CN106882792B - A kind of method that dry method shifts graphene in metal substrate - Google Patents
A kind of method that dry method shifts graphene in metal substrate Download PDFInfo
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- CN106882792B CN106882792B CN201510933644.0A CN201510933644A CN106882792B CN 106882792 B CN106882792 B CN 106882792B CN 201510933644 A CN201510933644 A CN 201510933644A CN 106882792 B CN106882792 B CN 106882792B
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Abstract
The present invention provides the method for graphene in a kind of dry method transfer metal substrate, comprising: 1) metal substrate with graphene is placed in target substrate, and by the graphene face towards target substrate；2) metal substrate with graphene will be placed and target substrate is put into reactor; under protective atmosphere; it is warming up to metal substrate fusion temperature or more; the metal substrate fusing is set to be shrunk to prill; the graphene is attached in target substrate; room temperature is dropped in protective atmosphere after heat preservation preset time, the graphene is transferred in target substrate.Method repeatability of the invention is high, simple and easy, shifts for the scale of microelectronics and optoelectronic areas high-quality graphene batch；Transfer process of the present invention belongs to physical process and assists without other liquid or solid state reagents, and transfer process will not introduce other impurities, can effectively avoid unintentional doping, reduce influence of the transfer process to graphene electric property.
Description
Technical field
The invention belongs to graphene film preparation technical fields, more particularly to graphite in a kind of dry method transfer metal substrate
The method of alkene.
Background technique
It is delivered from two scientist Andre Geim and the Konstantin Novoselov in Russia's birth in 2004
After first paper in relation to graphene, graphene has evoked huge great waves in scientific circles, its appearance is expected in modern electricity
Sub- sciemtifec and technical sphere causes new round revolution.Graphene has many superior performances, for example, high transparency, high electron mobility,
High current density, high mechanical strength, be easy to modify etc..Just because of these characteristics, it be acknowledged as manufacture transparent conductive film,
The ideal material of high frequency transistor, hydrogen storage battery or even integrated circuit, has a vast market application prospect.
So far, in the preparation method of many graphenes, CVD method can get high quality, big face on the metallic substrate
The graphene of long-pending graphene, this method preparation is most suitable for the application of microelectronics and optoelectronic areas.Due to metal substrate
Electric conductivity, the graphene in metal substrate are generally required to be transferred in other target substrates and could be used.Currently, by metal substrate
The wet process transfer eroded is the most common transfer method of CVD graphene in metal substrate, and recently, researcher has developed again
Bubbling method shifts graphene, and this method does not have to corrosion metal substrate, can effectively reduce graphene cost.However, either passing
The wet process transfer of system or Bubbling method transfer, graphene can be all immersed in solution, cause the unintentional doping of graphene.
The dry method transfer that the present invention refers to, whole process can avoid graphene and contact with other solution or solid matter,
Avoid unintentional doping.Moreover, this method is easy to operate, reproducible, high quality needed for being suitable for microelectronics and optoelectronic applications
The preparation of graphene.
Summary of the invention
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide in a kind of dry method transfer metal substrate
The method of graphene, for solving the problems, such as that graphene transfer be easy to cause unintentional doping in the prior art.
In order to achieve the above objects and other related objects, the present invention provides graphene in a kind of dry method transfer metal substrate
Method, comprising steps of step 1), the metal substrate with graphene is placed in target substrate, and by the graphene face court
Target substrate, wherein do not infiltrated after the metal substrate fusing with graphene；Step 2), by what is placed with graphene
Metal substrate and target substrate are put into reactor, under protective atmosphere, are warming up to metal substrate fusion temperature or more, are made institute
It states metal substrate fusing and is shrunk to prill, the graphene is attached in target substrate, is being protected after keeping the temperature preset time
Atmosphere drops to room temperature, and the graphene is transferred in target substrate.
As a kind of preferred embodiment of the method for graphene in dry method transfer metal substrate of the invention, the graphene
One or two kinds of combinations of domain and graphene continuous film are separated including graphene.
