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WO2014071693A1 - Procédé de positionnement et de croissance de nanotubes de carbone monoparoi - Google Patents

Procédé de positionnement et de croissance de nanotubes de carbone monoparoi Download PDF

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WO2014071693A1
WO2014071693A1 PCT/CN2013/001356 CN2013001356W WO2014071693A1 WO 2014071693 A1 WO2014071693 A1 WO 2014071693A1 CN 2013001356 W CN2013001356 W CN 2013001356W WO 2014071693 A1 WO2014071693 A1 WO 2014071693A1
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catalyst
oxide
carbon nanotubes
walled carbon
growth
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PCT/CN2013/001356
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Chinese (zh)
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李彦
秦校军
彭飞
杨娟
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北京大学
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Priority claimed from CN201210443891.9A external-priority patent/CN103803522B/zh
Priority claimed from CN201310544641.9A external-priority patent/CN104609386B/zh
Application filed by 北京大学 filed Critical 北京大学
Publication of WO2014071693A1 publication Critical patent/WO2014071693A1/fr

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    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
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    • B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/02—Single-walled nanotubes

Definitions

  • the present invention relates to single-walled carbon nanotubes, and more particularly to a method for growing single-walled carbon nanotubes, and more particularly to a method for positioning growth of semiconducting single-walled carbon nanotubes. Background technique
  • SWNTs single-walled carbon nanotubes
  • Single-walled carbon nanotubes have a high aspect ratio and are typical one-dimensional nanomaterials.
  • Single-walled carbon nanotubes consisting of a graphite layer rolled into a cylindrical shape have an extremely high aspect ratio.
  • This special tubular structure determines the excellent physical, chemical, electrical and mechanical properties of carbon nanotubes, such as: High Young's modulus, tensile strength and thermal conductivity, ideal one-dimensional quantum wire and direct bandgap optical properties, can modify other molecules and have good biocompatibility.
  • single-walled carbon nanotubes can only grow randomly, and it is not possible to perform local growth.
  • the single-walled carbon nanotubes that are positioned and grown will bring great convenience to their applications, and the device production will be more convenient. Therefore, development of a method for positioning growth of single-walled carbon nanotubes is expected.
  • single-walled carbon nanotubes can be classified into two types according to their different conductivity: metallic single-walled carbon nanotubes and semiconducting single-walled carbon nanotubes.
  • metallic single-walled carbon nanotubes When the Brillouin zone of the carbon nanotube passes through the K B point of the graphene Brillouin zone (ie, the Fermi level), the single-walled carbon nanotube exhibits metallicity; when the Brillouin zone of the carbon nanotube Single-walled carbon nanotubes exhibit semiconductivity when they do not pass the K B point of the graphene Brillouin zone.
  • Semiconducting single-walled carbon nanotubes can be used as a basic unit for constructing nano-scale logic circuits, such as field effect transistors, p-n junction diodes, and memory devices, and have broad application space and prospects.
  • the control of high-purity semiconducting single-walled carbon nanotubes is the core technology in the field of carbon nanotube research.
  • There are two ways to obtain a single-conducting single-walled carbon nanotube one is a method of separation after preparation, and the other is a method of direct growth.
  • the method of separation after preparation is usually cumbersome and easy to have impurities, so the development of a method for directly growing single-walled single-walled carbon nanotubes is undoubtedly more worthy of attention.
  • the methods for directly growing single-conducting single-walled carbon nanotubes reported in the literature can be divided into two categories: one is to obtain a single conductive carbon nanotube by selecting a suitable catalyst or to make one or several The chiral carbon nanotubes are enriched; the other is the destruction of a certain conductive single-walled carbon nanotube by using the different reactivity of the metallic single-walled carbon nanotubes and the semiconducting single-walled carbon nanotubes, preventing It grows to obtain another electrically conductive single-walled carbon nanotube.
  • the metallic carbon nanotubes have lower ionization energy than the semiconducting carbon nanotubes and are more susceptible to chemical reactions such as oxidation, it is possible to selectively prevent and destroy the growth of the metallic carbon nanotubes, thereby obtaining a sample of the semiconducting carbon nanotubes. . It has been studied to selectively prevent the growth of metallic carbon nanotubes by adding or generating certain reactive species in the gas phase. However, these methods have the disadvantage that the conditions are not easy to control and the growth window is narrow.
  • Single-walled carbon nanotubes introduce defects, resulting in a decrease in their performance.
  • the process of assembly to the surface of the substrate is a significant challenge to the direction and position control of single-walled carbon nanotubes.
  • the method of selectively preparing a single conductivity directly on the surface of the substrate is undoubtedly the most convenient for subsequent device fabrication because it avoids the process of purging, dispersing, and assembling the carbon nanotubes.
