CN104681801B - A kind of Graphene/Cu/Ni combination electrodes and preparation method thereof - Google Patents
A kind of Graphene/Cu/Ni combination electrodes and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of Graphene/Cu/Ni combination electrodes and preparation method thereof.Combination electrode includes Cu/Ni alloy-layers and the graphene film being covered on Cu/Ni alloy-layers；Wherein, Cu/Ni alloy-layers are by Ni films and be covered in Cu films on Ni films mutually diffuseing to form for Ni atoms and Cu atoms occurs, and Ni films are 1 with the thickness ratio of Cu films:(3~10).Destruction present invention, avoiding Graphene transfer process and patterning process to Graphene quality; reduce the number of Graphene defect; by the thickness for adjusting Ni films and Cu films; using the CVD techniques of temperature-gradient method; obtain high-quality Graphene; protective capability of the Graphene to Cu/Ni alloys is enhanced, the combination electrode for obtaining has excellent corrosion resistance.
Description
Technical field
The invention belongs to metal electrode protection technique field, more particularly, to a kind of Graphene/Cu/Ni combination electrodes
And preparation method thereof.
Background technology
Cu/Ni composition metals are easy to plastotype, processing and weld, in devices such as metal interconnection, aircraft component, implanted devices
It is middle to be widely used as electrode.Graphene is a kind of two-dimentional monoatomic layer material, because of its outstanding machinery, optics, electricity, change
Learn stability etc. and be widely used, especially its good chemical stability, can serve as anticorrosive to protect Cu/Ni to answer
Close metal electrode.
However, research shows that the fault location in Graphene can occur the phenomenon of serious corrosion lower metal, high-quality, nothing
The single-layer graphene of defect can efficiently reduce the generation of corrosion phenomenon.At present, through prepared frequently with CVD technology large area,
High-quality Graphene.With single transition metal (Cu, Ni etc.) as catalyst, with hydrocarbon compound as carbon source, deposit growth stone
Black alkene；Then the graphene film of growth is transferred in target substrate, by steps such as graphical treatments, carries out answering for device
With.But complicated, destructive Graphene transfer and patterning process can seriously damage the quality of Graphene, cause unnecessary lacking
Fall into, application of the influence Graphene in terms of metal electrode anti-corrosion.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, the invention provides a kind of Graphene/Cu/Ni combination electrodes
And preparation method thereof, it is to avoid the destruction of Graphene transfer process and patterning process to Graphene quality, reduce Graphene
The number of defect, by adjusting the thickness of Ni films and Cu films, using the CVD techniques of temperature-gradient method, obtains high-quality Graphene,
Protective capability of the Graphene to Cu/Ni alloys is enhanced, the combination electrode for obtaining has excellent corrosion resistance.
To achieve the above object, according to one aspect of the present invention, there is provided a kind of Graphene/Cu/Ni combination electrodes, its
It is characterised by, including Cu/Ni alloy-layers and the graphene film being covered on the Cu/Ni alloy-layers；Wherein, the Cu/Ni
Alloy-layer is by Ni films and be covered in Cu films on the Ni films mutually diffuseing to form for Ni atoms and Cu atoms occur, the Ni films and
The thickness ratio of the Cu films is 1:(3~10).
Preferably, the Cu/Ni alloy-layers and the graphene film are patterned structures.
It is another aspect of this invention to provide that providing a kind of preparation method of Graphene/Cu/Ni combination electrodes, its feature
It is to comprise the following steps：
(1) layer of Ni film is deposited in substrate, then one layer of Cu film is deposited on Ni films, obtain Cu/Ni composition metal substrates；
Wherein, Ni films and the thickness ratio of Cu films are 1:(3~10)；
(2) CVD method is utilized, graphene film is grown in Cu/Ni composition metal substrates；
The step (2) further includes following steps：
(A1) in Ar and H2Mixed atmosphere in, be warming up to 400 DEG C~800 DEG C, and be incubated 3h~5h；
(A2) 1000 DEG C~1050 DEG C are continuously heating to；
(A3) hydrocarbon is passed through as carbon source, is incubated 15min~30min；
(A4) in Ar and H2Mixed atmosphere in, be cooled to room temperature.
