CN104726846B - Large-area graphene preparation method based on the orderly copper nano-wire catalysis of high density - Google Patents
Large-area graphene preparation method based on the orderly copper nano-wire catalysis of high density Download PDFInfo
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Abstract
The invention discloses a kind of large-area graphene preparation method based on the orderly copper nano-wire catalysis of high density, mainly solves the problems, such as that existing Copper Foil is difficult to for preparing large-area graphene.Implementation step is：The method for first passing through secondary oxidation prepares through-hole anodic aluminum oxide template；One layer of copper film is deposited in the one side of through-hole anodic aluminum oxide template again, using copper film as electrode, and the orderly copper nano-wire of high density of size required for preparing in through-hole anodic aluminum oxide template；High density orderly copper nano-wire is made into catalyst finally, large-area Graphene is grown.The Graphene that the present invention is obtained is compared the Graphene of existing Copper Foil catalytic growth and has the advantages that area bigger, better quality, can be used for the manufacture of semiconductor devices.
Description
Technical field
The invention belongs to microelectronics technology, more particularly to a kind of preparation method of Graphene, can be used for semiconductor device
The preparation of part.
Technical background
With the development of integrated circuit, the critical size of current silicon-based devices has reached the theory and technology limit, quantum
Effect has become main mechanism, and traditional silicon-based devices based on diffusion-drift theory are subject to physics and the dual restriction of technology,
Cannot continue to undertake the important task for continuing Moore's Law, therefore, it is necessary to find base semiconductor material of new generation, develop new theory
And device model, to meet the needs that integrated circuit continues development.
Grapheme material is a kind of carbon-based two dimensional crystal, is to be currently known most light most thin material, individual layer only atomic thickness,
It has extremely excellent physicochemical properties, the such as high transparency and pliability, superpower mechanical performance, high load
Stream transport factor, it is theoretical to estimate graphene carrier mobility more than 200000cm2V-1s-1, it is the hundreds times of silicon.And it with
There are no mismatch problems in substrate, can be completely compatible with silicon-based devices technique, with prominent industrial advantage.Therefore, Graphene
Appear as industrial circle and scientific and technological circle bring dawn, it is that the substituted for silicon being most expected becomes base semiconductor material of future generation
New material.
But, also there are many difficulties in the preparation of current grapheme material, become the bottleneck that graphene device moves towards to apply.
It is with high costs compared to silicon carbide substrates high temperature pyrolytic cracking (HTP), the shortcoming of controllability and poor compatibility, magnesium-yttrium-transition metal catalysisization
The method that vapour deposition extension is prepared by large-area graphene widely used in the world is learned, it is not limited by substrate dimension,
Equipment is simple, can produce in enormous quantities.Magnesium-yttrium-transition metal chemical vapor deposition widely used at present is exactly in magnesium-yttrium-transition metal
Copper surface, the carbon atom that carbon source cracking is produced under high temperature are adsorbed in substrate surface, can form continuous stone through two-dimensional growth
Black alkene.
Although electrochemical polish has been carried out to copper foil surface, make the smooth of copper foil surface change, Copper Foil is still polycrystalline,
So or large-area Graphene can not be grown.
The content of the invention
It is an object of the invention to provide prepared by a kind of large-area graphene based on the orderly copper nano-wire catalysis of high density
Method, to solve the problems, such as that existing utilization Copper Foil is difficult to prepare large-area graphene.