  • some metal oxides and non-metal oxides have locating properties for the growth of single-walled carbon nanotubes, and are supported by a catalyst for growing single-walled carbon nanotubes.
  • the carrier of the localization property is fixed on the growth substrate, and the single-walled carbon nanotubes can be positioned and positioned; in particular, the metal oxides having the localization characteristics are oxidative, and the single-wall carbon can be selectively positioned and grown. Nanotubes, thereby completing the present invention.
  • a first aspect of the present invention provides a method for positioning growth of single-walled carbon nanotubes, the method comprising the steps of:
  • an oxide carrier having a positioning property providing a metal oxide or a non-metal oxide powder having a particle diameter of 1 nm - 1 000 ⁇ m, the metal oxide being selected from the group consisting of Ce0 2 , A1 2 0 3 , MgO , V 2 0 5, Mn0 2 , Cr 2 0 3, Zr0 2, Hf0 2, Sn0 2, Pb0 2, La 2 0 3, Y 2 0 3, praseodymium oxide (Pr x O "), Eu 2 0 3, Gd 2 0 3 and uranium oxide (U x O,), the non-metal oxide is Si0 2 ;
  • Catalyst (load of precursor ⁇ The oxide carrier having the locating property obtained in the step (1) and the catalyst nanoparticle or the catalyst precursor are dispersed in a solvent, sonicated, the upper layer is discarded, and the separation is dried.
  • a catalyst (precursor) powder supported by an oxide carrier is obtained: (3) administration of an oxide carrier loaded with a catalyst (precursor): an oxide carrier loaded with a catalyst (precursor) is subjected to photolithography, sputtering, Evaporation, microcontact printing, nanoimprinting or squeegee etching on the growth substrate;
  • the growth substrate obtained in the step (3) is pre-reduced with hydrogen at a temperature of 600-1 500 ° C, and then 10 - 1 000 ml /
  • the flow rate of the carbon source gas optionally, with the introduction of hydrogen, by chemical vapor deposition, grows single-walled carbon nanotubes.
  • a second aspect of the present invention provides a method for positioning growth of single-walled carbon nanotubes, the method comprising the steps of:
  • an oxide carrier having a positioning property providing a metal oxide or a non-metal oxide powder having a particle diameter of from 1 nm to 1 000 ⁇ m, the metal oxide being selected from the group consisting of Ce0 2 , A1 2 0 3 , MgO , V 2 0 5, Mn0 2 , Cr 2 0 3, Zr0 2, Hf0 2, Sn0 2, Pb0 2, La 2 0 3, Y 2 0 3, praseodymium oxide (PrxO - Eu 2 0 3, Gd 2 0 3 And uranium oxide ( U x O y ) , the non-metal oxide is Si0 2 ;
  • the deposition of the oxide carrier the above oxide carrier is deposited on the growth substrate by photolithography, sputtering, evaporation, microcontact printing, nanoimprinting or squeegee etching;
  • a third aspect of the present invention provides a method for positioning growth of a semiconducting single-walled carbon nanotube, the method comprising the steps of:
  • Providing an oxide carrier having a positioning property providing a metal oxide having a particle diameter of 1 nm - 1 000 ⁇ m, the metal oxide being selected from the group consisting of Ce0 2 , V 2 0 5 , Mn0 2 , Cr 2 0 3 , Zr0 2 , Hf0 2 , Instruction manual
  • catalyst Precursor loading: The oxide carrier having the positioning property obtained in the step (1) and the catalyst nanoparticle or the catalyst precursor are dispersed in a solvent, sonicated, the upper layer is discarded, and separated and dried to obtain an oxide carrier. Supported catalyst (precursor) powder; (3) delivery of oxide carrier with catalyst (precursor): catalyst
  • the (precursor) oxide carrier is deposited on the growth substrate by photolithography, sputtering, evaporation, microcontact printing, nanoimprinting or squeegee etching;
  • the growth substrate obtained in the step (3) is pre-reduced with hydrogen at a temperature of 600-1500 ° C, and then 10-1000 ml/min.
  • the flow rate carbon source gas optionally with the introduction of hydrogen, is grown by chemical vapor deposition to grow single-walled carbon nanotubes.
