CN104726846A - Large-area graphene preparing method based on high-density ordered copper nanowire catalyst - Google Patents
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Abstract
The invention discloses a large-area graphene preparing method based on a high-density ordered copper nanowire catalyst, mainly aiming at solving the problem that graphene cannot be prepared from a copper foil in a large area at present. The preparing method comprises the following implementing steps: preparing a through-hole anodic aluminum oxide template by virtue of a method of secondary oxidation; depositing a layer of copper film on one surface of the through-hole anodic aluminum oxide template, using the copper film as an electrode, and preparing a high-density ordered copper nanowire in required size in the through-hole anodic aluminum oxide template; and finally catalyzing by taking the high-density ordered copper nanowire as a catalyst so as to promote the growth of graphene in a large area. Compared with graphene growing from existing copper foil catalyst, the graphene disclosed by the invention has the advantages of larger area and better quality, and the graphene is applicable to the manufacturing of semiconductor devices.
Description
Technical field
The invention belongs to microelectronics technology, particularly a kind of preparation method of Graphene, can be used for the preparation of semiconducter device.
Technical background
Along with the development of unicircuit, the critical size of current silicon-based devices has reached the theory and technology limit, quantum effect becomes main mechanism, traditional silicon-based devices based on diffusion-drift theory is subject to physics and the dual restriction of technology, the important task bearing continuity Moore's Law cannot be continued, therefore, base semiconductor material of new generation must be found, develop new theory and device model, to meet the needs that unicircuit continues development.
Grapheme material is a kind of carbon back two dimensional crystal, it is known the thinnest the lightest material at present, individual layer is atomic thickness only, it has extremely excellent physicochemical property, the such as high transparency and snappiness, superpower mechanical property, high carrier mobility, theoretical estimation graphene carrier mobility is more than 200000cm
2v
-1s
-1, be hundreds of times of silicon.And there is not mismatch problems in it and substrate, can be completely compatible with silicon-based devices technique, there is outstanding industrial advantage.Therefore, Graphene appear as industrial community and scientific and technological circle bring dawn, it is the novel material that the substituted for silicon be expected most becomes base semiconductor material of future generation.
But the preparation of current grapheme material also exists many difficulties, become the bottleneck that graphene device moves towards to apply.With high costs compared to silicon carbide substrates high temperature pyrolytic cracking (HTP), the shortcoming of controllability and poor compatibility, magnesium-yttrium-transition metal catalytic chemical gaseous phase deposition extension is method prepared by the large-area graphene extensively adopted in the world, and it is not by the restriction of substrate dimension, equipment is simple, can produce in enormous quantities.The magnesium-yttrium-transition metal chemical vapour deposition extensively adopted at present is exactly that the carbon atom that under high temperature, carbon source cracking produces is adsorbed on substrate surface, can form continuous print Graphene through two-dimensional growth on magnesium-yttrium-transition metal copper surface.
Although carried out electrochemical etching to copper foil surface, what copper foil surface was become is smooth, and Copper Foil is still polycrystalline, so or can not grow large-area Graphene.
Summary of the invention
The object of the present invention is to provide a kind of large-area graphene preparation method based on the orderly copper nano-wire catalysis of high-density, to solve the existing problem utilizing Copper Foil to be difficult to prepare large-area graphene.
