CN1948142A - Preparation method of carbon nano-tube array and its application in preparing antenna array - Google Patents
Preparation method of carbon nano-tube array and its application in preparing antenna array Download PDFInfo
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Abstract
The present invention relates to a carbon nano tube array, its preparation method and application in preparation of optical frequency dipole antenna array. The invented carbon nano tube optical frequency dipole antenna array is characterized by that the carbon nano tubes are perpendicular to the substrate material and arranged, the length and diameter ratio of carbon nano tube of fibre is greater then 10. The method for making the carbon nano tube array is characterized by that it uses transition metal film catalyst to regulate its thickness, and utilizes plasma chemical gas phase deposition system to regulate plasma energy density and distribution, controls reaction time, gas pressure and gas flow speed ratio so as to implement large-area perpendicular growth of carbon nano tube or fibre array on various substrates at lower temperature and accurately control length and diameter of produced carbon nano tube or fibre.
Description
Technical field
The present invention relates to the dipole antenna device that transmits and receives optical frequency hertzian wave (light wave) in nanometer photoelectronic material and device technology field, more specifically to a kind of carbon nano pipe array and carbon nanofiber array (the following carbon nano pipe array that all is called), its preparation method and the application in preparation aerial array or preparation optical frequency doublet antenna array.Or the carbon nano-pipe array of arranged vertical is listed in the application in the preparation optical frequency doublet antenna array.
Background technology
Use various plain conductors to transmit and receive the history in existing more than 100 year of technology of low-frequency electromagnetic wave, and went back less than 50 years so far about the research of optical frequency antenna as doublet antenna.Its mechanism all is, for receiving antenna, approach half of space electromagnetic wavelength or the integral multiple of any half-wavelength by the useful length of adjusting antenna, cause the exchange current generation resonance that is excited by hertzian wave (being alternating electromagnetic field) in the antenna, thereby realize being excited the strength of current maximization.This electric current by the rectification amplifying circuit after, can be reduced into original signal; Otherwise, for transmitting antenna, by be loaded with the exchange current of signal to doublet antenna input, and the frequency that makes this exchange current approaches a certain resonant frequency (half integer multiple of resonant frequency institute corresponding wavelength is an effective length of antenna) of antenna, the hertzian wave that antenna space-efficient ground emission towards periphery has this frequency.The low-frequency antenna technology has been widely used in fields such as radio-frequency communication, microwave energy transfer.But at the higher wave band of frequency, comprise optical frequency scopes such as Terahertz, infrared, visible light, ultraviolet, wavelength is contracted to micron even nanometer scale, and lack the effective means of making micron and nanoscale antenna technically always, therefore make slow progress so far about the research and the application of optical frequency antenna.
Up to now, the unique channel of manufacturing optical frequency antenna is to utilize conventional lithographic techniques to prepare metal nano conductor.Only about 250nm, the antenna of small scale then must use beamwriter lithography to the resolution limit of ultraviolet lithography if need prepare more, and resolving power can reach about 50nm.As make the half-wave doublet antenna of a visible frequency, its length should be between 200nm～350nm, and width should be less than 50nm.Even can realize with beamwriter lithography, its principle of operation requires on substrate each plain conductor successively to be completed one by one, and price is very expensive and efficient is extremely low, is not suitable for very much the broad scale research and the application of nano photoelectric integrated device.Moreover the long-width ratio of desirable doublet antenna should be greater than 10, and promptly length is the antenna of 350nm, and its width should be less than 35nm.If this antenna also needs to be under the media environments such as water or glass in actual applications, its yardstick must further be contracted to the degree that beamwriter lithography also can't be reached.
Summary of the invention
Technical problem to be solved by this invention is the shortcoming that overcomes prior art, a kind of optical-fibre communications that is widely used in is provided, photovoltaic device, near-field scanning optical microscope, Terahertz and infrared acquisition, the carbon nano pipe array in fields such as quantum calculation and polarizer or carbon nanofiber array (the following carbon nano pipe array that all is called), its manufacture method and carbon nano-pipe array are listed in the application in preparation aerial array or the preparation optical frequency doublet antenna array.