  • a fourth aspect of the invention resides in a method of locating a semiconductor single-walled carbon nanotube, the method comprising the steps of:
  • an oxide carrier having a positioning property providing a metal oxide having a particle diameter of 1 nm - ⁇ ⁇ , the metal oxide being selected from the group consisting of Ce0 2 , V 2 0 5 , Mn0 2 , Cr 2 0 3 , Zr0 2 , Hf0 2 , Sn0 2 , Pb0 2 , La 2 0 3 , Y 2 0 3 , yttrium oxide (Pr x O y ), Eu 2 0 3 , Gd 2 0 3 and uranium oxide (U, 0,);
  • the oxide carrier is deposited on the growth substrate by photolithography, sputtering, evaporation, microcontact printing, nanoimprinting or squeegee etching;
  • a fifth aspect of the present invention provides a method for preparing a semiconducting single-walled carbon nanotube, the method comprising the steps of:
  • oxide carrier hydrolysis reaction of soluble nitrate with sodium hydroxide of metal Ce, V, Mn, Cr, Zr, Hf, Sn, Pb, La, Y, Pr, Eu and Gd, using water prepared as follows hot synthesis of metal oxide: Ce0 2, V 2 0 5 , Mn0 2, Cr 2 0 3, Zr0 2, Hf0 2, Sn0 2, Pb0 2, La 2 0 3, Y 2 0 3, praseodymium oxide (Pr x O y ). Eu 2 0 3 and Gd 2 0 3 , the product is washed by water and centrifuged for use;
  • the oxide carrier-supported catalyst (precursor) powder prepared in the step (3) is placed in a ceramic or quartz boat-like or disk-shaped base container, Alternatively, the oxide carrier-supported catalyst (precursor) solution obtained in the step (4) is dropwise added to a silicon wafer, a quartz or a ceramic substrate, and optionally subjected to hydrogen gas at a temperature of 600 to 1500 ° C for prereduction. Then, the single-walled carbon nanotubes are grown by chemical vapor deposition (CVD) with a carbon source gas at a flow rate of 10 to 1000 ml/min, optionally with the introduction of hydrogen.
  • CVD chemical vapor deposition
  • the single-walled carbon nanotubes are grown on the oxide supported or deposited catalyst, which is difficult or hardly at other locations on the growth substrate, and therefore can be positioned by positioning the oxide support. Growth of single-walled carbon nanotubes.
  • Figure 1 shows a obtained in Example 1 serving catalyst precursor planted negative optical micrograph of Fe (N0 3) C 3 to e0 2 powder.
  • Fig. 2 shows a S EM photograph of the carbon nanotube obtained in Example 1.
  • Figure 3a shows the Raman spectrum of the carbon nanotubes obtained in the examples.
  • Figure 3b shows the Raman spectrum of the carbon nanotubes obtained in the examples.
  • Fig. 4 shows a S EM photograph of the carbon nanotube obtained in Example 3.
  • Figure 5a shows the Raman spectrum of the carbon nanotubes obtained in Example 3.
  • Fig. 5b shows the Raman spectrum of the carbon nanotubes obtained in Example 3.
  • Figure 6 shows an optical micrograph e0 2 powder serving the loaded catalyst precursor Fe C (N0 3) 3 obtained in Example 4.
  • Fig. 7 shows a S EM photograph of the carbon nanotube obtained in Example 4.
  • Fig. 8a shows the Raman pupil of the carbon nanotube obtained in Example 4.
  • Fig. 8b shows the Raman spectrum of the carbon nanotubes obtained in Example 4.
  • Fig. 9 shows a S EM photograph of the carbon nanotube obtained in Example 5.
  • Figure 10a shows the Raman spectrum of the carbon nanotubes obtained in Example 5.
  • Fig. 1 Ob shows the Raman optical term of the carbon nanotube obtained in Example 5.
  • Fig. 1 1 shows a S EM photograph of the carbon nanotube obtained in Comparative Example 1.
  • Fig. 1 2a shows the Raman spectrum of the carbon nanotube obtained in Comparative Example 1.
  • Fig. 1 2b shows the Raman spectrum of the carbon nanotube obtained in Comparative Example 1.
  • the positioning property of the oxide carrier is mainly utilized, and two methods are employed for this purpose. First, after the catalyst (precursor) is supported on the oxide carrier, the oxide carrier supporting the catalyst (precursor) is used. The carbon nanotubes are deposited on the growth substrate, and then the carbon nanotubes are grown. Second, the oxide carrier is placed on the growth substrate, and then the catalyst is deposited on the oxide carrier which has been placed on the growth substrate, and then the carbon nanotubes are grown.
  • the present invention as the metal oxide support such as oxides Ce0 2, A1 2 0 3, MgO, V 2 0 5, Mn ⁇ 2, Cr 2 0 3, Zr0 2, Hf0 2, Sn0 2, Pb0 2 , La 2 0 3 , Y 2 0 3 , praseodymium oxide (Pr x O v ), Eu 2 0 3 , Gd 2 0 3 , uranium oxide (U, O y ) or non-metal oxides such as SiO 2 for single-walled carbon
  • the growth of nanotubes has localization characteristics. When it is used to support catalysts for carbon nanotube growth, such metal oxides or non-metal oxides can be grown with single-walled carbon nanotubes at high temperatures.