Realizing the object of the invention key problem in technology is: utilize the orderly copper nano-wire of anodic oxidation aluminium formwork growing high density, then uses the high-density of gained orderly copper nano-wire catalytic growth Graphene.By changing the solute concentration of solution, temperature, electroplating current, graphene growth condition etc., realize large-area graphene growth.Implementation step comprises as follows:
(1) through-hole anodic aluminum oxide template is prepared:
(1a) smooth process is carried out to high-purity aluminium flake;
(1b) constant voltage DC pattern is utilized to carry out once oxidation, the processing condition of oxidation to the aluminium flake after smooth: voltage is 40V, and temperature is 3 ~ 6 DEG C, and the concentration of oxalic acid solution is 0.3 ~ 0.5mol/L, oxidization time 24 hours;
(1c) aluminium flake after once oxidation is put into chromium phosphoric acid solution, soak 24 hours at 45 DEG C of temperature, the anodised aluminium that removing surface has generated, then carry out secondary oxidation with the processing condition identical with once oxidation;
(1d) the aluminium base of the aluminium flake back side after secondary oxidation is removed with cupric chloride hydrochloric acid soln, be formed with the anodised aluminium on blocking layer, to be swum on the 4 ~ 6wt% phosphoric acid solution at 35 ~ 40 DEG C of temperature 10 ~ 20 minutes again, remove the blocking layer at the anodised aluminium back side, put it in 0.3 ~ 0.5mol/L oxalic acid solution the reaming carried out 1 ~ 2 hour again, obtaining thickness is 40um through-hole anodic aluminum oxide template;
(2) be the copper film of 40 ~ 50nm at a deposit thickness of through-hole anodic aluminum oxide template, sedimentation rate is
(3) through-hole anodic aluminum oxide template with copper film is placed in bottom the electroplanting device that electric current is 10 ~ 20mA, copper film is faced down, and this copper film is connected as negative electrode with power cathode, cupric chloride boric acid solution is gone up at the another side of through-hole anodic aluminum oxide template, and cupric chloride boric acid solution is connected with positive source, electroplate 100 minutes, obtain the orderly copper nano-wire of high-density that length is 10 ~ 20um;
(4) there is the copper film through-hole anodic aluminum oxide template of the orderly copper nano-wire of high-density to take out from electroplanting device by long, use 20g/L ammonium persulfate solution to remove the copper film deposited in through-hole anodic aluminum oxide template;
(5) with the high-density orderly copper nano-wire catalytic growth Graphene in through-hole anodic aluminum oxide template:
(5a) through-hole anodic aluminum oxide template removing copper film is put into chemical vapor deposition reaction chamber, be removed copper film and face up, in reaction chamber, pass into Ar and CH simultaneously
4two kinds of gases, the throughput ratio keeping two kinds of gases is 10:1 ~ 2:1, and wherein, the flow of Ar gas is 20 ~ 200sccm, CH
4the flow of gas is 10 ~ 20sccm, controls reaction chamber air pressure and maintains 0.1 ~ 1Torr;
(5b) with the catalyzer of the orderly copper nano-wire of high-density as growing graphene, setting reaction chamber temperature is 900 ~ 1100 DEG C, and control heating-up time and hold-time are in 20 ~ 60min;
(5c) Ar and CH in reaction chamber is kept
4the flow of two kinds of gases is constant, and reaction chamber air pressure maintains 0.1 ~ 1Torr, waits for that reaction chamber Temperature fall is to less than 100 DEG C, completes the growth of Graphene.
Tool of the present invention has the following advantages:
1. the anodised aluminium of the present invention owing to generating removing once oxidation, then carry out secondary oxidation, the anodised aluminium prepared is evenly distributed, and aperture is consistent.
2. the present invention prepares copper nano-wire by adopting the through-hole anodic aluminum oxide template with copper film, can obtain high-density and the copper nano-wire be evenly distributed.
3. the present invention is owing to using highdensity copper nano-wire as the catalyzer of growing graphene, effectively can regulate and control size and the lattice direction of Graphene, finally obtain large-area Graphene.
Accompanying drawing explanation
Fig. 1 is realization flow figure of the present invention;
Fig. 2 is the schematic cross-section that once oxidation obtains anodised aluminium;
Fig. 3 is the schematic cross-section that secondary oxidation obtains anodised aluminium;
Fig. 4 is the schematic cross-section of the anodic oxidation aluminium formwork after reaming.
Embodiment
In order to make objects and advantages of the present invention clearly understand, below in conjunction with drawings and Examples, the present invention is described in further detail.Should be appreciated that specific embodiment described herein only in order to explain the present invention, do not form limitation of the invention.
With reference to Fig. 1, the present invention is based on the large-area graphene preparation method based on the orderly copper nano-wire catalysis of high-density, provide following three kinds of embodiments.
Embodiment 1: making based on length is the Graphene of 10um copper nano-wire catalysis.
Step 1: pre-treatment is carried out to aluminium flake.
(1a) aluminium flake of 99.999% purity is put into acetone successively, in water and aqueous isopropanol, the grease on each ultrasonic 5 minutes removing surfaces;
(1b) by ultrasonic complete after aluminium flake put into mixed acid solution, at 60 DEG C of temperature soak 30 seconds remove surface impurity, the proportioning of this mixed acid solution is: concentrated hydrochloric acid 20mL, concentrated nitric acid 10mL, hydrofluoric acid 1mL, water 69mL;
(1c) aluminium flake of removing surface impurity is put into polishing fluid, adopt constant voltage mode polishing 4 minutes under 20V voltage, make aluminium flake become smooth, this polishing fluid is mixed by the perchloric acid stoste of 25mL and 75mL dehydrated alcohol.
