CN109850873B - Preparation method of single-walled carbon nanotube intramolecular junction - Google Patents
Preparation method of single-walled carbon nanotube intramolecular junction Download PDFInfo
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Abstract
The invention discloses a preparation method of a single-walled carbon nanotube intramolecular junction, which comprises the following steps of 1) growing an airflow-oriented single-walled carbon nanotube as a nanometer barrier by using a rapid temperature rise method, 2) loading a catalyst with a top growth mode on a substrate on which the airflow-oriented single-walled carbon nanotube grows, and growing a carbon nanotube horizontal array by using the lattice orientation effect of the substrate, 3) stopping growing when the carbon nanotube horizontal array meets the airflow-oriented single-walled carbon nanotube in the growth process, 4) welding two carbon nanotubes by using a catalyst nanoparticle at the top of the carbon nanotube, and 5) seamlessly dividing the junction grown according to the steps into a semiconductor tube-semiconductor tube junction. The invention provides a brand new method for preparing the single-walled carbon nanotube intramolecular nodules, solves the problem of limitation of control preparation of the single-walled carbon nanotube intramolecular nodules, and has extremely wide application prospect in the fields of nano electronic devices and the like.
Description
Technical Field
The invention belongs to the technical field of micro-nano material preparation, and particularly relates to a preparation method of a single-walled carbon nanotube intramolecular junction, wherein the single-walled carbon nanotube intramolecular junction has rectification performance.
Background
Since the discovery of single-walled carbon nanotubes (SWNTs) in 1993, they have made significant progress in various fields of synthesis and applications. SWNTs are one-dimensional macromolecular systems with the most remarkable electrical and mechanical properties. In particular their high carrier mobility, high on-off ratio and high current carrying capacity make them one of the attractive candidates for the realization of high performance nanoelectronics. Single-walled carbon nanotubes currently have a wide range of applications in various fields, including Field Effect Transistors (FETs), ultra-sensitive chemical and biological sensors, interconnect and transparent conductive films, etc. In particular, in the field of nanoelectronics, many studies have shown that silicon-based CMOS (Complementary Metal Oxide semiconductor) technology will reach its physical limit around 2020, and among few candidates, carbon nanotubes are the only material that can continue to improve the overall performance of the system by reducing the devices to 5 nm nodes. However, the device performance is based on materials, single-walled carbon nanotube junctions are a bottleneck limiting their application in the field of nanoelectronics, and carbon nanotube intramolecular junctions are promising candidates for functional elements in molecular electronics and their development is considered to be the ultimate way to drive miniaturization beyond the limits of integrated circuits.
Among all forms of intramolecular junctions, SWNT-based intramolecular junctions have been studied most extensively and extensively. SWNTs can be classified as metallic or semiconducting tubes, which exhibit different electrical transport behavior. Metallic SWNTs have high carrier mobilities, comparable to highly conductive metals, suggesting that they will form ideal interconnects in nanoelectronics. Meanwhile, the inherent characteristics of the semiconductor SWNT are controlled by the topological structure of the semiconductor SWNT, so that a nanoscale functional device can be constructed. By introducing pentagons and heptagons into a hexagonal carbon lattice, two pipe segments with different atomic and electronic structures can be seamlessly fused together to create intramolecular semiconductor pipe-semiconductor pipe junctions, metal pipe-metal pipe junctions.
The interaction between carbon nanotubes affects the structure and properties of the carbon nanotubes, and the formation of intramolecular junctions affects the change in the structure and properties of the carbon nanotubes.
At present, much work is done on the aspect of controlling and preparing the carbon nanotube intramolecular junctions, but the carbon nanotube intramolecular junctions prepared by physical or chemical methods and the like are not perfect, a large number of various defects exist, and the built nano device also has defects at the connecting part. Therefore, the invention of a brand-new control preparation method of the single-walled carbon nanotube intramolecular junction is urgently needed and is very important for basic research and large-scale application of the carbon nanotube.
Disclosure of Invention
The technical problem to be solved by the embodiment of the invention is to provide a preparation method for synthesizing single-walled carbon nanotube intramolecular junctions with rectification performance by a two-step method.