A kind of carbon nano pipe array, it is characterized in that: this carbon nanotube is perpendicular to that substrate material arranges, above-mentioned substrate material is: various metals and semiconductor material, soda-lime glass, Kapton, transparent conductive oxide, and this oxide compound is: indium stannum alloy and zinc oxide; The length of this carbon nanotube is 50nm-50000nm, and its diameter is 5nm-300nm.
A kind of manufacture method of carbon nano pipe array is characterized in that:
1) Preparation of Catalyst:
A) select for use in metal or semi-conductor or oxide compound or the polymerizable molecular material any as conductive substrate material earlier;
B) any preparation method in employing electrochemical deposition, heat (or electron beam) hydatogenesis, sputtering sedimentation or other any scientific research and the industrial metallic film of using always is directly at above-mentioned conductive substrate material surface deposition one deck transition-metal catalyst film 1; And regulate its thickness;
2) adopt following DC plasma and chemical gas-phase deposition system architecture:
A) in vacuum chamber, vertical columnar electrode and horizontal circular electrode or sample table are set; The spacing of two electrodes is 1-3 centimetre, is connected to the two ends of direct supply 10 respectively;
B) above horizontal electrode, place the sample 3 of waiting to grow, thereunder be well heater 5 to this electrode even heating;
C) well heater 5 connects standard electric alternating current source 11;
D) NH
3And C
2H
2Reactant gases is flowed through by source of the gas 7 in the mediation valve 6 feeding vacuum chambers 1 ';
E) end of vacuum chamber is connected to the vacuum pump 9 of control chamber internal gas pressure by valve 8;
3) growth of the carbon nanotube of arranged vertical or carbon nanofiber array:
A) will wait to grow after sample 3 puts into system;
B) air pressure in the vacuum chamber 1 ' is extracted into 10
-2Torr-10
-6The vacuum of Torr or basic vacuum;
C) connect heater power source and also sample table is warming up to 300-600 ℃ gradually;
D) feed 160 standard cm simultaneously
3/ minute (be designated hereinafter simply as: NH sccm)
3, and the system air pressure of making remains on 1-20Torr;
E) temperature reach 300-500 ℃ preset value and stable after, connect direct supply, voltage is remained between the 400-650V, and makes plasma electrically intensity of flow between two electrodes at 0.5-500mA;
F) through behind 0.5-5 minute the pre-etching time, feed 20 standard cm
3/ minute-80 standard cm
3/ minute C
2H
2, make carbon nano pipe array (or carbon nanofiber array) vertical-growth;
G) in above-mentioned heating and plasma etching process, make above-mentioned catalyst film 1 split into nano particle, thus catalyzed carbon nanotube or fiber growth; Regulate the length of carbon nanotube or fiber by the length of control growing time; By above-mentioned plasma body is formed high-intensity electric field at above-mentioned substrate surface, and make direction of an electric field carbon nanotube or fiber be grown perpendicular to substrate perpendicular to the substrate surface setting;
H) and accurately control the length of the carbon nanotube that produces or fiber at 50nm-50000nm, diameter is at 5nm-300nm, and makes its length: diameter is between 10-10000 or equal 10.
The manufacture method of carbon nano pipe array as previously discussed is characterized in that: above-mentioned vertical electrode 2 be shaped as column, plate-like or needle-like.
The manufacture method of carbon nano pipe array as previously discussed is characterized in that: the various growth parameter(s)s of above-mentioned carbon nano pipe array are: silicon substrate, and 40nm Ni catalyst film 1, temperature is 300-500 ℃, gas ratio is: the NH of 160sccm
3: the C of 80sccm
2H
2, plasma current is: 0.4A, air pressure are 8Torr, growth time is 5 minutes.
The manufacture method of carbon nano pipe array as previously discussed, it is characterized in that: above-mentioned semi-conductor is a silicon semiconductor, above-mentioned oxide compound is: SiO2, ITO, ZnO, above-mentioned polymerizable molecular material is: Polyimide, above-mentioned transition-metal catalyst film is: any in iron, cobalt, nickel and their alloy.
The manufacture method of carbon nano pipe array as previously discussed is characterized in that: when adopting glass insulation substrate 3, be after substrate surface deposit one deck chromium, titanium conductive layer 2, and the deposited catalyst film 1 again.