According to another aspect of the present invention, there is provided a kind of preparation method of Graphene/Cu/Ni combination electrodes, its feature
It is to comprise the following steps：
(1) patterned photoresist is prepared in substrate；
(2) layer of Ni film is deposited, then one layer of Cu film is deposited on Ni films；Wherein, Ni films and the thickness ratio of Cu films are 1:(3
~10)；
(3) photoresist is removed, patterned Cu films and Ni films is obtained；
(4) CVD method is utilized, graphene film is grown on patterned Cu films；
The step (4) further includes following steps：
(A1) in Ar and H2Mixed atmosphere in, be warming up to 400 DEG C~800 DEG C, and be incubated 3h~5h；
(A2) 1000 DEG C~1050 DEG C are continuously heating to；
(A3) hydrocarbon is passed through as carbon source, is incubated 15min~30min；
(A4) in Ar and H2Mixed atmosphere in, be cooled to room temperature.
In general, by the contemplated above technical scheme of the present invention compared with prior art, with following beneficial effect
Really：
1st, Graphene is directly grown on metal, realizes growth in situ and the application of single-layer graphene, it is to avoid graphite
Destruction of the alkene transfer process to Graphene quality, reduces the number of Graphene defect, enhances the protection energy to Cu/Ni alloys
Power.
2nd, the Ni atoms in composition metal at high temperature with Cu atom phase counterdiffusion, serve smooth metallic substrate surface,
Increase the effect of crystallite dimension, be conducive to individual layer, the growth of zero defect Graphene, by adjusting the thickness of Ni films and Cu films, energy
High-quality Graphene is obtained, there is more preferable protecting effect to lower metal.
3rd, growing patterned single-layer graphene, it is to avoid the Graphene patterning process in device application is to Graphene matter
The destruction of amount, reduces the number of Graphene defect, enhances the protective capability to Cu/Ni alloys.
4th, Graphene is grown using the CVD techniques of temperature-gradient method, reduces destruction of the high temperature to Cu/Ni alloys, go forward side by side one
Step improves the growth quality of Graphene.
Brief description of the drawings
Fig. 1 is the preparation technology schematic flow sheet of the Graphene/Cu/Ni combination electrodes of one embodiment of the invention；
Fig. 2 is the preparation technology schematic flow sheet of the Graphene/Cu/Ni combination electrodes of another embodiment of the present invention；
Fig. 3 is the Raman spectrograms of the Graphene of the growth of embodiment 6；
Fig. 4 is the SEM figures of the Graphene of the growth of embodiment 6.
In all of the figs, identical reference be used for represent identical element or structure, wherein：1- substrates, 2- light
Photoresist, 3-Ni films, 4-Cu films, 5- graphene films.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as additionally, technical characteristic involved in invention described below each implementation method
Not constituting conflict each other can just be mutually combined.
The Graphene of the embodiment of the present invention/Cu/Ni combination electrodes include Cu/Ni alloy-layers and are covered in Cu/Ni alloy-layers
On graphene film；Wherein, Cu/Ni alloy-layers are by Ni films and are covered in the phase that Cu films on Ni films occur Ni atoms and Cu atoms
Counterdiffusion is formed, and Ni films are 1 with the thickness ratio of Cu films:(3~10).Preferably, Cu/Ni alloy-layers and graphene film are figure
Shape structure.
As shown in figure 1, the preparation method of the Graphene of one embodiment of the invention/Cu/Ni combination electrodes includes following step
Suddenly：
(1) layer of Ni film 3 is deposited on the base 1, then one layer of Cu film 4 is deposited on Ni films 3, obtain Cu/Ni composition metals
Substrate.
Wherein, substrate typically Si, glass etc..
Preferably, Ni films and the thickness ratio of Cu films are 1:(3~10).
(2) CVD method is utilized, graphene film 5 is grown in Cu/Ni composition metal substrates.
Step (2) further includes following steps：
(A1) in Ar and H2Mixed atmosphere in, be warming up to 400 DEG C~800 DEG C, and be incubated 3h~5h.
(A2) 1000 DEG C~1050 DEG C are continuously heating to.
(A3) hydrocarbon is passed through as carbon source, is incubated 15min~30min.
Wherein, hydrocarbon typically CH4、C2H4Deng.
(A4) in Ar and H2Mixed atmosphere in, be cooled to room temperature.
As shown in Fig. 2 the preparation method of the Graphene of another embodiment of the present invention/Cu/Ni combination electrodes is including as follows
Step：
(1) patterned photoresist 2 is prepared on the base 1.