As a kind of preferred embodiment of the method for graphene in dry method transfer metal substrate of the invention, the metal substrate
Material include copper, nickel, cobalt and ruthenium one or more kinds of alloys.
As a kind of preferred embodiment of the method for graphene in dry method transfer metal substrate of the invention, the target substrate
Fusing point be higher than the fusing point of corresponding metal substrate, there is the silicon substrate of silica, silicon substrate and sapphire lining including surface
One of bottom.
As a kind of preferred embodiment of the method for graphene in dry method transfer metal substrate of the invention, in step 1), if
The metal substrate back side also has graphene, then is first removed the graphene at the back side with oxygen plasma lithographic method.
As a kind of preferred embodiment of the method for graphene in dry method transfer metal substrate of the invention, the target substrate
Placement direction can be it is horizontal to vertical any angle.
As a kind of preferred embodiment of the method for graphene in dry method transfer metal substrate of the invention, the protective atmosphere
A kind of mixing for the gas or two or more gases that avoid graphene from etching in the high temperature environment.
A kind of preferred embodiment of the method for graphene in metal substrate, the liter in step 2) are shifted as dry method of the invention
Mild cooling rate is 0.01~1000 degrees celsius/minute.
It, will in step 2) as a kind of preferred embodiment of the method for graphene in dry method transfer metal substrate of the invention
Target substrate is tilted a certain angle placement, so that the prill after fusing is rolled into other than graphene under the effect of gravity
Region.
As a kind of preferred embodiment of the method for graphene in dry method transfer metal substrate of the invention, in step 2), lead to
It crosses and removes the prill with mechanical external force or the method for chemical attack.
As described above, the method that dry method of the invention shifts graphene in metal substrate, has the advantages that
1) method of the invention repeatability is high, simple and easy, for microelectronics and optoelectronic areas high-quality graphene
Scale batch shift；
2) transfer process of the present invention belongs to physical process and assists without other liquid or solid state reagents, and transfer process is not
Other impurities can be introduced, can effectively avoid unintentional doping, reduce influence of the transfer process to graphene electric property.
Detailed description of the invention
Fig. 1 is shown as the step flow diagram that dry method of the invention shifts the method for graphene in metal substrate.
What each step that Fig. 2~Fig. 6 is shown as the method for graphene in dry method transfer metal substrate of the invention was presented
Structural schematic diagram.
Fig. 7 is shown with conventional wet transfer and graphene in copper substrate is transferred to SiO2Graphene on/Si substrate
Light microscopic picture.
Fig. 8 is shown with dry method transfer of the present invention and graphene in copper substrate is transferred to SiO2Graphene on/Si substrate
Light microscopic picture.
Fig. 9 is shown with dry method transfer of the present invention and graphene in copper substrate is transferred to graphene in Sapphire Substrate
Light microscopic picture.
Component label instructions
101 metal substrates
102 graphenes
103 target substrates
104 prills
S11~S12 step 1)~step 2)
Specific embodiment
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing from
Various modifications or alterations are carried out under spirit of the invention.
Please refer to FIG. 1 to FIG. 9.It should be noted that diagram provided in the present embodiment only illustrates this in a schematic way
The basic conception of invention, only shown in diagram then with related component in the present invention rather than package count when according to actual implementation
Mesh, shape and size are drawn, when actual implementation kenel, quantity and the ratio of each component can arbitrarily change for one kind, and its
Assembly layout kenel may also be increasingly complex.
Embodiment 1
As shown in FIG. 1 to FIG. 8, the present embodiment provides the methods of graphene in a kind of dry method transfer metal substrate, including step
It is rapid:
As shown in Figure 1 to 4, step 1) S11 is carried out first, and the metal substrate 101 with graphene 102 is placed in target
On substrate 103, and the graphene 102 is faced into target substrate 103, wherein the metal substrate 101 melt after with graphene
102 do not infiltrate.
As an example, the graphene 102 includes the one or two of graphene separation domain and graphene continuous film
Combination.In the present embodiment, the graphene 102 is graphene continuous film.
