base comprises any one of a hydrophobic or hydrophilic silicon/silica substrate, a ST-tangential or Z-tangential quartz substrate, and a polymer thin film flexible substrate.
6. The method according to any one of claims 1 to 4, wherein in 3), the temperature of the high-temperature drying is 60 to 120 ℃ and the time is 10 to 60 min.
7. The method according to any one of claims 1 to 4, wherein in 3) the substrate is pulled vertically from the biphasic solution at a rate of 1 to 20 mm/min.
8. The method according to any one of claims 1 to 4, wherein in 4), the organic solvent comprises any one of toluene, xylene and tetrahydrofuran; the high purity gas includes high purity nitrogen or high purity air.
9. A semiconducting carbon nanotube array film prepared according to the method of any one of claims 1-8.
10. A logic device and/or radio frequency device comprising the semiconducting carbon nanotube array film of claim 9.
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