  • ruthenium oxide (Pr x O y ) means a gas of a metal ruthenium, wherein X and y represent the number of metal ruthenium atoms and oxygen atoms in the ruthenium oxide chemical formula, respectively.
  • the number, X * valence valence 2v ; as ruthenium oxide (Pr x O y ⁇ ⁇ example, mention Pr 2 0 3 , Pr 6 O n . Pr 3 0 4 and the like.
  • uranium oxide (u x o,.) refers to an oxide of metal uranium, wherein X and y represent the number of metal uranium atoms and oxygen atoms in the uranium oxide chemical formula, respectively.
  • the number of X * uranium valence 2y.
  • uranium oxide mention U0 2 , U 2 0 5 , U 3 0 7 , U 3 0 8 ,
  • the oxide support such as metal oxides Ce0 2, V 2 0 5, Mn0 2, Cr 2 0 3, Zr0 2, Hf0 2, Sn0 2, Pb0 2, La 2 0 3 , Y 2 0 3 , yttrium oxide (Pr, 0,), Eu 2 0 3 , Gd 2 0 3 and uranium oxide (U., O v ) also have oxygen storage capacity, when used to support carbon nanotube growth When a catalyst is used, the semiconductor single-walled carbon nanotubes can be selectively positioned and grown.
  • the inventors have also found that when the catalyst for carbon nanotube growth is supported on the oxide carrier, the catalyst is not in direct contact with the growth substrate, and the oxide functions as a barrier catalyst and a substrate, thereby, as a carbon source.
  • the cracking nucleates on the surface of the catalyst particle to grow carbon nanotubes
  • the carbon nanotubes are suspended on the surface of the substrate, which is more susceptible to the influence of the gas flow and grows in the direction of the gas flow to form carbon nanotubes oriented in the direction of the gas flow. That is, carbon nanotubes having orientation selectivity are obtained.
  • the surface of the substrate is not very clean, and obvious catalyst carrier particles can be seen, and generally obtained Non-oriented carbon nanotubes.
  • the inventors have found through research and a large number of experiments that among a large number of metal oxides, Ce0 2 , A1 2 0 3 , MgO, V 2 0 5 , Mn0 2 , Cr 2 0 3 , Zr0 2 , Hf0 2 , Sn0 2 , Pb0 2 , La 2 0 3 , Y 2 0 3 , yttrium oxide (Pr x O,), Eu 2 0 3 , Gd 2 0 3 and uranium oxide ( U x O v ) are suitable as oxides
  • the carrier which helps to selectively position and grow semiconducting carbon nanotubes, in particular Ce0 2 , has a very obvious effect of selectively positioning and growing semiconducting carbon nanotubes: in non-metal oxides, Si0 2 is for carbon nanotubes. Growth has positioning characteristics.
  • uranium oxide U x O an oxide of the isotope 238 U is used.
  • any one of the above metal oxides and non-metal oxides may be used, or two or more of them may be used in combination.
  • the particle diameter is suitably in the range of 1 nm to 1 000 ⁇ m, that is, the nano- or micro-scale oxide powder is suitable as an oxide carrier.
  • the oxide carrier has a particle diameter of 1 Onm - 1 ⁇ m.
  • a nano- or micro-scale oxide powder may be directly synthesized by a chemical reaction method, or a nano- or micro-scale oxide powder may be obtained by grinding large oxide particles, a bulk or the like.
  • the following metal oxides can be prepared by a hydrothermal synthesis method by a hydrolysis reaction of a soluble nitrate of each metal with sodium hydride: Ce0 2 , A1 2 0 3 , MgO, V 2 ⁇ 5 , Mn0 2, Cr 2 0 3 , Zr0 2, Hf0 2 -. Sn0 2, Pb0 2, La 2 0 3, Y 2 0 3, praseodymium oxide (PrxC ⁇ ) E u 2 0 3, Gd 2 0 3 oxide Uranium (U x O y ), the product can be ground by washing and centrifuging.
  • the soluble Ce salt solution may be mixed with a soluble inorganic base solution, reacted at a temperature of 25-24 CTC, and dried to obtain a Ce0 2 support.
  • soluble Ce 3 + salt a nitrate, a chloride, a sulfate, an acetate or the like can be used.
  • Ce(N0 3 ); 6H 2 0 is used.
  • NaOH or KOH can be used as the soluble inorganic base. Any one of them may be used, or any combination of the two may be used.