Step 2: utilize constant voltage DC pattern to be oxidized pretreated aluminium flake.
(2a) oxalic acid solution that concentration is 0.3mol/L put into by the aluminium flake after polishing is complete, be 40V at voltage, temperature is 6 DEG C, processing condition under soak 24 hours, complete once oxidation, as shown in Figure 2, B in Fig. 2 is aluminium flake used, A is the anodised aluminium that once oxidation generates, because be once oxidation, so the anodised aluminium skewness of Surface Creation;
(2b) aluminium flake after once oxidation is put into chromium phosphoric acid solution, soak 24 hours at 45 DEG C of temperature, the anodised aluminium that removing surface has generated, the proportioning of this chromium phosphoric acid solution is: chromic oxide 3.6g, strong phosphoric acid 14.2g;
(2c) secondary oxidation is carried out with the processing condition identical with once oxidation again, obtain the anodised aluminium that thickness is 40um, as shown in Figure 3, D in Fig. 3 is aluminium flake used, C is the anodised aluminium that secondary oxidation generates, because be secondary oxidation, so the anodised aluminium of Surface Creation is evenly distributed.
Step 3: remove the aluminium base of the anodised aluminium back side.
Anodised aluminium is put into cupric chloride hydrochloric acid soln and remove the aluminium base of the aluminium flake back side, its proportioning of cupric chloride hydrochloric acid soln is: Copper dichloride dihydrate 6.8g, concentrated hydrochloric acid 200mL, water 200mL.
Step 4: form through-hole anodic aluminum oxide template.
Anodised aluminium aluminium base for the removing back side is swum in 4wt% phosphoric acid solution upper 20 minute at 35 DEG C of temperature, remove the blocking layer at the anodised aluminium back side, put it in 0.3mol/L oxalic acid solution the reaming carried out 1 hour again, forming thickness is 40um through-hole anodic aluminum oxide template, as shown in Figure 4, the E in Fig. 4 is the through hole anodised aluminium after removing blocking layer and through hole.
Step 5: utilize the copper film that the mode of thermal evaporation is 40nm at a deposit thickness of through-hole anodic aluminum oxide template, sedimentation rate is
Step 6: electro-coppering nano wire.
Through-hole anodic aluminum oxide template with copper film is placed in bottom the electroplanting device that electric current is 10mA, copper film is faced down, and this copper film is connected as negative electrode with power cathode, cupric chloride boric acid solution is gone up at the another side of through-hole anodic aluminum oxide template, and cupric chloride boric acid solution is connected with positive source, electroplate 100 minutes, obtain the orderly copper nano-wire of high-density that length is 10um, this cupric chloride boric acid solution, its proportioning is: Salzburg vitriol 0.25g, boric acid 3.1g, deionized water 100mL.
Step 7: have the copper film through-hole anodic aluminum oxide template of the orderly copper nano-wire of high-density to take out from electroplanting device by long, uses 20g/L ammonium persulfate solution to remove the copper film deposited in through-hole anodic aluminum oxide template.
Step 8: with the high-density orderly copper nano-wire catalytic growth Graphene in through-hole anodic aluminum oxide template.
(8a) through-hole anodic aluminum oxide template removing copper film is put into chemical vapor deposition reaction chamber, that making to be removed copper film faces up, in reaction chamber, pass into Ar and CH simultaneously
4two kinds of gases, the throughput ratio keeping two kinds of gases is 2:1, and wherein, the flow of Ar gas is 20sccm, CH
4the flow of gas is 10sccm, controls reaction chamber air pressure and maintains 0.1Torr;
(8b) with the catalyzer of the orderly copper nano-wire of high-density as growing graphene, setting reaction chamber temperature is 900 DEG C, and control heating-up time and hold-time are in 20min;
(8c) Ar and CH in reaction chamber is kept
4the flow of two kinds of gases is constant, and reaction chamber air pressure maintains 0.1Torr, waits for that reaction chamber Temperature fall is to less than 100 DEG C, completes the growth of Graphene.
Embodiment 2: making based on length is the Graphene of 15um copper nano-wire catalysis.
The first step: pre-treatment is carried out to aluminium flake.
