CN102267693A - Low-temperature preparation method of carbon nanotube - Google Patents
Low-temperature preparation method of carbon nanotube Download PDFInfo
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Abstract
A low-temperature preparation method of carbon nanotubes by a chemical vapor deposition method with Ni/MgO as a catalyst comprises the following steps: dissolving nicdel nitrate hexahydrate and magnesium nitrate hexahydrate in ethanol according to different ratios and concentrations to obtain a mixed solution of nicdel nitrate and magnesium nitrate which is used as a catalyst precursor for carbon nanotube growth; spraying the catalyst precursor solution on a substrate such as silicon, glass, and the like, placing the substrate on a sample stage of a chemical vapor deposition system, heating and decomposing to generate nickel oxide and magnesium oxide, introducing hydrogen, performing reduction in hydrogen plasma of the plasma chemical vapor deposition system to generate nickel nanometer metal particles and to obtain a Ni/MgO catalyst system; introducing hydrocarbons, preparing carbon nanotubes for various demands under different process conditions. The advantages of the invention are that the carbon nanotube preparation process is simple, high in yield, and low in synthetic temperature, and the obtained carbon nanotubes have good quality, high purity, uniform tube diameter distribution, and microelectronic process compatibility.
Description
Technical field
The present invention relates to the low temperature preparation method of the technology of preparing of carbon nanotube, particularly a kind of carbon nanotube.
Background technology
Carbon nanotube is since 1991 are found, because of its unique mechanical, calorifics and electric property, it has had huge potential in application as interconnection line in nano electron devices such as field-effect transistor, Field Emission Display, single-electronic transistor and unicircuit.But want to prepare these electron devices, the synthesis temperature of carbon nanotube must be lower than the temperature that baseplate material can bear.For example, carbon nanotube is applied on the cold-cathode plane indicating meter as the field-causing electron emissive source, and the synthesis temperature of carbon nanotube should be lower than 550 ℃ of the transition temperatures of display glass so.But the growth temperature of carbon current nanotube is generally all at 700～1000 ℃, far above the fusing point of common metal Al in the unicircuit and the transition temperature of display glass.Even if so in-situ preparing has gone out one carbon nanotube nanometer electronic device under this hot conditions, also be difficult to the highly compatible of realization and traditional microelectronic technique.Carbon current nanotube synthetic method mainly contains: arc process, laser evaporation method and chemical Vapor deposition process.For arc process and laser evaporation method, the chemical Vapor deposition process growth temperature is lower, and with ic process compatibility, especially the plasma enhanced chemical vapor deposition method has very big advantage aspect the low temperature synthesizing carbon nanotubes.Therefore the low-temperature epitaxy of chemical Vapor deposition process research carbon nanotube is subjected to the attention of domestic and international researcher.At present, the catalyzer in the chemical Vapor deposition process adopts prepared such as magnetron sputtering method or ion sputtering method mostly, and its growth temperature also is difficult to drop to the temperature that integrated circuit technology can bear.Therefore, how to improve under the technology and to realize that the low-temperature epitaxy carbon nanotube is a urgent problem.
Summary of the invention
The objective of the invention is at above-mentioned technical Analysis, a kind of low temperature preparation method of carbon nanotube is provided, and this method can realize the direct preparation of carbon nanotube at low temperatures, and technological process is simple, preparation cost is low, gained carbon nano pipe purity height is especially with the microelectronic technique compatibility.