The manufacture method of carbon nano pipe array as previously discussed, it is characterized in that: accurately the step of the length of the control carbon nanotube that produces and diameter is as follows: control prepared carbon nanotube diameter: 1) be the catalyst film by the deposition suitable thickness, 2) be in the time will preparing diameter less than the carbon nanotube of 20nm, also will be by changing the state of process of growth ionic medium body: the light emitting discharge state that is used by routine be adjusted into the dark discharge state, setting the direct supply output state is the constant current state, the output current intensity that reduces power supply then is till observing plasma body and becoming the dark discharge state, and the diameter range of the carbon nanotube that described method can prepare is 5-300nm; Control prepared length of carbon nanotube: 1) be to change growth velocity by changing growth temperature: temperature high growth rates more is fast more, 2) be the control growing time: growth velocity is 200nm/min, then the growth time of the carbon nanotube needs of 2000nm length is 10min, the moment that growth time calculates to feed acetylene is initial, with moment of stopping to feed acetylene or eliminating plasma body be termination, the length range of the carbon nanotube that described method can prepare is 50-50000nm.
As the optical frequency doublet antenna, the yardstick of carbon nanotube is according to its needed operating frequency, and present working order and media environment and decide do not have optimum range to say, but length and diameter ratio should or equal 10 between 10-10000.Example 1: operating frequency is the ruddiness frequency, and working order is a half-wave doublet antenna, and media environment is a vacuum, and then length of carbon nanotube should be 350nm (i.e. 1/2nd vacuum red light wavelengths), and diameter should be at 5-35nm; Example 2: operating frequency is a green frequencies, and state is the all-wave doublet antenna, and medium is a glass, and then length of carbon nanotube should be 333nm (i.e. green wavelength in glass), and diameter should be at 5-33nm.The carbon nanotube that this preparation method produces no matter its texture quality of scale size all can satisfy needs as the optical frequency antenna applications.
The carbon nanotube as previously discussed or the manufacture method of fiber array is characterized in that: when adopting glass insulation substrate 3, the thickness of above-mentioned catalyst film 1 is: during 19-34nm, and direct deposited catalyst film 1 on glass insulation substrate 3.
The manufacture method of carbon nano pipe array as previously discussed is characterized in that: the various growth parameter(s)s of above-mentioned carbon nano pipe array are: silicon substrate, and 40nm Ni catalyst film 1, temperature is 500 ℃, gas ratio is: the NH of 160sccm
3: the C of 80sccm
2H
2, plasma current is: 0.4A, air pressure are 8Torr, growth time is 5 minutes.
A kind of carbon nano pipe array or the application of carbon nanofiber array in preparation optical frequency doublet antenna array as previously discussed.
Carbon nano pipe array of the present invention, its method for making and the application in making the optical frequency aerial array have following beneficial effect compared with prior art:
1, adopt the basic material of carbon nanotube as the optical frequency antenna, loss is lower than common metal;
2, the accurate yardstick of controlling carbon nanotube optical frequency antenna improves long-width ratio, and the I of diameter reaches 5nm, and even with an array interior diameter;
3, by changing the length of carbon nanotube (fiber), the optical frequency operating frequency of antenna is adjustable interval Terahertz, infrared, visible light and UV spectrum (the wavelength region 100nm～100000nm) that covers;
4, highdensity carbon nano pipe array helps improving the optical signal receiving efficiency;
5, all carbon nanotubes are arranged perpendicular to substrate and are simplified the circuit connection;
6, the carbon nano tube growth temperature is 300-500 ℃, is applicable to multiple substrate material, comprises soda-lime glass, Kapton and transparent conductive oxide such as indium stannum alloy and zinc oxide etc.;
7, preparation technology is simple, high-level efficiency, low cost, is applicable to scale operation.
Description of drawings
Fig. 1 is a deposited catalyst film synoptic diagram on conductive substrates;
Fig. 2 is depositing conducting layer and a catalyst film synoptic diagram on insulating substrate;
Fig. 3 is a direct current plasma chemical gas-phase deposition system structural representation;
Fig. 4 is the electron scanning micrograph of the carbon nano pipe array of typical arranged vertical.Scale length is represented 1 μ m;
Fig. 5 is the transmission electron microscope photo of typical single-root carbon nano-tube.