(A1) aluminium flake of 99.999% purity is put into acetone successively, in water and aqueous isopropanol, within each ultrasonic 7 minutes, remove surperficial grease;
(A2) by ultrasonic complete after aluminium flake put into mixed acid solution, at 60 DEG C of temperature soak 32 seconds remove surface impurity, the proportioning of this mixed acid solution is: concentrated hydrochloric acid 20mL, concentrated nitric acid 10mL, hydrofluoric acid 1mL, water 69mL;
(A3) aluminium flake of removing surface impurity is put into polishing fluid, adopt constant voltage mode polishing 4 minutes 30 seconds under 20V voltage, make aluminium flake become smooth, this polishing fluid is mixed by the perchloric acid stoste of 25mL and 75mL dehydrated alcohol.
Second step: utilize constant voltage DC pattern to be oxidized pretreated aluminium flake.
(B1) once oxidation, the oxalic acid solution that concentration is 0.4mol/L put into by aluminium flake after complete by polishing, be 40V at voltage, temperature is 5 DEG C, processing condition under soak 24 hours, as shown in Figure 2, B in Fig. 2 is aluminium flake used, A is the anodised aluminium that once oxidation generates, because be once oxidation, so the anodised aluminium skewness of Surface Creation;
(B2) aluminium flake after oxidation is carried out anodised aluminium removal;
This step is identical with the step 2b in embodiment 1.
(B3) secondary oxidation obtains the anodised aluminium of 40um, the processing condition of secondary oxidation are identical with the processing condition of once oxidation, as shown in Figure 3, D in Fig. 3 is aluminium flake used, C is the anodised aluminium that secondary oxidation generates, because be secondary oxidation, so the anodised aluminium of Surface Creation is evenly distributed.
3rd step: remove the aluminium base of the anodised aluminium back side.
This step is identical with the step 3 in embodiment 1.
4th step: anodised aluminium aluminium base for the removing back side is swum in 5wt% phosphoric acid solution upper 15 minute at 37 DEG C of temperature, remove the blocking layer at the anodised aluminium back side, put it in 0.4mol/L oxalic acid solution the reaming carrying out 1 hour 30 minutes again, forming thickness is 40um through-hole anodic aluminum oxide template, as shown in Figure 4, the E in Fig. 4 is the through hole anodised aluminium after removing blocking layer and through hole.
5th step: utilize the copper film that the mode of thermal evaporation is 45nm at a deposit thickness of through-hole anodic aluminum oxide template, sedimentation rate is
6th step: the through-hole anodic aluminum oxide template with copper film is placed in bottom the electroplanting device that electric current is 15mA, copper film is faced down, and this copper film is connected as negative electrode with power cathode, cupric chloride boric acid solution is gone up at the another side of through-hole anodic aluminum oxide template, and cupric chloride boric acid solution is connected with positive source, electroplate 100 minutes, obtain the orderly copper nano-wire of high-density that length is 15um, this cupric chloride boric acid solution, its proportioning is: Salzburg vitriol 0.25g, boric acid 3.1g, deionized water 100mL.
7th step: the copper film on removing anodic oxidation aluminium formwork surface.
This step is identical with the step 7 in embodiment 1.
8th step: with the high-density orderly copper nano-wire catalytic growth Graphene in through-hole anodic aluminum oxide template.
(H1) through-hole anodic aluminum oxide template removing copper film is put into chemical vapor deposition reaction chamber, be removed copper film and face up, in reaction chamber, pass into Ar and CH simultaneously
4two kinds of gases, the throughput ratio keeping two kinds of gases is 5:1, and wherein, the flow of Ar gas is 60sccm, CH
4the flow of gas is 12sccm, controls reaction chamber air pressure and maintains 0.5Torr;
(H2) with the catalyzer of the orderly copper nano-wire of high-density as growing graphene, setting reaction chamber temperature is 1000 DEG C, and control heating-up time and hold-time are in 40min;
(H3) Ar and CH in reaction chamber is kept
4the flow of two kinds of gases is constant, and reaction chamber air pressure maintains 0.5Torr, waits for that reaction chamber Temperature fall is to less than 100 DEG C, completes the growth of Graphene.
Embodiment 3: making based on length is the Graphene of 20um copper nano-wire catalysis.
Step one, carries out pre-treatment to aluminium flake.