Realize that the object of the invention key problem in technology is：Using the orderly copper nano-wire of anodic oxidation aluminium formwork growing high density, then
With the orderly copper nano-wire catalytic growth Graphene of the high density of gained.By the solute concentration for changing solution, temperature, plating electricity
Stream, graphene growth condition etc., realize that large-area graphene grows.Implementation step includes as follows：
(1) prepare through-hole anodic aluminum oxide template：
(1a) smooth process is carried out to high-purity aluminium flake；
(1b) once oxidation, the process conditions of oxidation are carried out to the aluminium flake after smooth using constant voltage DC pattern：Voltage is
40V, temperature are 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 in chromium phosphoric acid solution, is soaked 24 hours at a temperature of 45 DEG C, remove table
The anodised aluminium that face has generated, then to carry out secondary oxidation with once oxidation identical process conditions；
(1d) aluminium base at the aluminium flake back side after secondary oxidation is removed with copper chloride hydrochloric acid solution, the anode on barrier layer is formed with
Aluminum oxide, then swum in 10～20 minutes on the 4～6wt% phosphoric acid solutions at a temperature of 35～40 DEG C, remove anodic oxidation
The barrier layer at the aluminium back side, then the reaming of 1～2 hour in putting it into 0.3～0.5mol/L oxalic acid solutions, is carried out, obtaining thickness is
40um through-hole anodic aluminum oxide templates；
(2) the face deposit thickness in through-hole anodic aluminum oxide template is the copper film of 40～50nm, and sedimentation rate is
(3) through-hole anodic aluminum oxide template with copper film is placed in into the electroplanting device bottom that electric current is 10～20mA, is made
Copper film faces down, and the copper film is connected as negative electrode with power cathode, goes up in the another side of through-hole anodic aluminum oxide template
Copper chloride BAS, and copper chloride BAS is connected with positive source, electroplates 100 minutes, obtain length for 10～
The orderly copper nano-wire of high density of 20um；
(4) the copper film through-hole anodic aluminum oxide template that length is had the orderly copper nano-wire of high density is taken out from electroplanting device, is made
The copper film in through-hole anodic aluminum oxide template in deposition is removed with 20g/L ammonium persulfate solutions；
(5) with the orderly copper nano-wire catalytic growth Graphene of high density in through-hole anodic aluminum oxide template：
(5a) through-hole anodic aluminum oxide template for having been removed copper film is put in chemical vapor deposition reaction chamber, is removed copper
Film faces up, and in reative cell is passed through Ar and CH simultaneously4Two kinds of gases, the flow-rate ratio for keeping two kinds of gases are 10:1～2:1,
Wherein, the flow of Ar gases is 20～200sccm, CH4The flow of gas is 10～20sccm, controls reative cell air pressure and maintains
0.1～1Torr；
(5b) with the orderly copper nano-wire of high density as growth Graphene catalyst, set reaction chamber temperature as 900～
1100 DEG C, control the heating-up time and the retention time in 20～60min；
(5c) Ar and CH in holding reative cell4The flow of two kinds of gases is constant, and reative cell air pressure maintains 0.1～
1Torr, waits reative cell Temperature fall to less than 100 DEG C, completes the growth of Graphene.
The invention has the advantages that：
1. the present invention is due to removing the anodised aluminium that once oxidation is generated, then carrying out secondary oxidation so that preparation
Anodised aluminium is evenly distributed, and aperture is consistent.
2. the present invention is obtained high density by preparing copper nano-wire using the through-hole anodic aluminum oxide template with copper film
And the copper nano-wire being evenly distributed.
3. the present invention can effectively regulate and control stone due to using highdensity copper nano-wire as the catalyst of growth Graphene
The size and lattice direction of black alkene, finally gives large-area Graphene.
Description of the drawings
Fig. 1 is the flowchart 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.
Specific embodiment
In order that objects and advantages of the present invention become more apparent, below in conjunction with drawings and Examples the present invention is made into
One step is described in detail.It should be appreciated that specific embodiment described herein is only constituted to the present invention to explain the present invention, not
Restriction.
With reference to Fig. 1, the present invention is based on the large-area graphene preparation method of the orderly copper nano-wire catalysis of high density, gives
Go out following three kinds of embodiments.
Embodiment 1：Make based on the Graphene that length is the catalysis of 10um copper nano-wires.
Step 1：Aluminium flake is pre-processed.