Fig. 6 is that diameter is the electron scanning micrograph of carbon nanofiber array of the arranged vertical of 5nm～15nm;
Fig. 7 is that diameter is the transmission electron microscope photo of carbon nanofiber array of the arranged vertical of 5nm～15nm;
Fig. 8 is the electron scanning micrograph of the carbon nanofiber of the arranged vertical of growing on the thick Polyimide layer of 1 μ m;
Fig. 9 is the electron scanning micrograph of the carbon nanofiber of the arranged vertical of growing on thick ZnO of 100nm and ITO layer.Wherein substrate all is a soda-lime glass;
Figure 10 is the polarization effect of showing carbon nanotube optical frequency antenna;
Figure 11 is colored for the carbon nanotube aerial array with certain-length distribution of growing on silicon substrate;
Figure 12 is that the carbon nanofiber aerial array (middle section) with length distribution that has grown after having deposited the ITO layer on the glass substrate is colored;
Figure 13 is carbon nanotube (fiber) optical frequency dipole length resonance effect principle schematic;
Figure 14 is different positions (A among Figure 11 on the same sample under the white light
1To A
7) the visible light frequency band reflectance spectrum of carbon nano pipe array second-order radiation.Wherein transverse axis is a wavelength, and the longitudinal axis is a reflection strength;
Figure 15 is length of carbon nanotube and corresponding reflection spectrum peak value institute corresponding wavelength data.Straight line is represented I=λ/2 respectively, λ, 3 λ/2,2 λ.All testing datas are all followed each straight line trend substantially;
Figure 16 is the theory and the experiment contrast figure of the reflection spectrum of different lengths carbon nanotube.Solid line is a gross data, and open squares is an experimental data.
The arrow indication is each crest position among Figure 16 a.
Figure 16 b changes the wavelength axis among Figure 16 a into frequency axis.
Embodiment
All experiment parameters are exemplary values in following examples, and any simple change to this experiment parameter all can be considered and do not exceed the notion of the present invention and the scope of application.
Embodiment 1: Preparation of Catalyst
The substrate that is used for carbon nano-tube can adopt the solid material that can bear growth temperature (being generally 300 ℃～500 ℃) arbitrarily, comprises metal (or alloy), semi-conductor (as silicon), and oxide compound is (as SiO
2, ITO, ZnO etc.) and polymerizable molecular material etc. (as Polyimide), above-mentioned ITO is meant indium tin oxide: indium tin oxide.As shown in Figure 2, if adopt conductive substrates 2 such as metal or semi-conductor, then can be directly at substrate surface deposition one deck transition-metal catalyst film 1 (as iron, cobalt, nickel and their alloy), deposition method can adopt electrochemical deposition, heat (or electron beam) hydatogenesis, sputtering sedimentation, and other any scientific research and industrial common metal method for manufacturing thin film.As shown in Figure 2, if adopt insulating substrate 3 (as glass etc.), then need behind present substrate surface deposition one deck conductive layer 2 (as chromium, titaniums etc.) deposited catalyst film 1 again.But, also can omit conductive layer 2 if sedimentary catalyst film is thicker.
Embodiment 2: direct current plasma chemical gas-phase deposition system structure
The growth of the carbon nanotube of arranged vertical (fiber) can be finished by the direct current plasma chemical gas-phase deposition system.The basic structure of this system as shown in Figure 3.In vacuum chamber 1 ', vertical columnar electrode 2 and horizontal circular electrode (being sample table) 4 arranged.About 1～3 centimetre of two interelectrode distances divide to be connected to direct supply 10 two ends.Vertical electrode 2 shapes also can be plate-like, needle-like etc., and its shape and scale size are decided on practical situation.The sample 3 of waiting to grow is placed in horizontal electrode (sample table) 4 tops, and the below is the well heater 5 that can give this electrode even heating.Well heater can connect standard electric alternating current source 11.Reactant gases is (as NH
3And C
2H
2) feed in the chamber through flow velocity mediation valve 6 by source of the gas 7.One end in chamber connects vacuum pump 9 with the control chamber internal gas pressure by valve 8.This apparatus structure is simple, and is cheap, is suitable for the industry member widespread use.