First the aluminium flake of 99.999% purity is put into acetone successively, in water and aqueous isopropanol, within each ultrasonic 10 minutes, remove surperficial grease; Again by ultrasonic complete after aluminium flake put into mixed acid solution, at 60 DEG C of temperature soak 35 seconds remove surface impurity, the proportioning of this mixed acid solution is: concentrated hydrochloric acid 20mL, concentrated nitric acid 10mL, hydrofluoric acid 1mL, water 69mL; Again the aluminium flake of removing surface impurity is put into polishing fluid, adopt constant voltage mode polishing 5 minutes under 20V voltage, make aluminium flake become smooth, this polishing fluid is mixed by the perchloric acid stoste of 25mL and 75mL dehydrated alcohol.
Step 2: utilize constant voltage DC pattern to be oxidized pretreated aluminium flake.
The oxalic acid solution that concentration is 0.5mol/L put into by aluminium flake after first polishing is complete, be 40V at voltage, temperature is 3 DEG C, processing condition under soak 24 hours, complete once oxidation, as shown in Figure 2, B in Fig. 2 is aluminium flake used, A is the anodised aluminium that once oxidation generates, because be once oxidation, so the anodised aluminium skewness of Surface Creation; Again the aluminium flake after once oxidation is put into chromium phosphoric acid solution, soak 24 hours at 45 DEG C of temperature, the anodised aluminium that removing surface has generated, the proportioning of this chromium phosphoric acid solution is: chromic oxide 3.6g, strong phosphoric acid 14.2g; Finally carried out secondary oxidation, obtain the anodised aluminium that thickness is 40um, the processing condition of secondary oxidation are identical with the processing condition of once oxidation, as shown in Figure 3, D in Fig. 3 is aluminium flake used, C is the anodised aluminium that secondary oxidation generates, because be secondary oxidation, so the anodised aluminium of Surface Creation is evenly distributed.
Step 3: remove the aluminium base of the anodised aluminium back side.
This step is identical with the step 3 in embodiment 1.
Step 4: form through-hole anodic aluminum oxide template, 6wt% phosphoric acid solution upper 10 minute at 40 DEG C of temperature is swum in by the anodised aluminium that the removing back side is aluminium base, remove the blocking layer at the anodised aluminium back side, put it in 0.5mol/L oxalic acid solution the reaming carried out 2 hours again, forming thickness is 40um through-hole anodic aluminum oxide template, as shown in Figure 4, the E in Fig. 4 is the through hole anodised aluminium after removing blocking layer and through hole.
Step 5: at a depositing copper film of anodic oxidation aluminium formwork.
Utilize the copper film that the mode of magnetron sputtering is 50nm at a deposit thickness of through-hole anodic aluminum oxide template, sedimentation rate is
Step 6: electro-coppering nano wire.
Through-hole anodic aluminum oxide template with copper film is placed in bottom the electroplanting device that electric current is 20mA, copper film is faced down, and this copper film is connected as negative electrode with power cathode, cupric chloride boric acid solution is gone up at the another side of through-hole anodic aluminum oxide template, and cupric chloride boric acid solution is connected with positive source, electroplate 100 minutes, obtain the orderly copper nano-wire of high-density that length is 20um, this cupric chloride boric acid solution, its proportioning is: Salzburg vitriol 0.25g, boric acid 3.1g, deionized water 100mL.
Step 7: the copper film on removing anodic oxidation aluminium formwork surface.
This step is identical with the step 7 in embodiment 1.
Step 8: with the high-density orderly copper nano-wire catalytic growth Graphene in through-hole anodic aluminum oxide template.
The through-hole anodic aluminum oxide template removing copper film is put into chemical vapor deposition reaction chamber, and that making to be removed copper film faces up, in reaction chamber, pass into Ar and CH simultaneously
4two kinds of gases, the throughput ratio keeping two kinds of gases is 10:1, and wherein, the flow of Ar gas is 200sccm, CH
4the flow of gas is 20sccm, controls reaction chamber air pressure and maintains 1Torr;
Again with the catalyzer of the orderly copper nano-wire of high-density as growing graphene, setting reaction chamber temperature is 1100 DEG C, and control heating-up time and hold-time in 60min, and keep Ar and CH in reaction chamber
4the flow of two kinds of gases is constant, and reaction chamber air pressure maintains 1Torr, waits for that reaction chamber Temperature fall is to less than 100 DEG C, completes the growth of Graphene.