  • the reaction temperature of the soluble Ce 3 + salt solution and the soluble inorganic alkali solution is 25-240, preferably 166-200 °. C, particularly preferably about 1 80 °C. If the reaction temperature is lower than 25 ° C, it is difficult to form Ce0 2 , and if the reaction temperature is higher than 240 ° C, the performance of the obtained CeO 2 carrier deteriorates.
  • a conventional catalyst for carbon nanotube growth such as iron, copper, lead, nickel, cobalt, manganese, chromium or molybdenum or the like can be used.
  • a powder of these catalyst metals or a powder of a catalyst precursor may be used, which is supported on an oxide carrier and then placed on a growth substrate; or these catalyst metals may be used as they are.
  • the catalyst metal is deposited directly on the oxide support on the growth substrate.
  • the term "catalyst (precursor)" means a catalyst and a catalyst precursor.
  • the catalyst is a carbon nanotube growth catalyst such as iron, copper, lead, nickel, cobalt, manganese, chromium or molybdenum
  • the catalyst precursor is reactable to obtain a carbon nanotube growth catalyst such as iron, copper, lead, nickel, Cobalt, manganese, chromium or molybdenum soluble salts such as iron, copper, lead, nickel, cobalt, manganese, chromium or molybdenum oxides or nitrates, chlorides, sulfates, acetates, such as Fe(N0 3 ) 3 '9H 2 0, FeC l 6H 2 0, CuCl 2 , Cu(N0 3 ) 2 -3H 2 0, (CH 3 COO) 2 Pb, Pb(N0 3 ) 2 , NiCl 2 -6H 2 0, Co(N0 3 ) 2 '6H 2 0, (
  • an iron salt such as Ce(N0 3 ) 3 -6H 2 0 , Fe(N0 3 ) 3 -9H 2 0, FeC l 3 '6H 2 0 ; a copper salt such as CuCl 2 , Cu(N0 3 ) 2 3 H 2 0, (CH 3 COO) 2 Pb ; a lead salt such as Pb(N0 3 ) 2 ; a nickel salt such as NiCl 2 '6H 2 0 ; a cobalt salt such as Co(N0 3 ) 2 '6H 2 0 , ( CH 3 COO) 2 Co-4H 2 0 : manganese salt, such as MnCl 2 , MnS0 4 ; chromium salt, such as CrCl 3 ; molybdenum salt, such as ( ⁇ ⁇ 4 ) (, ⁇ 7 0 24 ⁇ 4 ⁇ 2 0 and so on.
  • a copper salt such as CuCl 2 , Cu(N0 3 ) 2 3 H 2
  • the oxide support and the catalyst (precursor) powder are dissolved in an organic solvent, sonicated, the upper layer is discarded, and separated and dried to obtain an oxide supported catalyst (precursor). body).
  • an inorganic solvent such as water or an organic solvent such as an alcohol solvent such as ethanol, decyl alcohol, ethylene glycol or the like, or acetone or furfural may be used. Any one of them may be used, or a plurality of them may be used in combination.
  • the sonication time is preferably from 10 to 40 minutes, more preferably from 1 to 5 to 30 minutes, particularly preferably from about 20 minutes. If the sonication time is less than 10 minutes, it may cause uneven dispersion of the catalyst (precursor). If the sonication time exceeds 40 minutes, the dispersion effect is hardly improved.
  • steps (1) and (2) may be replaced by:
  • a nitrate solution of the metal or a mixed solution with a catalyst precursor is provided;
  • a mixed solution containing the ester of the non-metal silicon and the catalytic precursor is provided.
  • an inorganic solvent such as water or an organic solvent such as an alcohol such as ethanol, decyl alcohol, ethylene glycol or the like, or acetone or furfural may be used. Any one of them may be used, or a plurality of them may be used in combination. It is preferred to use ethanol.
  • a silicate such as an alkyl silicate chain ester can be used, and for example, (n-)ethyl silicate, (n-) yttrium silicate, tetrakis (octadecyl) silicate can be mentioned. Ester and the like.
  • a catalyst such as by photolithography, splashing Injection, evaporation, microcontact printing, nanoimprinting or squeegee etching are applied to the growth substrate.
  • Photolithography, sputtering, evaporation, microcontact printing, nanoimprinting, or squeegee etching are all conventional positioning methods, which have been disclosed or disclosed in the prior art.
  • micron-level positioning control can be realized by sputtering, evaporation, and microcontact printing
  • nano-level positioning control can be realized by photolithography, nanoimprinting, or squeegee etching.
  • the oxide book carrier is placed on the growth substrate by means of, for example, photolithography, sputtering, evaporation, microcontact printing, nanoimprinting or squeegee etching, and then by CVD or the like.