Embodiment 3: the growth of vertically aligning carbon nanotubes (fiber) array
After in the sample imbedding system, the chamber internal gas pressure is evacuated to 10
-2Torr～10
-6The basic vacuum of Torr.Connect heater power source then and gradually sample table is warming up to 400 ℃～600 ℃, feed the NH of 160sccm simultaneously
3, and keep system's air pressure to 1～20Torr.After temperature reached desired value and stablizes, connecting direct supply also increased the plasma body that produces certain intensity between voltage to two electrode.Through behind the suitably pre-etching time (generally being no more than several minutes), feed the C of 20sccm～80sccm
2H
2, impel the vertical-growth of carbon nanotube (fiber) array.Heating and plasma etch process make catalyst film split into nano particle, thus the growth of catalyzed carbon nanotube (fiber).Can regulate the length of carbon nanotube (fiber) by the control growing time.Carbon nanotube (fiber) is because plasma body forms high field at substrate surface perpendicular to the substrate growth, and direction of an electric field is perpendicular to substrate surface.
Fig. 4 is the electron scanning micrograph of the carbon nano pipe array after growing.
Fig. 5 is the transmission electron microscope photo.Each growth parameter(s) of this carbon nano pipe array is: silicon substrate, 40nm Ni catalyst film, 500 ℃ of temperature, gas ratio 160sccm (NH
3): 80sccm (C
2H
2), plasma current 0.4A, air pressure 8TOrr, growth time 5 minutes.
By reducing below the growth temperature to 400 ℃, carbon nanotube structure changes, and is promptly gradually become the carbon nanofiber of amorphous carbon structure by many walls bamboo knot shaped structure, as shown in Figure 5.This structural modification will be not can its optical frequency antenna performance of remarkably influenced, see Figure 12.
By reducing catalyst film thickness to 3nm, and reduce plasma intensity, the diameter of carbon nanotube (fiber) can be decreased to below the 10nm, and I reaches about 5nm, shown in Fig. 6,7.Table 1 has been listed carbon nanotube (fiber) diameter that the different catalysts film thickness is produced under the same terms.By the accurate mean diameter of controlling carbon nanotube (fiber) of this method, error is in 5%.
| Ni film thickness (nm) | Average carbon nanotube (fiber) diameter (nm) |
| 3 | 10 |
| 6 | 30 |
| 12 | 60 |
| 19 | 75 |
| 26 | 100 |
| 34 | 130 |
Table 1
By reducing the plasma electrically intensity of flow, can make plasmoid is the dark discharge state by the light emitting discharge state-transition, finally can reduce current density to 6.2 μ Acm
-2Below, increase the distribution area of plasma body and improve its homogeneity, make carbon nanotube (fiber) in entire sample platform scope, big area evenly to grow.Low current density can also be alleviated superheated and the corrasion of plasma body to substrate surface greatly, allow carbon nanotube (fiber) vertical-growth on the specialized substrates material, as Polyimide (Fig. 8), indiumtin oxide) and ZnO (Fig. 9) etc. ITO (indium tin oxide:.
Embodiment 4: the optical frequency antenna effect detects
Carbon nanotube (fiber) has very strong polarization effect to the absorption and the emission of light wave.As shown in figure 10, the vertical carbon nanotube array of having grown in the left side of surface of silicon, one deck chromium film has only been precipitated on the right side.Under natural light irradiation, by the catoptrical intensity in polarizer observation sample both sides of a rotation.When polarizer direction during perpendicular to sample surfaces, carbon nanotube one side brightness is higher than chromium film one side (left hand view); When polarizer direction during perpendicular to sample surfaces, the brightness of chromium film side is higher than carbon nanotube one side (right part of flg).The excitation current direction that produces in this explanation carbon nanotube is along the length of carbon nanotube direction, and its second-order radiation polarisation of light direction also must be along this direction promptly perpendicular to substrate surface; And excitation current is in the chromium membrane plane in the chromium film, and its second-order radiation light polarization direction must be parallel to substrate surface.Therefore, when polarizer direction vertical substrates, the brightness maximum of carbon nanotube one side, chromium film one side is then just the opposite.