(2) deposit layer of Ni film 3, then one layer of Cu film 4 is deposited on Ni films 3.
Wherein, substrate typically Si, glass etc..
Preferably, Ni films and the thickness ratio of Cu films are 1:(3~10).
(3) photoresist is removed, patterned Cu films and Ni films is obtained.
(4) CVD method is utilized, graphene film 5 is grown on patterned Cu films.
Step (4) further includes following steps：
(A1) in Ar and H2Mixed atmosphere in, be warming up to 400 DEG C~800 DEG C, and be incubated 3h~5h.
(A2) 1000 DEG C~1050 DEG C are continuously heating to.
(A3) hydrocarbon is passed through as carbon source, is incubated 15min~30min.
Wherein, hydrocarbon typically CH4、C2H4Deng.
(A4) in Ar and H2Mixed atmosphere in, be cooled to room temperature.
To make those skilled in the art more fully understand the present invention, with reference to specific embodiment, to graphite of the invention
The preparation method of alkene/Cu/Ni combination electrodes is described in detail.
Embodiment 1
One layer of 300nm of the sputtering deposit thick Ni films in Si substrates, then the thick Cu films of one layer of 900nm are sputtered on Ni films
(Ni films are 1 with the thickness ratio of Cu films:3) Cu/Ni composition metal substrates, are obtained；By Cu/Ni composition metals substrate in Ar and H2's
In mixed atmosphere, it is warming up to 400 DEG C and is incubated 5h, be continuously heating to 1000 DEG C, is passed through CH4As carbon source, 30min is incubated, most
Afterwards in Ar and H2Mixed atmosphere in, room temperature is cooled to, so as to growing graphene film in Cu/Ni composition metal substrates.
Embodiment 2
One layer of 100nm of the sputtering deposit thick Ni films in Si substrates, then one layer of 1 Cu films (Ni of μ m-thick is sputtered on Ni films
Film is 1 with the thickness ratio of Cu films:10) Cu/Ni composition metal substrates, are obtained；By Cu/Ni composition metals substrate in Ar and H2It is mixed
Close in atmosphere, be warming up to 800 DEG C and be incubated 3h, be continuously heating to 1050 DEG C, be passed through CH4As carbon source, 15min is incubated, finally
In Ar and H2Mixed atmosphere in, room temperature is cooled to, so as to growing graphene film in Cu/Ni composition metal substrates.
Embodiment 3
One layer of 200nm of the sputtering deposit thick Ni films in Si substrates, then the thick Cu films of one layer of 900nm are sputtered on Ni films
(Ni films are 1 with the thickness ratio of Cu films:4.5) Cu/Ni composition metal substrates, are obtained；By Cu/Ni composition metals substrate in Ar and H2
Mixed atmosphere in, be warming up to 600 DEG C and be incubated 4h, be continuously heating to 1020 DEG C, be passed through CH4As carbon source, 25min is incubated,
Finally in Ar and H2Mixed atmosphere in, room temperature is cooled to, so as to growing graphene film in Cu/Ni composition metal substrates.
Embodiment 4
Patterned photoresist is prepared in Si substrates, the thick Ni films of one layer of 300nm is then sputtered, then sputtered on Ni films
(Ni films are 1 with the thickness ratio of Cu films to one layer of Cu film of 900nm thickness:3)；Removal photoresist, obtains patterned Cu films and Ni films；
By substrate in Ar and H2Mixed atmosphere in, be warming up to 400 DEG C and be incubated 5h, be continuously heating to 1000 DEG C, be passed through CH4As carbon
Source, is incubated 30min, finally in Ar and H2Mixed atmosphere in, room temperature is cooled to, so as to growing graphite on patterned Cu films
Alkene film.
Embodiment 5
Patterned photoresist is prepared in Si substrates, the thick Ni films of one layer of 100nm is then sputtered, then sputtered on Ni films
(Ni films are 1 with the thickness ratio of Cu films to one layer of 1 Cu film of μ m-thick:10)；Removal photoresist, obtains patterned Cu films and Ni films；
By substrate in Ar and H2Mixed atmosphere in, be warming up to 800 DEG C and be incubated 3h, be continuously heating to 1050 DEG C, be passed through CH4As carbon
Source, is incubated 15min, finally in Ar and H2Mixed atmosphere in, room temperature is cooled to, so as to growing graphite on patterned Cu films
Alkene film.