  • a catalyst is deposited.
  • the deposition of a catalyst by means of CVD or the like is a conventional metal deposition method.
  • a catalyst precursor solution such as a CuCl 2 ethanol solution
  • a metal such as Cu or the like
  • these metal catalyst particles are selectively deposited on the surface of the oxide support during the pre-reduction process or growth process, instead of growing the surface of other smooth portions of the substrate, thereby realizing the metal catalyst. Positioning deposition.
  • the object of the step (4) is to dispose the oxide carrier of the supported catalyst (precursor) as a solution, which can be directly added to the growth. On the substrate, used to grow carbon nanotubes.
  • carbon nanotubes are grown by chemical vapor deposition (CVD) techniques.
  • the growth substrate also referred to as a growth substrate
  • a conventional growth substrate such as ceramic, silicon wafer, quartz, sapphire or the like can be used, and there is no particular limitation thereto.
  • a p-type heavily doped silicon wafer is preferably used, and further preferably, the surface thereof may be formed into a silicon oxide layer of several hundred nanometers, for example, 500 nm thick by a thermal oxidation method.
  • the growth substrate it can be cleaned using conventional methods, for example, by ultrasonication, before use.
  • the silicon wafer may be thinned with a glass knife and impregnated with a mixed solution of concentrated sulphuric acid and hydrogen peroxide, for example, a thick stone charge of 7:3 by volume.
  • a mixed solution of acid and hydrogen peroxide also referred to as "Piranha solution”
  • heat-heated at a temperature of 90-15 CTC preferably 110-130 ° C, more preferably about 120 ° C, to hydroxylate the surface of the silicon wafer, which is more hydrophilic , to facilitate the dispersion of the subsequent catalyst.
  • the heating and holding time is from 10 to 60 minutes, more preferably from 15 to 30 minutes.
  • the substrate may be repeatedly washed with ethanol and ultrapure water in sequence, and blown with N 2 gas.
  • the catalyst may be pre-reduced with hydrogen prior to the introduction of the carbon source gas, so that the catalytic precursor is reacted to obtain a catalyst, however, due to the growth of the carbon nanotubes Description
  • the catalyst When hydrogen is generally supplied for assisted growth, the catalyst may not be pre-reduced; if the catalyst itself is used, the hydrogen pre-reduction process is not required. However, the pre-reduction of hydrogen gas at this time has an influence on the conductivity selectivity of the obtained carbon nanotubes, and if the pre-reduction time is too long, the obtained carbon nanotubes do not have conductivity selectivity. The reason for this may be that: the pre-reduction process may cause some or all of the oxide support to be reduced, reduce its oxygen storage capacity, and weaken its oxidizing ability, so that it cannot be used when the single-walled carbon nanotubes grow from the catalyst surface. Metallic single-walled carbon nanotubes are removed by oxidation.
  • the pre-reduction of hydrogen gas is carried out for no more than 15 minutes, more preferably less than 5 minutes.
  • the carbon source gas decane, ethanol, an ethylene block or the like is used.
  • methane is used.
  • the inventors have found that when other carbon source gases are used, only a small amount of carbon nanotubes can be obtained, and even carbon nanotubes cannot be obtained. However, the reason for this is not clear.
  • the temperature at which the single-walled carbon nanotubes are grown by chemical vapor deposition is 600 to 1500 ° C, preferably 700 to 1300 ⁇ , more preferably 900 to ⁇ 100 ° C. Within the temperature range, the desired single-walled carbon nanotubes can be positioned to grow. If the temperature is lower than 600 ° C, the carbon source gas will be cleaved into amorphous carbon or multi-walled carbon nanotubes due to the too low growth temperature; conversely, if the temperature is higher than 1500 ° C, the catalyst will be caused by excessive temperature. The activity is reduced, which in turn affects the catalytic effect, the conductivity selectivity is lowered, and it is difficult to grow single-walled carbon nanotubes. It is also possible that the carbon source is strongly decomposed due to high temperature, which poisons the catalyst and is not conducive to carbon tube nucleation growth.
  • the carbon source gas has a flow rate of from 10 to 1000 ml/min, preferably from 10 to 800 ml/min, still more preferably from 300 to 500 ml/min.
  • the carbon source gas flow rate is within this range, it is more suitable for positioning and growing carbon nanotube growth.
  • the resulting carbon nanotubes have a desired conductivity selectivity. If the flow rate of the carbon source gas is higher than 1000 ml/min, the carbon supply rate will be too large, and amorphous carbon will be formed to entrap the catalyst and cause poisoning; on the contrary, if the carbon source gas flow rate is lower than 10 ml/min, the carbon supply rate is reduced. Small, unable to meet the carbon supply rate of the growth of semiconducting carbon tubes.