Foregoing description is several preferred embodiment of the present invention; be not construed as limiting the invention; for those skilled in the art; after understanding content of the present invention and principle; can when not deviating from the principle and scope of the present invention; carry out various correction in form and details and change according to method of the present invention, but these are based on correction of the present invention with change still within claims of the present invention.
Claims (8)
1., based on the large-area graphene preparation method of the orderly copper nano-wire catalysis of high-density, comprise the steps:
(1) through-hole anodic aluminum oxide template is prepared:
(1a) smooth process is carried out to high-purity aluminium flake;
(1b) constant voltage DC pattern is utilized to carry out once oxidation, the processing condition of oxidation to the aluminium flake after smooth: voltage is 40V, and temperature is 3 ~ 6 DEG C, and the concentration of oxalic acid solution is 0.3 ~ 0.5mol/L, oxidization time 24 hours;
(1c) aluminium flake after once oxidation is put into chromium phosphoric acid solution, soak 24 hours at 45 DEG C of temperature, the anodised aluminium that removing surface has generated, then carry out secondary oxidation with the processing condition identical with once oxidation;
(1d) the aluminium base of the aluminium flake back side after secondary oxidation is removed with cupric chloride hydrochloric acid soln, be formed with the anodised aluminium on blocking layer, to be swum on the 4 ~ 6wt% phosphoric acid solution at 35 ~ 40 DEG C of temperature 10 ~ 20 minutes again, remove the blocking layer at the anodised aluminium back side, put it in 0.3 ~ 0.5mol/L oxalic acid solution the reaming carried out 1 ~ 2 hour again, obtaining thickness is 40um through-hole anodic aluminum oxide template;
(2) be the copper film of 40 ~ 50nm at a deposit thickness of through-hole anodic aluminum oxide template, sedimentation rate is
(3) through-hole anodic aluminum oxide template with copper film is placed in bottom the electroplanting device that electric current is 10 ~ 20mA, copper film is faced down, and this copper film is connected as negative electrode with power cathode, cupric chloride boric acid solution is gone up at the another side of through-hole anodic aluminum oxide template, and cupric chloride boric acid solution is connected with positive source, electroplate 100 minutes, obtain the orderly copper nano-wire of high-density that length is 10 ~ 20um;
(4) there is the copper film through-hole anodic aluminum oxide template of the orderly copper nano-wire of high-density to take out from electroplanting device by long, use 20g/L ammonium persulfate solution to remove the copper film deposited in through-hole anodic aluminum oxide template;
(5) with the high-density orderly copper nano-wire catalytic growth Graphene in through-hole anodic aluminum oxide template:
(5a) through-hole anodic aluminum oxide template removing copper film is put into chemical vapor deposition reaction chamber, be removed copper film and face up, in reaction chamber, pass into Ar and CH simultaneously
4two kinds of gases, the throughput ratio keeping two kinds of gases is 10:1 ~ 2:1, and wherein, the flow of Ar gas is 20 ~ 200sccm, CH
4the flow of gas is 10 ~ 20sccm, controls reaction chamber air pressure and maintains 0.1 ~ 1Torr;
(5b) with the catalyzer of the orderly copper nano-wire of high-density as growing graphene, setting reaction chamber temperature is 900 ~ 1100 DEG C, and control heating-up time and hold-time are in 20 ~ 60min;
(5c) Ar and CH in reaction chamber is kept
4the flow of two kinds of gases is constant, and reaction chamber air pressure maintains 0.1 ~ 1Torr, waits for that reaction chamber Temperature fall is to less than 100 DEG C, completes the growth of Graphene.
2. the large-area graphene preparation method based on the orderly copper nano-wire catalysis of high-density according to claim 1, is characterized in that: carry out smooth process to high-purity aluminium flake in step (1a), carry out as follows:
(1a1) high-purity aluminium flake is put into acetone successively, in water and aqueous isopropanol, within ultrasonic 5 ~ 10 minutes, remove surperficial grease;
(1a2) by ultrasonic complete after aluminium flake put into mixed acid solution, at 60 DEG C of temperature soak 30 ~ 35 seconds remove surface impurity;
(1a3) aluminium flake of removing surface impurity is put into polishing fluid, adopt constant voltage mode polishing 4 ~ 5 minutes under 20V voltage, make aluminium flake become smooth.
3. the large-area graphene preparation method based on the orderly copper nano-wire catalysis of high-density according to claim 1, is characterized in that: chromium phosphoric acid solution in step (1c), its proportioning is: chromic oxide 3.6g, strong phosphoric acid 14.2g.