In order to achieve the purpose, the invention adopts the technical scheme that
(1) Preparing a precursor solution containing a catalyst precursor;
(2) loading the precursor solution on a single crystal growth substrate suitable for the growth of single-walled carbon nanotubes;
(3) and (3) growing the single crystal growth substrate in the step (2) by a chemical vapor deposition method in a gas directional growth mode, wherein in the growth composition, catalyst atoms of a precursor solution are fused into the two single-walled carbon nanotubes to form a single-walled carbon nanotube intramolecular junction by utilizing the top growth mode of the carbon nanotubes.
The catalyst precursor is soluble salt of Fe, Co, Ni, Cu, Au, Mo, Zn, W, Ru, Cr, Rh, V, Ti, Al, Mg, Pd, B, P and As.
The concentration of the precursor solution is further set to be 0.05 mMol/L.
The substrate suitable for the horizontal array growth of the single-walled carbon nanotubes comprises a single crystal growth substrate made of st-cut quartz, r-cut quartz, alpha alumina on a surface, alpha alumina on r surface or magnesium oxide
Further setting the parameters of the chemical vapor deposition in the step (3) as follows: 830 deg.C, selected CH of 10-100sccm4，C2H4Ethanol or isopropanol as a carbon source, 300sccm inert gas as a carrier gas, 300sccm H2Then the growth is carried out for 1 min-1 h.
H2As a reducing gas, the reduction stepIn the step, the reducing atmosphere is a hydrogen atmosphere; the gas flow of the hydrogen gas is 300 sccm; the reduction time is 30 min; the purpose of this step is to reduce the ions acting as catalyst.
The method is further characterized in that the single crystal growth substrate is subjected to primary treatment before being loaded with the precursor solution, and the primary treatment method comprises the following steps: ultrasonic cleaning the substrate in ultrapure water, acetone, ethanol and ultrapure water for 10min respectively in sequence, drying the substrate by using high-purity nitrogen, putting the cleaned substrate into a muffle furnace, annealing the substrate at high temperature in air, heating the substrate to 900 ℃ for 2h, keeping the temperature of the substrate constant at 900 ℃ for 8h, cooling the substrate to 300 ℃ for 10 h, and naturally cooling the substrate, wherein the process is used for repairing lattice defects generated in the production and processing process of the substrate.
The prepared single-walled carbon nanotube intramolecular junctions comprise a semiconductor tube-semiconductor tube junction, a metal tube-semiconductor tube junction and a metal tube-metal tube junction.
Further setting that annealing treatment is carried out on the single-walled carbon nanotube intramolecular junction after the step (3), and the process steps are as follows: the gas flow rate of argon gas was 300sccm and the gas flow rate of hydrogen gas was 300sccm at 300 deg.c, and the purpose of this step was to bring the flight tube, which drifted on the surface of quartz, into close contact with the substrate. Flight tubes, for short, are also referred to as flow directing tubes.
In addition, the method of the invention also comprises the following steps: after the chemical vapor deposition step, the system is cooled. The cooling is natural cooling or program control cooling.
In addition, the single-wall carbon nanotube junction prepared by the method also belongs to the protection scope of the invention.
The innovative principle of the invention is as follows:
1) growing airflow-oriented single-walled carbon nanotubes as a nano barrier by using a rapid temperature rise method, 2) loading a catalyst in a top growth mode on a substrate on which the airflow-oriented single-walled carbon nanotubes are grown, and growing a carbon nanotube horizontal array by using the lattice orientation of the substrate, 3) stopping growth when the carbon nanotube horizontal array meets the airflow-oriented single-walled carbon nanotubes in the growth process, 4) seamlessly welding two carbon nanotubes by using catalyst nanoparticles at the top of the carbon nanotubes, 5) dividing the junction grown by the steps into a semiconductor tube-semiconductor tube junction, a metal tube-semiconductor tube junction and a metal tube-metal tube junction, wherein the semiconductor tube-semiconductor tube junction and the metal tube-semiconductor tube junction have rectification performance, and the rectification ratio of the semiconductor tube-semiconductor tube junction can reach 57, the rectification ratio of the metal tube-semiconductor tube junction can reach 26.
Compared with the common preparation method, the preparation method for synthesizing the intramolecular junctions of the single-walled carbon nanotubes has the advantages of simplicity, high efficiency, compatibility with the existing micro-nano process and seamless connection of two single-walled carbon nanotubes by using the metal catalyst in the top growth mode. The method is simple and easy to control, has good repeatability, and has wide application prospect in high-end fields of nano-electronic devices, biomedicine, catalytic synthesis and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is within the scope of the present invention for those skilled in the art to obtain other drawings based on the drawings without inventive exercise.