(1a) aluminium flake of 99.999% purity is sequentially placed into into acetone, in water and aqueous isopropanol, is removed within each ultrasonic 5 minutes
The grease on surface；
(1b) aluminium flake after will be ultrasound complete is put in mixed acid solution, soaks 30 seconds and remove the miscellaneous of surface at a temperature of 60 DEG C
Matter, the proportioning of the mixed acid solution is：Concentrated hydrochloric acid 20mL, red fuming nitric acid (RFNA) 10mL, hydrofluoric acid 1mL, water 69mL；
(1c) aluminium flake for removing surface impurity is put in polishing fluid, polishes 4 points using constant voltage mode under 20V voltages
Clock, makes aluminium flake become smooth, and the polishing fluid is mixed by the perchloric acid stoste and 75mL absolute ethyl alcohols of 25mL.
Step 2：Pretreated aluminium flake is aoxidized using constant voltage DC pattern.
(2a) aluminium flake after having polished is put in the oxalic acid solution that concentration is 0.3mol/L, is 40V in voltage, temperature is
6 DEG C, process conditions under soak 24 hours, complete once oxidation, as shown in Fig. 2 the B in Fig. 2 is aluminium flake used, A is one
The anodised aluminium that secondary oxidation is generated, because being once oxidation, the anodised aluminium skewness of Surface Creation；
(2b) aluminium flake after once oxidation is put in chromium phosphoric acid solution, is soaked 24 hours at a temperature of 45 DEG C, remove table
The anodised aluminium that face has generated, the proportioning of the chromium phosphoric acid solution is：Chromium oxide 3.6g, SPA 14.2g；
(2c) obtain the anodic oxidation that thickness is 40um secondary oxidation is carried out with once oxidation identical process conditions again
Aluminium, as shown in figure 3, the D in Fig. 3 is aluminium flake used, C is the anodised aluminium that secondary oxidation is generated, because being secondary oxidation,
So the anodised aluminium of Surface Creation is evenly distributed.
Step 3：Remove the aluminium base at the anodised aluminium back side.
Anodised aluminium is put in copper chloride hydrochloric acid solution the aluminium base for removing the aluminium flake back side, copper chloride hydrochloric acid solution its match somebody with somebody
Than for：Copper dichloride dihydrate 6.8g, concentrated hydrochloric acid 200mL, water 200mL.
Step 4：Form through-hole anodic aluminum oxide template.
The anodised aluminium for removing back side aluminium base is swum in into 4wt% phosphoric acid solutions upper 20 minute at a temperature of 35 DEG C, is gone
Except the barrier layer at the anodised aluminium back side, then the reaming of 1 hour in putting it into 0.3mol/L oxalic acid solutions, is carried out, form thickness
For 40um through-hole anodic aluminum oxide templates, as shown in figure 4, the E in Fig. 4 is to remove barrier layer and the through hole anodic oxidation after through hole
Aluminium.
Step 5：Using thermal evaporation mode through-hole anodic aluminum oxide template a face deposit thickness for 40nm copper film,
Sedimentation rate is
Step 6：Plating copper nano-wire.
Through-hole anodic aluminum oxide template with copper film is placed in into the electroplanting device bottom that electric current is 10mA, faces copper film
Under, and the copper film is connected as negative electrode with power cathode, copper chloride boron is gone up in the another side of through-hole anodic aluminum oxide template
Acid solution, and copper chloride BAS is connected with positive source, electroplate 100 minutes, obtaining the high density that length is 10um has
Sequence copper nano-wire, the copper chloride BAS, its proportioning is：Salzburg vitriol 0.25g, boric acid 3.1g, deionized water
100mL。
Step 7：The copper film through-hole anodic aluminum oxide template that length has the orderly copper nano-wire of high density is taken out from electroplanting device,
The copper film in through-hole anodic aluminum oxide template in deposition is removed using 20g/L ammonium persulfate solutions.