Shown in Figure 11,12, carbon nanotube (fiber) array by the preparation of method as previously mentioned presents colour when length during less than 2 μ m under white light.Its reason is to illustrate the mean length difference of the carbon nanotube (fiber) of different positions on the sample, makes that the most effective being absorbed with the visible light emitted frequency becomes with the position, thereby produces multiple color distribution.And the physical basis of this phenomenon is, under irradiate light, inspires exchange current along its length in the carbon nanotube (fiber).According to final condition, strength of current is vibrated with the form of dextrorotation ripple along its length, and forms when the length of carbon nanotube (fiber) approaches the integral multiple of incident light half-wavelength and live ripple, and resonance (Figure 13) promptly takes place.The strength of current of this moment is maximum than the situation of other incident light frequency.Carbon nano pipe array (A to different lengths
1, A
2..., A
7) the visible frequency spectroscopic analysis (Figure 14) of second-order radiation light under white light shows, the mean length of the interior carbon nanotube of array all approaches the half integer multiple of the pairing wavelength of its radiant light intensity peak arbitrarily, promptly approaches λ/2, λ, 3 λ/2,2 λ ... or the like (Figure 15).This result proves that fully carbon nanotube (fiber) has tangible length resonance effect, can be used as reliable optical frequency doublet antenna and sends and receive the optical frequency hertzian wave.Because the doublet antenna operating frequency depends on its length, and the grown length of interval of using this preparation method carbon nanotube (fiber) is 50nm～50000nm, so carbon nanotube (fiber) optical frequency antenna can conveniently work in Terahertz, infrared, visible light and the ultraviolet frequencies scope.Simultaneously, owing to the diameter of carbon nanotube (fiber) can be controlled at 5nm～300nm, guaranteed to satisfy long-width ratio greater than 10 doublet antenna form requirement.In addition, if the hypothesis carbon nanotube is the infinitely-great idealized conductor doublet antenna of specific conductivity, then can uses classical electromagnetic theory and calculate the radiation spectrum of different lengths antenna under identical intensity of illumination, the result as shown in figure 16.
The formed crest of open squares among the figure is that length is the experiment gained data of 350nm antenna, and the result meets very much with Theoretical Calculation.In addition, this experimental data width of also demonstrating crest is about 10
15s
-1, the scattering frequency that conduction electrons in the antenna is described is smaller or equal to 10
14s
-1, prove that thus carbon nanotube is equivalent to copper as the wastage rate of optical frequency antenna, and be lower than other metal.
If change the wavelength axis among Figure 16 a (the μ m of unit) into shown in Figure 16 b the frequency axis (s of unit
-1, identical with scattering frequency unit) and insert experimental data again, the width that then can record crest is about 10
15s
-1Because experimental data and gross data meet finely, and gross data has been supposed antenna specific conductivity infinity,, but come from the heterogeneity of radiation loss and space structure so the width of the crest of surveying not is to be caused by resistance losses.This means that just the scattering frequency of the conduction electrons that influences resistance losses in the carbon nanotube approaches or is lower than 10
15s
-1, promptly inevitable 10
14s
-1Magnitude or lower.
Claims (10)
1, a kind of carbon nanotube or fiber array, it is characterized in that: this carbon nanotube or fiber are perpendicular to that substrate material arranges, above-mentioned substrate material is: various metals and semiconductor material, soda-lime glass, Kapton, transparent conductive oxide, this oxide compound is: indium stannum alloy and zinc oxide; The length of this carbon nanotube or fiber is 50nm-50000nm, and its diameter is 5nm-300nm.