4. the large-area graphene preparation method based on the orderly copper nano-wire catalysis of high-density according to claim 1, it is characterized in that: the cupric chloride hydrochloric acid soln in step (1d), its proportioning is: Copper dichloride dihydrate 6.8g, concentrated hydrochloric acid 200mL, water 200mL.
5. the large-area graphene preparation method based on the orderly copper nano-wire catalysis of high-density according to claim 1, it is characterized in that: at a depositing copper film of through-hole anodic aluminum oxide template in described step (2), adopt the mode of thermal evaporation methods or magnetron sputtering to deposit.
6. the large-area graphene preparation method based on the orderly copper nano-wire catalysis of high-density according to claim 1, it is characterized in that: the cupric chloride boric acid solution in step (3), its proportioning is: Salzburg vitriol 0.25g, boric acid 3.1g, deionized water 100mL.
7. the large-area graphene preparation method based on the orderly copper nano-wire catalysis of high-density according to claim 2, it is characterized in that: the mixed acid solution in step (1a2), its proportioning is: concentrated hydrochloric acid 20mL, concentrated nitric acid 10mL, hydrofluoric acid 1mL, water 69mL.
8. the large-area graphene preparation method based on the orderly copper nano-wire catalysis of high-density according to claim 2, is characterized in that: the polishing fluid in step (1a3), is mixed by the perchloric acid stoste of 25mL and 75mL dehydrated alcohol.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6440288B1 (en) * | 2000-01-13 | 2002-08-27 | Korea Advanced Institute Of Science And Technology | Method for preparing anode electrode for high voltage electrolytic capacitor |
| CN102864476A (en) * | 2012-09-29 | 2013-01-09 | 南京理工大学 | Preparation method of through-hole anodic aluminum oxide template |
| CN103183335A (en) * | 2013-03-12 | 2013-07-03 | 西安电子科技大学 | Cu film annealing based method for preparing large-area graphene on SiC substrate |
| CN103241728A (en) * | 2012-02-14 | 2013-08-14 | 中国科学院上海微系统与信息技术研究所 | Method for preparing graphene nanopore array through chemical vapor deposition by using porous anodic alumina (PAA) as template |
| CN103840003A (en) * | 2014-02-21 | 2014-06-04 | 西安电子科技大学 | Double-gate graphene transistor with aluminum oxide as gate dielectric and manufacturing method thereof |
-
2015
- 2015-03-06 CN CN201510100988.3A patent/CN104726846B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6440288B1 (en) * | 2000-01-13 | 2002-08-27 | Korea Advanced Institute Of Science And Technology | Method for preparing anode electrode for high voltage electrolytic capacitor |
| CN103241728A (en) * | 2012-02-14 | 2013-08-14 | 中国科学院上海微系统与信息技术研究所 | Method for preparing graphene nanopore array through chemical vapor deposition by using porous anodic alumina (PAA) as template |
| CN102864476A (en) * | 2012-09-29 | 2013-01-09 | 南京理工大学 | Preparation method of through-hole anodic aluminum oxide template |
| CN103183335A (en) * | 2013-03-12 | 2013-07-03 | 西安电子科技大学 | Cu film annealing based method for preparing large-area graphene on SiC substrate |
| CN103840003A (en) * | 2014-02-21 | 2014-06-04 | 西安电子科技大学 | Double-gate graphene transistor with aluminum oxide as gate dielectric and manufacturing method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 史永贵等: "化学气相沉积法生长石墨烯的研究", 《人工晶体学报》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106770160A (en) * | 2016-12-13 | 2017-05-31 | 中国计量大学 | A kind of noble metal/Graphene SERS substrate fabrication methods |
| CN106856228A (en) * | 2016-12-27 | 2017-06-16 | Tcl集团股份有限公司 | A kind of QLED devices and preparation method thereof |
| CN108359234A (en) * | 2017-07-31 | 2018-08-03 | 安徽旭升新材料有限公司 | Waste recovery type electroconductive nylon composite thermoplastic carbon fiber material and preparation method thereof |
| CN111575761A (en) * | 2020-05-26 | 2020-08-25 | 苏州凌威新能源科技有限公司 | Alumina template, highly vertical ordered antimony nanowire array and preparation method thereof |
| CN111996560A (en) * | 2020-07-10 | 2020-11-27 | 深圳先进技术研究院 | Metal wire preparation method, metal wire and clamp |
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