Technical scheme of the present invention:
A kind of low temperature preparation method of carbon nanotube, step is as follows
1) with six water nickelous nitrate (Ni (NO
3)
26H
2O) and magnesium nitrate hexahydrate (Mg (NO
3)
26H
2O) be dissolved in and make mixing solutions in the ethanol as the complex catalyst precursor thing;
2) above-mentioned mixing solutions evenly is sprayed on the substrate, after oven dry under 50～100 ℃ of temperature, places on the sample table of chemical vapour deposition (PECVD) system vacuum chamber;
3) close vacuum chamber and vacuumizing, when vacuum tightness during less than 0.1Pa, feed hydrogen to vacuum chamber, hydrogen flowing quantity is 20-200mL/min, when pressure reaches 100～500Pa, with sample table heating 0.5～3 hour, Heating temperature was 350～500 ℃, so that the complex catalyst precursor thing on the substrate decomposes and formation NiO and MgO;
4) apply the radio frequency power of 50～500W, under the hydrogen plasma effect of PECVD system, NiO is reduced to the Ni nano-metal particle, obtain the required Ni/MgO catalyst system of carbon nano tube growth, the recovery time is 0.5～3 hour;
5) keeping feeding hydrocarbon polymer under the hydrogen flowing quantity condition as reactant gases, the hydrocarbon gas flow is 20-200mL/min, at pressure is that 10～1000pa and underlayer temperature are under 450～900 ℃ of conditions, apply radio frequency power 50-500W, in 0.5～5 hour reaction times, directly prepare carbon nanotube by carrying out plasma reaction at catalyst surface.
Ni (NO in the described mixing solutions
3)
2And Mg (NO
3)
2Mol ratio be 1: 1-10, Ni (NO
3)
2Volumetric molar concentration be 0.05～2mol/mL.
Described substrate is Si, glass, quartz or copper.
Described hydrocarbon polymer is methane, acetylene or ethene.
The preparation of described Preparation of catalysts and carbon nanotube is carried out in the PECVD system continuously.
Be provided with sample table, bleeding point, well heater, gas inlet, radio-frequency electrode and substrate in the vacuum chamber in the described PECVD system, bleeding point is located at the bottom of vacuum chamber and is connected with air-bleed system; Well heater adopts the graphite heating mode, and well heater is located at below the sample table and by lead and is connected with power supply; The top center position of vacuum chamber is located in the gas inlet; Radio-frequency electrode comprises top electrode and lower electrode, top electrode is located at the top center position of vacuum chamber and is connected with radio-frequency power supply, power on and very be provided with the disk of uniform distribution aperture, reactant gases is introduced from these apertures, and lower electrode is located at the bottom centre position of vacuum chamber, and lower electrode is a T type base spline structure, plane is as sample table on it, lower electrode ground connection is furnished with thermopair, and substrate places on the sample table.
Technical Analysis of the present invention:
Traditional technology adopts equipment such as magnetron sputtering, ion beam sputtering catalyst films such as sputter Ni, Fe on silicon or quartz substrate mostly, and then adopt prepared carbon nanotubes such as arc process, laser evaporation method and chemical Vapor deposition process, so preparation technology is comparatively loaded down with trivial details.And the present invention adopts and to be soluble in ethanol and can labile at low temperatures Ni (NO
3)
2And Mg (NO
3)
2As the complex catalyst precursor thing, under heating and hydrogen plasma effect, obtain the Ni/MgO catalyst system, wherein Ni is as catalyzer, and MgO feeds hydrocarbon polymer again and prepares carbon nanotube as support of the catalyst.In the vacuum chamber structure of PECVD provided by the invention system, because acting on up and down of rf bias produces glow plasma between two electrodes, substrate is warming up to preset temperature jointly by the well heater and the plasma bombardment of sample table below, underlayer temperature is by thermocouple measurement, and the actual temperature of sediment chamber is by the control of automatic temperature measurement system.
Advantage of the present invention is: when adopting the PECVD system to obtain catalyzer, direct growth goes out carbon nanotube, and whole process one gas can become; Can obtain the big area catalyst surface in addition, thus the growing large-area carbon nanotube.The carbon nanotube production technology that the present invention relates to, preparation technology is simple, cost is low and ic process compatibility, can prepare the carbon nanotube of different demands at low temperatures.
Description of drawings
Fig. 1 is the vacuum chamber structure synoptic diagram of the radio-frequency plasma chemical vapor depsotition equipment of the present invention's employing.