2, the manufacture method of a kind of carbon nanotube or fiber array is characterized in that:
1) Preparation of Catalyst:
A) select for use in metal or semi-conductor or oxide compound or the polymerizable molecular material any as conductive substrate material earlier;
B) any preparation method in employing electrochemical deposition, heat or electron-beam evaporation, sputtering sedimentation or other any scientific research and the industrial metallic film of using always is directly at above-mentioned conductive substrate material surface deposition one deck transition-metal catalyst film (1); And regulate its thickness;
2) adopt following DC plasma and chemical gas-phase deposition system architecture:
A) in vacuum chamber, vertical columnar electrode and horizontal circular electrode or sample table are set; The spacing of two electrodes is 1-3 centimetre, is connected to the two ends of direct supply 10 respectively;
B) above horizontal electrode, place sample to be grown (3), thereunder be well heater (5) to this electrode even heating;
C) well heater (5) connects standard electric alternating current source (11);
D) NH
3And C
2H
2Reactant gases is flowed through by source of the gas (7) in mediation valve (6) the feeding vacuum chamber (1);
E) end of vacuum chamber (1) array is connected to the vacuum pump (9) of control chamber internal gas pressure by valve (8);
3) growth of the carbon nanotube of arranged vertical or carbon nanofiber array:
A) after will sample be grown (3) putting into system;
B) air pressure in the vacuum chamber (1) is extracted into 10
-2Torr-10
-6The vacuum of Torr;
C) connect heater power source and also sample table is warming up to 300-600 ℃ gradually;
D) feed the NH of 160sccm simultaneously
3, and the system air pressure of making remains on 1-20Torr;
E) temperature reach above-mentioned 300-500 ℃ preset value and stable after, connect direct supply, voltage is remained between the 400-650V, and makes plasma electrically intensity of flow between two electrodes at 0.5-500mA;
F) through behind 0.5-5 minute the pre-etching time, feed 20 standard cm
3/ minute-80 standard cm
3The C of/minute (sccm)
2H
2, make carbon nanotube or fiber array vertical-growth;
G) in above-mentioned heating and plasma etching process, make above-mentioned catalyst film (1) split into nano particle, thus catalyzed carbon nanotube or fiber growth; Regulate the length of carbon nanotube or fiber by the length of control growing time; By above-mentioned plasma body is formed high-intensity electric field at above-mentioned substrate surface, and make direction of an electric field carbon nanotube or fiber be grown perpendicular to substrate perpendicular to the substrate surface setting;
H) and accurately control the length of the carbon nanotube that produces or fiber at 50nm-50000nm, diameter is at 5nm-300nm, and makes its length: diameter is between 10-10000 or equal 10.
3, the manufacture method of carbon nanotube as claimed in claim 2 or fiber array is characterized in that: above-mentioned vertical electrode (2) be shaped as column, plate-like or needle-like.
4, the manufacture method of carbon nanotube as claimed in claim 2 or fiber array, it is characterized in that: the various growth parameter(s)s of above-mentioned carbon nanotube or fiber array are: silicon substrate, 40nm Ni catalyst film (1), temperature are 300-500 ℃, and gas ratio is: the NH of 160sccm
3: the C of 80sccm
2H
2, plasma current is: 0.4A, air pressure are 8Torr, growth time is 5 minutes.
5, the manufacture method of carbon nanotube as claimed in claim 2 or fiber array is characterized in that: above-mentioned semi-conductor is a silicon semiconductor, and above-mentioned oxide compound is: SiO
2, ITO, ZnO, above-mentioned polymerizable molecular material is: Polyimide, above-mentioned transition-metal catalyst film is: any in iron, cobalt, nickel and their alloy.
6, the manufacture method of carbon nanotube as claimed in claim 2 or fiber array is characterized in that: when adopting glass insulation substrate (3), be after substrate surface deposit one deck chromium, titanium conductive layer (2), and deposited catalyst film (1) again.
7, the manufacture method of carbon nanotube as claimed in claim 2 or fiber array, it is characterized in that: accurately the step of the length of control institute's carbon nanotube that produces or fiber and diameter is as follows: control prepared carbon nanotube diameter: 1) be by depositing the catalyst film of suitable thickness, 2) be in the time will preparing diameter less than the carbon nanotube of 20nm, also will be by changing the state of process of growth ionic medium body: the light emitting discharge state that is used by routine be adjusted into the dark discharge state, setting the direct supply output state is the constant current state, the output current intensity that reduces power supply then is till observing plasma body and becoming the dark discharge state, and the diameter range of the carbon nanotube that described method can prepare is 5-300nm; Control prepared length of carbon nanotube, 1) be to change growth velocity by changing growth temperature: temperature high growth rates more is fast more, 2) be the control growing time: growth velocity is 200nm/min, then the growth time of the carbon nanotube needs of 2000nm length is 10min, the moment that growth time calculates to feed acetylene is initial, with moment of stopping to feed acetylene or eliminating plasma body be termination, the length range of the carbon nanotube that described method can prepare is 50-50000nm.