Step 8：With the orderly copper nano-wire catalytic growth Graphene of high density in through-hole anodic aluminum oxide template.
(8a) through-hole anodic aluminum oxide template for having been removed copper film is put in chemical vapor deposition reaction chamber, makes to be removed
That of copper film faces up, and in reative cell is passed through Ar and CH simultaneously4Two kinds of gases, the flow-rate ratio for keeping two kinds of gases are 2:1,
Wherein, the flow of Ar gases is 20sccm, CH4The flow of gas is 10sccm, controls reative cell air pressure and maintains 0.1Torr；
(8b) reaction chamber temperature is set as 900 DEG C as the catalyst of growth Graphene with the orderly copper nano-wire of high density,
Control heating-up time and retention time are in 20min；
(8c) Ar and CH in holding reative cell4The flow of two kinds of gases is constant, and reative cell air pressure maintains 0.1Torr,
Reative cell Temperature fall to less than 100 DEG C is waited, the growth of Graphene is completed.
Embodiment 2：Make based on the Graphene that length is the catalysis of 15um copper nano-wires.
The first step：Aluminium flake is pre-processed.
(A1) aluminium flake of 99.999% purity is sequentially placed into into acetone, is removed within each ultrasonic 7 minutes in water and aqueous isopropanol
The grease on surface；
(A2) aluminium flake after will be ultrasound complete is put in mixed acid solution, soaks 32 seconds and remove the miscellaneous of surface at a temperature of 60 DEG C
Matter, the proportioning of the mixed acid solution is：Concentrated hydrochloric acid 20mL, red fuming nitric acid (RFNA) 10mL, hydrofluoric acid 1mL, water 69mL；
(A3) aluminium flake for removing surface impurity is put in polishing fluid, is polished 4 minutes under 20V voltages using constant voltage mode
30 seconds, aluminium flake is made to become smooth, the polishing fluid is mixed by the perchloric acid stoste and 75mL absolute ethyl alcohols of 25mL.
Second step：Pretreated aluminium flake is aoxidized using constant voltage DC pattern.
(B1) once oxidation, the aluminium flake after will having polished are put in the oxalic acid solution that concentration is 0.4mol/L, in voltage
For 40V, temperature is 5 DEG C, process conditions under soak 24 hours, as shown in Fig. 2 the B in Fig. 2 is aluminium flake used, A is for once
The anodised aluminium that oxidation is generated, because being once oxidation, the anodised aluminium skewness of Surface Creation；
(B2) aluminium flake after oxidation is carried out into anodised aluminium removal；
This step is identical with step 2b in embodiment 1.
(B3) secondary oxidation obtains the anodised aluminium of 40um, the process conditions of secondary oxidation and the technique bar of once oxidation
Part is identical, as shown in figure 3, the D in Fig. 3 is aluminium flake used, C is the anodised aluminium that secondary oxidation is generated, because being secondary
Oxidation, so the anodised aluminium of Surface Creation is evenly distributed.
3rd step：Remove the aluminium base at the anodised aluminium back side.
This step is identical with the step 3 in embodiment 1.
4th step：15 on the 5wt% phosphoric acid solutions for swimming at a temperature of 37 DEG C by the anodised aluminium for removing back side aluminium base
Minute, the barrier layer at the anodised aluminium back side is removed, then in putting it into 0.4mol/L oxalic acid solutions, carries out 30 minutes 1 hour
Reaming, it is 40um through-hole anodic aluminum oxide templates to form thickness, as shown in figure 4, after the E in Fig. 4 is for removing barrier layer and through hole
Through hole anodised aluminium.
5th step：Using thermal evaporation mode through-hole anodic aluminum oxide template a face deposit thickness for 45nm copper
Film, sedimentation rate is
6th step：Through-hole anodic aluminum oxide template with copper film is placed in into the electroplanting device bottom that electric current is 15mA, is made
Copper film faces down, and the copper film is connected as negative electrode with power cathode, goes up in the another side of through-hole anodic aluminum oxide template
Copper chloride BAS, and copper chloride BAS is connected with positive source, electroplate 100 minutes, length is obtained for 15um's
The orderly copper nano-wire of high density, the copper chloride BAS, its proportioning is：Salzburg vitriol 0.25g, boric acid 3.1g, go from
Sub- water 100mL.