Among the figure: 1. vacuum chamber 2. sample table 3. bleeding points 4. well heaters 5. gas inletes 6. lower electrodes, 7. substrates, 8. top electrodes, 9. thermopairs
The carbon nanotube SEM photo of Fig. 2 for preparing under the processing condition of embodiment 1.
The carbon nanotube HRTEM photo of Fig. 3 for preparing under the processing condition of embodiment 1.
The carbon nanotube SEM photo of Fig. 4 for preparing under the processing condition of embodiment 2.
Embodiment
Below embodiments of the invention are elaborated, present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
A kind of low temperature preparation method of carbon nanotube, adopt the PECVD systems produce, this system vacuum cell structure as shown in Figure 1, be provided with sample table 2, bleeding point 3, well heater 4, gas inlet 5, radio-frequency electrode and substrate 7 in the vacuum chamber 1, bleeding point 3 is located at the bottom of vacuum chamber 1 and is connected with air-bleed system; Well heater 4 adopts the graphite heating mode, and well heater 4 is located at below the sample table 2 and by lead and is connected with power supply; The top center position of vacuum chamber 1 is located in gas inlet 5; Radio-frequency electrode comprises top electrode 8 and lower electrode 6, top electrode 8 is located at the top center position of vacuum chamber 1 and is connected with radio-frequency power supply, top electrode 8 is for being provided with the disk of uniform distribution aperture, introduce gas inlet 5 through hole of the utmost point 8 from power on, lower electrode 6 is located at the bottom centre position of vacuum chamber 1, and lower electrode 6 is a T type base spline structure, and plane is as sample table 2 on it, lower electrode 6 ground connection are furnished with thermopair 9; Substrate 7 places on the sample table 2.
Utilize above-mentioned PECVD system hypothermia to prepare carbon nanotube.
Embodiment 1:
A kind of low temperature preparation method of carbon nanotube, step is as follows
1) 2.91g six water nickelous nitrates and 2.56g magnesium nitrate hexahydrate are dissolved in make mixing solutions in the 100mL ethanol, be made into Ni (NO as the complex catalyst precursor thing
3)
2And Mg (NO
3)
2Concentration be the Ni (NO of 0.1mol/L
3)
2/ Mg (NO
3)
2Mixing solutions;
2) above-mentioned mixing solutions evenly is sprayed on the glass substrate, after oven dry under 80 ℃ of temperature, places on the sample table of chemical vapour deposition (PECVD) system vacuum chamber;
3) close vacuum chamber, vacuumize with mechanical pump and lobe pump, when vacuum tightness reaches 0.1Pa when following, feeding flow to vacuum chamber is the hydrogen of 40mL/min, when pressure reaches 300Pa, sample table is heated to 400 ℃, makes Ni (NO
3)
2And Mg (NO
3)
2Decompose and form NiO and MgO down at 400 ℃;
4) decomposition reaction was opened radio-frequency power supply after 2 hours, applied the radio frequency power of 200W, form hydrogen plasma, under the hydrogen plasma effect of PECVD system, NiO is reduced to the Ni nano-metal particle, obtain the required Ni/MgO catalyst system of carbon nano tube growth;
5) keeping feeding methane gas under the hydrogen flowing quantity condition as reactant gases, gas flow is 40mL/min, is that 300pa and underlayer temperature are under 500 ℃ of conditions at pressure, applies radio frequency power 200W, reaction 0.5h directly prepares carbon nanotube by carrying out plasma reaction at catalyst surface.
The carbon nanotube SEM photo of Fig. 2 for preparing under these processing condition, show among the figure: the carbon nanotube caliber of preparation is about 20nm.
The carbon nanotube HRTEM photo of Fig. 3 for preparing under these processing condition, show among the figure: the carbon nanotube crystallinity of preparation is good.