8, the manufacture method of carbon nanotube as claimed in claim 6 or fiber array, it is characterized in that: when adopting glass insulation substrate (3), the thickness of above-mentioned catalyst film (1) is: during 19-34nm, can directly go up deposited catalyst film (1) at glass insulation substrate (3).
9, the manufacture method of carbon nanotube as claimed in claim 4 or fiber array, it is characterized in that: the various growth parameter(s)s of above-mentioned carbon nanotube or fiber array are: silicon substrate, 40nm Ni catalyst film (1), temperature are 500 ℃, and gas ratio is: the NH of 160sccm
3: the C of 80sccm
2H
2, plasma current is: 0.4A, air pressure are 8Torr, growth time is 5 minutes.
10, a kind of carbon nano pipe array or the application of carbon nanofiber array in preparation optical frequency doublet antenna array as previously discussed.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101308889B (en) * | 2007-05-16 | 2010-08-18 | 中国科学院半导体研究所 | Method for enhancing light-emitting efficiency of semiconductor type carbon nano-tube |
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| CN1214974C (en) * | 2002-01-25 | 2005-08-17 | 中国科学院化学研究所 | Process for preparing strip type array carbon nano tube |
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| CN101308889B (en) * | 2007-05-16 | 2010-08-18 | 中国科学院半导体研究所 | Method for enhancing light-emitting efficiency of semiconductor type carbon nano-tube |
| CN102223140A (en) * | 2010-04-13 | 2011-10-19 | 中国科学院上海微系统与信息技术研究所 | Terahertz oscillation method based on carbon nanometer tube and terahertz oscillator |
| CN102223140B (en) * | 2010-04-13 | 2013-10-02 | 中国科学院上海微系统与信息技术研究所 | Terahertz oscillation method based on carbon nanometer tube and terahertz oscillator |
| CN102646734A (en) * | 2011-02-21 | 2012-08-22 | 中兴通讯股份有限公司 | Antenna device and mobile terminal |
| WO2012113322A1 (en) * | 2011-02-21 | 2012-08-30 | 中兴通讯股份有限公司 | Antenna device and mobile terminal |
| US9343813B2 (en) | 2011-09-06 | 2016-05-17 | Digican (Shanghai) Corp., Ltd. | Antenna with high light transmittance |
| WO2013033963A1 (en) * | 2011-09-06 | 2013-03-14 | 数伦计算机技术（上海）有限公司 | Antenna with high light transmittance |
| CN102709399A (en) * | 2012-06-21 | 2012-10-03 | 上海理工大学 | Manufacturing method of high-efficiency nano antenna solar battery |
| CN102709399B (en) * | 2012-06-21 | 2014-10-15 | 上海理工大学 | Manufacturing method of high-efficiency nano antenna solar battery |
| CN104445140A (en) * | 2014-11-05 | 2015-03-25 | 华文蔚 | Method for making carbon nano tube |
| CN104810609A (en) * | 2015-04-24 | 2015-07-29 | 天津理工大学 | CNT (Carbon Nano Tube) terahertz antenna |
| CN104810609B (en) * | 2015-04-24 | 2018-03-30 | 天津理工大学 | A kind of CNT Terahertz antenna |
| CN106832766A (en) * | 2016-12-19 | 2017-06-13 | 西北大学 | Array carbon nano tube polymer composites, preparation method and applications |
| CN106832766B (en) * | 2016-12-19 | 2019-06-04 | 西北大学 | Array carbon nano tube polymer composites, preparation method and applications |
| CN108736295A (en) * | 2017-04-20 | 2018-11-02 | 清华大学 | A method of generating Terahertz modulating wave |
| CN108736296A (en) * | 2017-04-20 | 2018-11-02 | 清华大学 | A kind of THz wave emitter |
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