7th step：Remove the copper film on anodic oxidation aluminium formwork surface.
This step is identical with the step 7 in embodiment 1.
8th step：With the orderly copper nano-wire catalytic growth Graphene of high density in through-hole anodic aluminum oxide template.
(H1) through-hole anodic aluminum oxide template for having been removed copper film is put in chemical vapor deposition reaction chamber, is removed copper
Film faces up, and in reative cell is passed through Ar and CH simultaneously4Two kinds of gases, the flow-rate ratio for keeping two kinds of gases are 5:1, wherein,
The flow of Ar gases is 60sccm, CH4The flow of gas is 12sccm, controls reative cell air pressure and maintains 0.5Torr；
(H2) reaction chamber temperature is set as 1000 as the catalyst of growth Graphene with the orderly copper nano-wire of high density
DEG C, control the heating-up time and the retention time in 40min；
(H3) Ar and CH in holding reative cell4The flow of two kinds of gases is constant, and reative cell air pressure maintains 0.5Torr,
Reative cell Temperature fall to less than 100 DEG C is waited, the growth of Graphene is completed.
Embodiment 3：Make based on the Graphene that length is the catalysis of 20um copper nano-wires.
Step one, pre-processes to aluminium flake.
The aluminium flake of 99.999% purity is sequentially placed into into acetone first, table is removed within each ultrasonic 10 minutes in water and aqueous isopropanol
The grease in face；Aluminium flake after again will be ultrasound complete is put in mixed acid solution, soaks 35 seconds and remove the miscellaneous of surface at a temperature of 60 DEG C
Matter, the proportioning of the mixed acid solution is：Concentrated hydrochloric acid 20mL, red fuming nitric acid (RFNA) 10mL, hydrofluoric acid 1mL, water 69mL；Surface will be removed again miscellaneous
The aluminium flake of matter is put in polishing fluid, is polished 5 minutes under 20V voltages using constant voltage mode, makes aluminium flake become smooth, the polishing fluid
It is to be mixed by the perchloric acid stoste and 75mL absolute ethyl alcohols of 25mL.
Step 2：Pretreated aluminium flake is aoxidized using constant voltage DC pattern.
First the aluminium flake after having polished is put in the oxalic acid solution that concentration is 0.5mol/L, is 40V in voltage, temperature is 3
DEG C, process conditions under soak 24 hours, complete once oxidation, as shown in Fig. 2 the B in Fig. 2 is aluminium flake used, A is for once
The anodised aluminium that oxidation is generated, because being once oxidation, the anodised aluminium skewness of Surface Creation；Again by one
Aluminium flake after secondary oxidation is put in chromium phosphoric acid solution, is soaked 24 hours at a temperature of 45 DEG C, removes the anodic oxygen that surface has generated
Change aluminium, the proportioning of the chromium phosphoric acid solution is：Chromium oxide 3.6g, SPA 14.2g；Secondary oxidation is finally carried out, thickness is obtained
The anodised aluminium for 40um is spent, the process conditions of secondary oxidation are identical with the process conditions of once oxidation, as shown in figure 3, Fig. 3
In D be aluminium flake used, C is the anodised aluminium that secondary oxidation is generated because being secondary oxidation, the sun of Surface Creation
Pole aluminum oxide is evenly distributed.
Step 3：Remove the aluminium base at the anodised aluminium back side.
This step is identical with the step 3 in embodiment 1.