Embodiment 2:
A kind of low temperature preparation method of carbon nanotube, step is as follows
1) 2.91g six water nickelous nitrates and 7.68g magnesium nitrate hexahydrate are dissolved in make mixing solutions in the 100mL ethanol as the complex catalyst precursor thing, Ni (NO
3)
2: Mg (NO
3)
2Mol ratio is 1: 3, Ni (NO
3)
2Concentration still is 0.1mol/L;
2) above-mentioned mixing solutions evenly is sprayed on the glass substrate, after oven dry under 80 ℃ of temperature, places on the sample table of chemical vapour deposition (PECVD) system vacuum chamber;
3) close vacuum chamber, vacuumize with mechanical pump and lobe pump, when vacuum tightness reaches 0.1Pa when following, feeding flow to vacuum chamber is the hydrogen of 30mL/min, when pressure reaches 300Pa, sample table is heated to 450 ℃, makes Ni (NO
3)
2And Mg (NO
3)
2Decompose and form NiO and MgO down at 450 ℃;
4) decomposition reaction was opened radio-frequency power supply after 2 hours, applied the radio frequency power of 300W, form hydrogen plasma, under the hydrogen plasma effect of PECVD system, NiO is reduced to the Ni nano-metal particle, obtain the required Ni/MgO catalyst system of carbon nano tube growth;
5) keeping feeding methane gas under the hydrogen flowing quantity condition as reactant gases, gas flow is 50mL/min, is that 300pa and underlayer temperature are under 500 ℃ of conditions at pressure, applies radio frequency power 300W, reaction 0.5h directly prepares carbon nanotube by carrying out plasma reaction at catalyst surface.
The carbon nanotube SEM photo of Fig. 4 for preparing under these processing condition shows among the figure: the carbon nanotube caliber of preparation is about 15nm and distributes more even.
Embodiment 3:
1) 2.91g six water nickelous nitrates and 2.56g magnesium nitrate hexahydrate are dissolved in make mixing solutions in the 100mL ethanol, be made into Ni (NO as the complex catalyst precursor thing
3)
2And Mg (NO
3)
2Concentration be the Ni (NO of 0.1mol/L
3)
2/ Mg (NO
3)
2Mixing solutions;
2) above-mentioned mixing solutions evenly is sprayed on the glass substrate, after oven dry under 80 ℃ of temperature, places on the sample table of chemical vapour deposition (PECVD) system vacuum chamber;
3) close vacuum chamber, vacuumize with mechanical pump and lobe pump, when vacuum tightness reaches 0.1Pa when following, feeding flow to vacuum chamber is the hydrogen of 40mL/min, when pressure reaches 300Pa, sample table is heated to 400 ℃, makes Ni (NO
3)
2And Mg (NO
3)
2Decompose and form NiO and MgO down at 400 ℃;
4) decomposition reaction was opened radio-frequency power supply after 2 hours, applied the radio frequency power of 200W, form hydrogen plasma, under the hydrogen plasma effect of PECVD system, NiO is reduced to the Ni nano-metal particle, obtain the required Ni/MgO catalyst system of carbon nano tube growth;
5) keeping feeding methane gas under the hydrogen flowing quantity condition as reactant gases, gas flow is 40mL/min, at pressure is that 300pa and underlayer temperature are under 650 ℃ of conditions, apply radio frequency power 300W, reaction 0.5h, directly prepare carbon nanotube by carrying out plasma reaction, obtain purity and be higher than 90% carbon nanotube at catalyst surface.
Through the experiment conclusive evidence, pass through the control growing condition among the present invention: as the concentration and the proportioning of control catalyst precursor, can obtain the granules of catalyst of different demands, controlling reaction time and underlayer temperature, reaction gas flow, processing condition such as reaction pressure, the carbon nanotube of the various demands of can growing.