  • the flow rate of hydrogen accompanying the introduction cannot be excessively high.
  • the hydrogen flow rate is controlled to be less than 150 ml/min, more preferably less than 100 ml/min.
  • the growth time is not particularly limited as long as it can satisfy the single-walled carbon nanotubes which can be grown to have conductivity selectivity.
  • the growth time is preferably 5-60 min, more preferably 15-30 min. This is because if the growth time is too short, the growth of the single-walled carbon nanotubes may be insufficient, and if the growth time is too long, the reaction materials and time are wasted.
  • the reaction vessel for performing chemical vapor deposition is not particularly limited, and a reaction vessel commonly used in the art, such as a quartz tube, may be used.
  • post-treatment can be carried out, for example, by reducing the temperature in a reducing gas such as hydrogen and/or an inert gas atmosphere.
  • a reducing gas such as hydrogen and/or an inert gas atmosphere.
  • a p-type heavily doped silicon wafer is used, and the crystal plane is Si (100).
  • the surface is thermally oxidized to form a silicon dioxide layer of about 500 nm thick.
  • Use a glass knife to divide the silicon wafer into 5 mm ⁇ 5 mm pieces and place them in a Piranha solution (a 7:3 mixed solution of concentrated acid and hydrogen peroxide) and heat at 120 °C for 20 minutes to make the surface of the silicon wafer. Hydroxylated, more hydrophilic, facilitates dispersion of the catalyst. Then, it was washed repeatedly with ethanol and ultrapure water (resistivity 18.2 ⁇ 'cm), and dried with N 2 gas.
  • the obtained growth substrate was placed in a quartz tube (inner diameter 2.5 cm) of a tube furnace, heated to 700 ° C in air, and then pushed into the heating center. After burning for 5 minutes, the temperature was raised to 950 Torr by Ar protection. After reaching the temperature, Ar was switched to 100 sccm H 2 and passed through 400 sccm CH 4 for 15 minutes, and then cooled to room temperature under Ar atmosphere to obtain carbon nanotubes.
  • FIG. 2 A SEM photograph of the obtained carbon nanotubes is shown in Fig. 2 . It can be seen from FIG. 2 that the single-walled carbon nanotubes are locally grown in the CeO 2 powder region on which the growth substrate is imprinted with the supported catalyst precursor, thereby realizing the localized growth of the single-walled carbon nanotubes. .
  • Figs. 3a and 3b The Raman spectrum of the obtained carbon nanotubes is shown in Figs. 3a and 3b, wherein Fig. 3a shows a spectrum having an excitation wavelength of 532 ⁇ , and Fig. 3b shows a spectrum with an excitation wavelength of 633 nm.
  • the Raman spectral region (shown as M in the corresponding) of the metallic single-walled carbon nanotubes has almost no RBM peak of a single straight-walled carbon nanotube, indicating the metal in the sample.
  • the content of single-walled carbon nanotubes is extremely low, and the semi-conductive body of the single-walled carbon nanotubes (shown as S in the figure) is more than 90%. .
  • a semiconducting single-walled carbon nanotube was prepared in the same manner as in Example 1 except that: Ce(N0 3 ) 3 and Fe(N03). were prepared at a concentration of 3:1 (0.3 mM: O.lmM) of ethanol. Mix the solution, use a micro-injector to draw 5 ⁇ L of the mixed solution onto the PDMS stamp with convex stripes on the surface, and after stamping it, imprint the stamp on the surface of the Si0 2 /Si substrate and then in the air at 200°. C was heated for 15 minutes to obtain a catalyst precursor stripe of Ce0 2 powder.
  • the SEM photograph of the obtained carbon nanotubes is similar to that of Fig. 2.
  • a semiconducting single-walled carbon nanotube was prepared in a manner similar to that of Example 1, except that:
  • FIG. 4 A SEM photograph of the obtained carbon nanotubes is shown in Fig. 4 .
  • single-walled carbon nanotubes were grown in a region where the growth substrate was imprinted with Ce0 2 0 to achieve localized growth.
  • Figs. 5a and 5b The Raman spectrum of the obtained carbon nanotubes is shown in Figs. 5a and 5b, wherein Fig. 5a shows that the excitation wavelength is
  • a semiconducting single-walled carbon nanotube was prepared in a manner similar to that of Example 1, except that:
  • TEOS ethyl silicate
  • Fe(N0 3 ) 3 in a concentration ratio of 3:1 (0.3 mM : O. l mM )
  • FIG. 6 An optical micrograph of the obtained SiO 2 powder to which the supported catalyst precursor was placed is shown in Fig. 6.