Step 4：Through-hole anodic aluminum oxide template is formed, the anodised aluminium that will remove back side aluminium base swims in 40 DEG C
At a temperature of 6wt% phosphoric acid solutions upper 10 minute, remove the barrier layer at the anodised aluminium back side, then to put it into 0.5mol/L careless
The reaming of 2 hours is carried out in acid solution, it is 40um through-hole anodic aluminum oxide templates to form thickness, as shown in figure 4, the E in Fig. 4 is
Remove barrier layer and the through hole anodised aluminium after through hole.
Step 5：In the one side deposition copper film of anodic oxidation aluminium formwork.
It is the copper film of 50nm in a face deposit thickness of through-hole anodic aluminum oxide template using the mode of magnetron sputtering, deposits
Speed is
Step 6：Plating copper nano-wire.
Through-hole anodic aluminum oxide template with copper film is placed in into the electroplanting device bottom that electric current is 20mA, faces copper film
Under, and the copper film is connected as negative electrode with power cathode, copper chloride boron is gone up in the another side of through-hole anodic aluminum oxide template
Acid solution, and copper chloride BAS is connected with positive source, electroplate 100 minutes, obtaining the high density that length is 20um has
Sequence copper nano-wire, the copper chloride BAS, its proportioning is：Salzburg vitriol 0.25g, boric acid 3.1g, deionized water
100mL。
Step 7：Remove the copper film on anodic oxidation aluminium formwork surface.
This step is identical with the step 7 in embodiment 1.
Step 8：With the orderly copper nano-wire catalytic growth Graphene of high density in through-hole anodic aluminum oxide template.
The through-hole anodic aluminum oxide template for having been removed copper film is put in chemical vapor deposition reaction chamber, makes to be removed copper film
That face up, be simultaneously passed through Ar and CH in reative cell4Two kinds of gases, the flow-rate ratio for keeping two kinds of gases are 10:1, its
In, the flow of Ar gases is 200sccm, CH4The flow of gas is 20sccm, controls reative cell air pressure and maintains 1Torr；
Reaction chamber temperature is set as 1100 DEG C as the catalyst of growth Graphene with the orderly copper nano-wire of high density again,
Control heating-up time and retention time are in 60min, and keep the Ar and CH in reative cell4The flow of two kinds of gases is constant, instead
Answer room air pressure to maintain 1Torr, wait reative cell Temperature fall to less than 100 DEG C, complete the growth of Graphene.
Foregoing description is several preferred embodiments of the present invention, is not construed as limiting the invention, for this area
For professional, after present invention and principle is understood, can in the case of without departing substantially from the principle and scope of the present invention,
The method according to the invention carries out various amendments and change in form and details, but these are based on amendment of the invention and change
Change is still within the claims of the present invention.
Claims (8)
1. the large-area graphene preparation method based on the orderly copper nano-wire catalysis of high density, comprises the steps：
(1) prepare through-hole anodic aluminum oxide template：
(1a) smooth process is carried out to high-purity aluminium flake；
(1b) once oxidation, the process conditions of oxidation are carried out to the aluminium flake after smooth using constant voltage DC pattern：Voltage is 40V,
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 in chromium phosphoric acid solution, is soaked 24 hours at a temperature of 45 DEG C, removed surface
The anodised aluminium of generation, then to carry out secondary oxidation with once oxidation identical process conditions；
(1d) aluminium base at the aluminium flake back side after secondary oxidation is removed with copper chloride hydrochloric acid solution, the anodic oxidation on barrier layer is formed with
Aluminium, then swum in 10～20 minutes on the 4～6wt% phosphoric acid solutions at a temperature of 35～40 DEG C, remove the anodised aluminium back of the body
The barrier layer in face, then the reaming of 1～2 hour in putting it into 0.3～0.5mol/L oxalic acid solutions, is carried out, thickness is obtained for 40 μm
Through-hole anodic aluminum oxide template；
(2) the face deposit thickness in through-hole anodic aluminum oxide template is the copper film of 40～50nm, and sedimentation rate is