Claims (6)
1. the low temperature preparation method of a carbon nanotube is characterized in that step is as follows
1) with six water nickelous nitrate (Ni (NO
3)
26H
2O) and magnesium nitrate hexahydrate (Mg (NO
3)
26H
2O) be dissolved in and make mixing solutions in the ethanol as the complex catalyst precursor thing;
2) above-mentioned mixing solutions evenly is sprayed on the substrate, after oven dry under 50～100 ℃ of temperature, places on the sample table of chemical vapour deposition (PECVD) system vacuum chamber;
3) close vacuum chamber and vacuumizing, when vacuum tightness during less than 0.1Pa, feed hydrogen to vacuum chamber, hydrogen flowing quantity is 20-200 mL/min, when pressure reaches 100～500 Pa, with sample table heating 0.5～3 hour, Heating temperature was 350～500 ℃, so that the complex catalyst precursor thing on the substrate decomposes and formation NiO and MgO;
4) apply the radio frequency power of 50～500 W, under the hydrogen plasma effect of PECVD system, NiO is reduced to the Ni nano-metal particle, obtain the required Ni/MgO catalyst system of carbon nano tube growth, the recovery time is 0.5～3 hour;
5) keeping feeding hydrocarbon polymer under the hydrogen flowing quantity condition as reactant gases, the hydrocarbon gas flow is 20-200 mL/min, at pressure is that 10～1000 pa and underlayer temperature are under 450～900 ℃ of conditions, apply radio frequency power 50-500W, in 0.5～5 hour reaction times, directly prepare carbon nanotube by carrying out plasma reaction at catalyst surface.
2. according to the low temperature preparation method of the described carbon nanotube of claim 1, it is characterized in that: Ni (NO in the described mixing solutions
3)
2And Mg (NO
3)
2Mol ratio be 1:1-10, Ni (NO
3)
2Volumetric molar concentration be 0.05～2 mol/mL.
3. according to the low temperature preparation method of the described carbon nanotube of claim 1, it is characterized in that: described substrate is Si, glass, quartz or copper.
4. according to the low temperature preparation method of the described carbon nanotube of claim 1, it is characterized in that: described hydrocarbon polymer is methane, acetylene or ethene.
5. according to the low temperature preparation method of the described carbon nanotube of claim 1, it is characterized in that: the preparation of described Preparation of catalysts and carbon nanotube is carried out in the PECVD system continuously.
6. according to the low temperature preparation method of the described carbon nanotube of claim 5, it is characterized in that: be provided with sample table, bleeding point, well heater, gas inlet, radio-frequency electrode and substrate in the vacuum chamber in the described PECVD system, bleeding point is located at the bottom of vacuum chamber and is connected with air-bleed system; Well heater adopts the graphite heating mode, and well heater is located at below the sample table and by lead and is connected with power supply; The top center position of vacuum chamber is located in the gas inlet; Radio-frequency electrode comprises top electrode and lower electrode, top electrode is located at the top center position of vacuum chamber and is connected with radio-frequency power supply, power on and very be provided with the disk of uniform distribution aperture, reactant gases is introduced from these apertures, and lower electrode is located at the bottom centre position of vacuum chamber, and lower electrode is a T type base spline structure, plane is as sample table on it, lower electrode ground connection is furnished with thermopair, and substrate places on the sample table.
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| CN113192762A (en) * | 2021-05-17 | 2021-07-30 | 安徽科技学院 | Carbon nanotube composite material with hierarchical structure and preparation method thereof |
| CN114883117A (en) * | 2021-05-17 | 2022-08-09 | 安徽科技学院 | Preparation method of composite carbon nano tube |
| CN114883117B (en) * | 2021-05-17 | 2023-04-21 | 安徽科技学院 | Preparation method of composite carbon nano tube |
| CN116808843A (en) * | 2023-08-30 | 2023-09-29 | 新乡学院 | Loaded MnO 2-X Carbon nano tube-polyvinyl chloride mixed matrix ultrafiltration membrane and preparation method thereof |
| CN116808843B (en) * | 2023-08-30 | 2023-11-21 | 新乡学院 | Loaded MnO 2-X Carbon nano tube-polyvinyl chloride mixed matrix ultrafiltration membrane and preparation method thereof |
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