FIG. 1 is a Scanning Electron Microscope (SEM) image of a flight tube grown by Chemical Vapor Deposition (CVD) using a rapid temperature rise method;
FIG. 2 is a representation of the growth of SWNT intramolecular junctions using Chemical Vapor Deposition (CVD); wherein, a) Scanning Electron Microscope (SEM) images, b) and c) are Atomic Force Microscope (AFM) images under different scales respectively, d) Raman spectra (Raman shift), e) and f) are high-resolution Transmission Electron Microscope (TEM) images under different scales respectively;
FIG. 3 is a Scanning Electron Micrograph (SEM) and an optical micrograph (b) of a SWNT intramolecular structured field effect transistor;
FIG. 4 is a graph of the characteristics of a SWNT intramolecular structure built field effect transistor, a), c), e) are the semiconductor-metal, semiconductor-semiconductor, metal-metal output graphs, respectively, b), d), f) are the semiconductor-metal, semiconductor-semiconductor, metal-metal transfer graphs, respectively;
FIG. 5 is an SEM image of a double growth horizontal array tube using Cu as a catalyst; where a) is the first growth, b) is the SEM after treatment of the tube in oxygen, and figure c) is the SEM image of the second growth.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
Example 1
1) Selecting a quartz substrate as a substrate for growing the carbon nano tube, sequentially carrying out ultrasonic cleaning in ultrapure water, acetone, ethanol and ultrapure water for 10min respectively, and then carrying out blow-drying by using high-purity nitrogen. And (3) putting the cleaned substrate into a muffle furnace, annealing at high temperature in the air, heating to 900 ℃ for 2h, keeping the temperature of 900 ℃ for 8h, cooling to 300 ℃ for 10 h, and naturally cooling, wherein the process is used for repairing the lattice defects generated in the production and processing process.
2) Loading a catalyst Fe on one side of a silicon wafer, then placing the silicon wafer into a chemical vapor deposition system, wherein a catalyst strip is vertical to the direction of gas flow, heating to 950 ℃, introducing 300sccm argon for 5min and 300sccm hydrogen, finally bubbling 30sccm argon for ethanol, growing for 15min, after the growth is finished, closing the argon for ethanol blowing, keeping the hydrogen and the rest argon continuously introduced, and naturally cooling to room temperature until the growth of the flight tube is finished.
The substrate was heated at 300 deg.C, 300Ar, 300H2And (4) annealing for 2h to enable the flying pipe to be in close contact with the substrate (shown in figure 3).
Loading Cu serving as a catalyst on the quartz substrate, placing the quartz substrate into a chemical vapor deposition system, heating to 830 ℃, introducing 300sccm argon for 5min, 300sccm hydrogen, bubbling 30sccm argon for ethanol, growing for 30min, closing the argon for ethanol blowing after the growth is finished, keeping the introduction of hydrogen and the rest of argon continuously, and naturally cooling to room temperature, so that the growth of the single-walled carbon nanotube intramolecular nodules is finished (as shown in figure 1), and we can see that almost all horizontal array tubes stop growing when encountering a flight tube.
3) Intramolecular transfer of SWNT on quartz to SiO2On a/Si (300nm/100nm) substrate, a field effect transistor (shown in figure 3) is constructed, and an electrical performance test (shown in figure 4) is carried out, so that a rectification phenomenon exists in a semiconductor-metal and semiconductor-semiconductor intramolecular junction, but the rectification phenomenon does not exist in a metal-metal intramolecular junction.