Embodiment 6
Patterned photoresist is prepared in Si substrates, the thick Ni films of one layer of 200nm is then sputtered, then sputtered on Ni films
(Ni films are 1 with the thickness ratio of Cu films to one layer of Cu film of 900nm thickness:4.5)；Removal photoresist, obtains patterned Cu films and Ni
Film；By substrate in Ar and H2Mixed atmosphere in, be warming up to 600 DEG C and be incubated 4h, be continuously heating to 1020 DEG C, be passed through CH4As
Carbon source, is incubated 25min, finally in Ar and H2Mixed atmosphere in, room temperature is cooled to, so as to growing stone on patterned Cu films
Black alkene film.
The Raman spectrograms of the Graphene of test above-described embodiment growth and SEM figures, as a result show respectively, of the invention
Method can grow individual layer, flawless graphene film, thus Cu/Ni alloy-layers to lower floor have preferably protection effect
Really, the Graphene for obtaining/Cu/Ni combination electrodes have excellent corrosion resistance.By taking embodiment 6 as an example, Fig. 3 is embodiment 6
The Raman spectrograms of the Graphene of growth, wherein, the ratio I of the intensity at 2D peaks and G peaks2D/IG>1, illustrate that Graphene is individual layer；
And the intensity at the D peaks of expression Graphene defect counts is zero, illustrates that the defect of Graphene is few.Fig. 4 is the stone of the growth of embodiment 6
The SEM figures of black alkene, it can be seen that the continuous Graphene of individual layer grows on Cu films.
As it will be easily appreciated by one skilled in the art that the foregoing is only presently preferred embodiments of the present invention, it is not used to
The limitation present invention, all any modification, equivalent and improvement made within the spirit and principles in the present invention etc., all should include
Within protection scope of the present invention.
Claims (2)
1. the preparation method of a kind of Graphene/Cu/Ni combination electrodes, it is characterised in that comprise the following steps：
(1) layer of Ni film is deposited in substrate, then one layer of Cu film is deposited on Ni films, obtain Cu/Ni composition metal substrates；Its
In, Ni films are 1 with the thickness ratio of Cu films:(3~10)；
(2) CVD method is utilized, graphene film is grown in Cu/Ni composition metal substrates；
The step (2) further includes following steps：
(A1) in Ar and H2Mixed atmosphere in, be warming up to 400 DEG C~800 DEG C, and be incubated 3h~5h；
(A2) 1000 DEG C~1050 DEG C are continuously heating to；
(A3) to Ar and H2Mixed atmosphere in be passed through hydrocarbon as carbon source, be incubated 15min~30min；
(A4) in Ar and H2Mixed atmosphere in, be cooled to room temperature.
2. the preparation method of a kind of Graphene/Cu/Ni combination electrodes, it is characterised in that comprise the following steps：
(1) patterned photoresist is prepared in substrate；
(2) layer of Ni film is deposited, then one layer of Cu film is deposited on Ni films；Wherein, Ni films and the thickness ratio of Cu films are 1:(3~
10)；
(3) photoresist is removed, patterned Cu films and Ni films is obtained；
(4) CVD method is utilized, graphene film is grown on patterned Cu films；
The step (4) further includes following steps：
(A1) in Ar and H2Mixed atmosphere in, be warming up to 400 DEG C~800 DEG C, and be incubated 3h~5h；
(A2) 1000 DEG C~1050 DEG C are continuously heating to；
(A3) to Ar and H2Mixed atmosphere in be passed through hydrocarbon as carbon source, be incubated 15min~30min；
(A4) in Ar and H2Mixed atmosphere in, be cooled to room temperature.
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| KR101999564B1 (en) * | 2017-06-02 | 2019-07-12 | 재단법인 나노기반소프트일렉트로닉스연구단 | METHOD FOR PREPARING THICKNESS-CONTROLLED GRAPHENE USING CHEMICAL VAPOR DEPOSITION AND Cu-Ni THIN FILM LAMINATE CATALYST |
| CN108658037B (en) * | 2018-04-27 | 2019-11-22 | 国家纳米科学中心 | A kind of graphene functionalized nanometer pinpoint and preparation method thereof |
| CN109742379A (en) * | 2019-01-28 | 2019-05-10 | 哈工大机器人（岳阳）军民融合研究院 | It is a kind of on Si/C composite material grow graphene method, utilize material made from this method and its application |
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