(3) through-hole anodic aluminum oxide template with copper film is placed in into the electroplanting device bottom that electric current is 10～20mA, makes copper film
Face down, and the copper film is connected as negative electrode with power cathode, chlorination is gone up in the another side of through-hole anodic aluminum oxide template
Copper BAS, and copper chloride BAS is connected with positive source, electroplate 100 minutes, it is 10～20 μm to obtain length
The orderly copper nano-wire of high density；
(4) the copper film through-hole anodic aluminum oxide template that length is had the orderly copper nano-wire of high density is taken out from electroplanting device, is used
20g/L ammonium persulfate solutions remove the copper film in through-hole anodic aluminum oxide template in deposition；
(5) with the orderly copper nano-wire catalytic growth Graphene of high density in through-hole anodic aluminum oxide template：
(5a) through-hole anodic aluminum oxide template for having been removed copper film is put in chemical vapor deposition reaction chamber, be removed copper film that
Face up, Ar and CH is passed through simultaneously in reative cell4Two kinds of gases, the flow-rate ratio for keeping two kinds of gases are 10:1～2:1, its
In, the flow of Ar gases is 20～200sccm, CH4The flow of gas is 10～20sccm, controls reative cell air pressure and maintains
0.1～1Torr；
(5b) reaction chamber temperature is set as 900～1100 as the catalyst of growth Graphene with the orderly copper nano-wire of high density
DEG C, control the heating-up time and the retention time in 20～60min；
(5c) Ar and CH in holding reative cell4The flow of two kinds of gases is constant, and reative cell air pressure maintains 0.1～1Torr, etc.
Question response room Temperature fall to less than 100 DEG C, completes the growth of Graphene.
2. the large-area graphene preparation method based on the catalysis of high density orderly copper nano-wire according to claim 1, its
It is characterised by：Smooth process is carried out to high-purity aluminium flake in step (1a), is carried out as follows：
(1a1) high-purity aluminium flake is sequentially placed into into acetone, ultrasound removes the grease on surface for 5～10 minutes in water and aqueous isopropanol；
(1a2) aluminium flake after will be ultrasound complete is put in mixed acid solution, soaks 30～35 seconds and remove surface at a temperature of 60 DEG C
Impurity；
(1a3) aluminium flake for removing surface impurity is put in polishing fluid, polishes 4～5 points using constant voltage mode under 20V voltages
Clock, makes aluminium flake become smooth.
3. the large-area graphene preparation method based on the catalysis of high density orderly copper nano-wire according to claim 1, its
It is characterised by：Chromium phosphoric acid solution in step (1c), its proportioning is：Chromium oxide 3.6g, SPA 14.2g.
4. the large-area graphene preparation method based on the catalysis of high density orderly copper nano-wire according to claim 1, its
It is characterised by：Copper chloride hydrochloric acid solution 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 catalysis of high density orderly copper nano-wire according to claim 1, its
It is characterised by：One side in the step (2) in through-hole anodic aluminum oxide template deposits copper film, using thermal evaporation methods or magnetic control
The mode of sputtering is deposited.
6. the large-area graphene preparation method based on the catalysis of high density orderly copper nano-wire according to claim 1, its
It is characterised by：Copper chloride BAS in step (3), its proportioning is：Salzburg vitriol 0.25g, boric acid 3.1g, deionization
Water 100mL.
7. the large-area graphene preparation method based on the catalysis of high density orderly copper nano-wire according to claim 2, its
It is characterised by：Mixed acid solution in step (1a2), its proportioning is：Concentrated hydrochloric acid 20mL, red fuming nitric acid (RFNA) 10mL, hydrofluoric acid 1mL, water
69mL。
8. the large-area graphene preparation method based on the catalysis of high density orderly copper nano-wire according to claim 2, its
It is characterised by：Polishing fluid in step (1a3), is mixed by the perchloric acid stoste and 75mL absolute ethyl alcohols of 25mL.
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| 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 |
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