Example 2
1) Preparing an alpha-alumina single crystal substrate with a surface a according to the method of the embodiment 1, loading a catalyst Cu, placing the substrate into a chemical vapor deposition system, heating the substrate to 830 ℃, introducing 300sccm argon gas for 5min, introducing 300sccm hydrogen gas, bubbling 30sccm argon gas into ethanol, growing the substrate for 15min, closing the argon gas for ethanol blowing after the growth is finished, keeping the introduction of hydrogen gas and the rest of argon gas continuously, and naturally cooling the substrate to room temperature to obtain a single-walled carbon nanotube horizontal array (as shown in fig. 5 a);
2) placing the substrate in the step 1) into a chemical vapor deposition system, and calcining the substrate at 500 ℃ for 2h under oxygen (as shown in figure 5 b), wherein the existence of the single-walled carbon nanotubes can not be seen on the substrate;
3) placing the substrate treated in the step 2) into a chemical vapor deposition system, heating to 830 ℃, introducing 300sccm argon gas for 5min, introducing 300sccm hydrogen gas, bubbling ethanol by using 30sccm argon gas, growing for 5min, after the growth is finished, closing the argon gas for ethanol bubbling, keeping the introduction of hydrogen gas and the rest of argon gas, and naturally cooling to room temperature, wherein the appearance of a new single-walled carbon nanotube at the top end of the single-walled carbon nanotube grown in the step 1) can be seen (as shown in fig. 5 c), which indicates that the catalyst Cu is used for growing the single-walled carbon nanotube in a top end growth mode.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention, and it is therefore to be understood that the invention is not limited by the scope of the appended claims.
Claims (8)
1. A method for preparing single-walled carbon nanotube intramolecular nodules is characterized by comprising the following steps:
(1) preparing a precursor solution containing a catalyst precursor;
(2) loading the precursor solution on a single crystal growth substrate suitable for the growth of single-walled carbon nanotubes;
(3) selecting a gas directional growth mode for the single crystal growth substrate in the step (2) through a chemical vapor deposition method to grow single-walled carbon nanotubes, and in the growth composition, utilizing the top growth mode of the carbon nanotubes to melt catalyst atoms of a precursor solution to seamlessly weld two single-walled carbon nanotubes together to form a single-walled carbon nanotube intramolecular junction;
and (4) the precursor solution in the step (3) is a soluble salt solution of Cu.
2. The method for preparing single-walled carbon nanotube intramolecular junctions according to claim 1, wherein: the catalyst precursor in the step (2) is soluble salt of Fe, Co, Ni, Cu, Au, Mo, Zn, W, Ru, Cr, Rh, V, Ti, Al, Mg, Pd, B, P and As.
3. The method for preparing single-walled carbon nanotube intramolecular junctions according to claim 1, wherein: the concentration of the precursor solution is 0.05 mMol/L.
4. The method for preparing single-walled carbon nanotube intramolecular junctions according to claim 1, wherein: the substrate suitable for the horizontal array growth of the single-walled carbon nanotube comprises a single crystal growth substrate made of st-cut quartz, r-cut quartz, alpha alumina on a surface, alpha alumina on an r surface or magnesium oxide.
5. The method for preparing single-walled carbon nanotube intramolecular junctions according to claim 1, wherein: the parameters of the chemical vapor deposition in the step (3) are as follows: 830 deg.C, selected CH of 10-100sccm4，C2H4Ethanol or isopropanol as a carbon source, 300sccm inert gas as a carrier gas, 300sccm H2Then, the growth is carried out for 1 min-1 h.
6. The method for preparing single-walled carbon nanotube intramolecular junctions according to claim 1, wherein: the single crystal growth substrate is also subjected to primary treatment before loading a precursor solution, and the primary treatment method comprises the following steps: ultrasonic cleaning the substrate in ultrapure water, acetone, ethanol and ultrapure water for 10min respectively in sequence, drying the substrate by using high-purity nitrogen, putting the cleaned substrate into a muffle furnace, annealing the substrate at high temperature in air, heating the substrate to 900 ℃ for 2h, keeping the temperature of the substrate constant at 900 ℃ for 8h, cooling the substrate to 300 ℃ for 10 h, and naturally cooling the substrate, wherein the process is used for repairing lattice defects generated in the production and processing process of the substrate.
7. The method for preparing single-walled carbon nanotube intramolecular junctions according to claim 1, wherein: the prepared single-walled carbon nanotube intramolecular junctions comprise a semiconductor tube-semiconductor tube junction, a metal tube-semiconductor tube junction and a metal tube-metal tube junction.
8. The method for preparing single-walled carbon nanotube intramolecular junctions according to claim 1, wherein: annealing treatment is also carried out on the intramolecular junctions of the single-walled carbon nanotubes after the step (3), and the process comprises the following steps: the gas flow rate of argon gas was 300sccm and the gas flow rate of hydrogen gas was 300sccm at 300 deg.c, and the purpose of this step was to bring the flight tube, which drifted on the surface of quartz, into close contact with the substrate.
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