  • the Si0 book 2 powder supporting the catalyst precursor is preferably arranged on the surface of the S i 0 2 /Si substrate in accordance with the stamp pattern, and the positioning on the surface of the substrate to the micron level is achieved.
  • FIG. 7 A SEM photograph of the obtained carbon nanotubes is shown in FIG. As can be seen from Fig. 7, single-walled carbon nanotubes were grown in a region where the growth substrate was imprinted with SiO 2 to achieve localized growth.
  • Figs. 8a and 8b The Raman spectrum of the obtained carbon nanotube is shown in Figs. 8a and 8b, wherein Fig. 8a shows that the excitation wavelength is
  • a semiconducting single-walled carbon nanotube was prepared in the same manner as in Example 1, except that: the Ce0 2 powder loaded with the catalyst precursor Fe(N0 3 ) 3 was weighed, 2 ml of ethanol was added, and Si was used to prepare a catalyst solution. l L Fe/Ce0 2 ethanol solution was dropped on the Si0 2 /Si substrate.
  • FIG. 9 A SEM photograph of the obtained carbon nanotubes is shown in Fig. 9. As can be seen from Fig. 9, the catalyst-laden CeO 2 powder was randomly distributed on the surface of the growth substrate, and a large number of random single-walled carbon nanotubes having no positioning growth properties were grown.
  • Figs. 10a and 10b The Raman spectra of the obtained carbon nanotubes are shown in Figs. 10a and 10b, wherein Fig. 10a shows a spectrum having an excitation wavelength of 532 nm, and Fig. 1 Ob shows a spectrum having an excitation wavelength of 633 nm.
  • Fig. 10a shows a spectrum having an excitation wavelength of 532 nm
  • Fig. 1 Ob shows a spectrum having an excitation wavelength of 633 nm.
  • the selectivity of the semiconducting single-walled carbon nanotubes was over 90%. Comparative Example 1 Random growth of non-conductive selective single-walled carbon nanotubes
  • a semiconducting single-walled carbon nanotube was prepared in the same manner as in Example 1, except that: 0.5 mM FeCl 3 .6H 2 0 catalyst precursor ethanol solution was prepared, and about ly L FeCl r 6H 2 0 ethanol solution was dropped on Si0 2 /Si substrate.
  • FIG. 11 An SEM photograph of the obtained carbon nanotubes is shown in Fig. 11. As can be seen from Fig. 1, the catalyst is randomly distributed on the surface of the growth substrate, and a large number of random single-walled carbon nanotubes having no positioning growth properties are grown.
  • Figs. 12a and 12b The Raman spectrum of the obtained carbon nanotubes is shown in Figs. 12a and 12b, wherein Fig. 12a shows a spectrum having an excitation wavelength of 532 nm, and Fig. 12b shows a spectrum with an excitation wavelength of 633 nm. Similar to Example 3, it can be seen that a certain proportion of metallic single-walled carbon nanotubes have an RB M peak, indicating the obtained single-wall carbon Description
  • Nanotube samples do not have semiconducting selectivity.
  • the incident laser energy at 532 nm is 2.33 eV.
  • the detected RBM peak is between 100-Ocm or 206-275 cm, it can be considered as metallic single-walled carbon nanotubes.
  • the RBM peak position is between ⁇ 1 and can be considered as a semiconducting single-walled carbon nanotube; the incident laser energy at 633 nm is 1.96 eV.
  • the detected RBM peak is 180-220 cm "Between 1 , it can be considered as a metallic single-walled carbon nanotube.
  • the detected RBM peak is between 100-180 cm-' or 220-280 cm" 1 , it can be considered as a semi-conducting single-wall carbon. nanotube.

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Abstract

La présente invention concerne un procédé de positionnement et de croissance de nanotubes de carbone monoparoi, permettant de positionner et de faire croître des nanotubes de carbone monoparoi en fournissant un catalyseur pour faire croître les nanotubes de carbone monoparoi sur un support présentant une caractéristique de positionnement pour la croissance des nanotubes de carbone monoparoi, et en fixant le support sur un substrat de croissance ; plus particulièrement, les oxydes métalliques qui présentent la caractéristique de positionnement présentent en outre une propriété d'oxydation, permettant ainsi à la présente invention de positionner et de faire croître sélectivement les nanotubes de carbone monoparoi.
PCT/CN2013/001356 2012-11-08 2013-11-08 Procédé de positionnement et de croissance de nanotubes de carbone monoparoi WO2014071693A1 (fr)

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CN201310544641.9 2013-11-05
CN201310544641.9A CN104609386B (zh) 2013-11-05 2013-11-05 单壁碳纳米管的定位生长方法

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