As an example, the material of the metal substrate 101 includes one or more kinds of alloys of copper, nickel, cobalt and ruthenium.
In the present embodiment, the material of the metal substrate 101 is copper.
As an example, the fusing point of the target substrate 103 is higher than the fusing point of corresponding metal substrate 101, including surface tool
There are one of the silicon substrate, silicon substrate and Sapphire Substrate of silica.In the present embodiment, the target substrate 103 is
Surface has the silicon substrate of silica.
As an example, first the graphene 102 at the back side is used if 101 back side of the metal substrate also has graphene 102
Oxygen plasma lithographic method is removed.
As shown in Fig. 1 and Fig. 5~Fig. 6, step 2) S12, the metal liner with graphene 102 that will be placed then are carried out
Bottom 101 and target substrate 103 are put into reactor, under protective atmosphere, are warming up to 101 melt temperature of metal substrate or more,
The fusing of metal substrate 101 is set to be shrunk to prill 104, the graphene 102 is attached in target substrate 103, heat preservation
Room temperature is dropped in protective atmosphere after preset time, the graphene 102 is transferred in target substrate 103.
As an example, the placement direction of the target substrate 103 can be level to vertical any angle.
As an example, the protective atmosphere be a kind of gas for avoiding graphene 102 from etching in the high temperature environment or
The mixing of the two or more gases of person.
As an example, the heating and cooling rate in step 2) are 0.01~1000 degrees celsius/minute.
As an example, by removing the prill 104 with the method for mechanical external force or chemical attack.
Certainly, in other implementation processes, target substrate 103 can also be tilted a certain angle placement, so that fusing
Prill 104 afterwards is rolled into the region other than graphene 102 under the effect of gravity.It can save in this way
Except the additional technique of prill 104, cost is substantially reduced.
Below with graphene on dry method transfer copper to SiO2/ Si substrate (i.e. surface have silicon dioxide layer silicon substrate) be
Example further illustrates specific implementation process of the invention:
Copper substrate with graphene is placed on SiO by step 1)2/ Si substrate (SiO2With a thickness of 300 nanometers) on, with stone
The one side of black alkene closely target substrate.
The metal substrate put well and target substrate are put into togerther in common CVD growth system, are evacuated down to by step 2)
1Pa then passes to argon gas to normal pressure.
Step 3) is warming up to 1200 under 1000sccm argon gas, 20sccm hydrogen, the protection of 0.1sccm methane mixed gas
Degree Celsius, and maintain 30 minutes at this temperature, heating rate is selected as 5 degrees celsius/minutes.
Step 4), 1000sccm argon gas, 20sccm hydrogen, 0.1sccm methane mixed gas protection under fast cooling extremely
Room temperature, the speed of cooling are selected as 10 degrees celsius/minutes.
Step 5) obtains being transferred to SiO2Graphene on/Si substrate.The SiO that the present embodiment obtains2Stone on/Si substrate
The light microscopic figure of black alkene is as shown in Figure 8, it can be seen that.Compared to the transfer of Fig. 7 conventional wet as a result, result of the invention does not have glue residual
It stays, surface is cleaner.
Embodiment 2
As shown in FIG. 1 to FIG. 6 and Fig. 9, the present embodiment provides a kind of dry method transfer metal substrate on graphene method,
Its basic step such as embodiment 1, wherein in the present embodiment, by dry method transfer copper for graphene to Sapphire Substrate into
One step is illustrated.Specifically, comprising the following steps:
Step 1) puts the copper substrate with graphene on a sapphire substrate, the closely target of the one side with graphene
Substrate.
The metal substrate put well and target substrate are put into togerther in common CVD growth system, are evacuated down to by step 2)
1Pa then passes to argon gas to normal pressure.
Step 3) is warming up to 1200 under 1000sccm argon gas, 20sccm hydrogen, the protection of 0.1sccm methane mixed gas
Degree Celsius, it maintains 30 minutes, heating rate is selected as 5 degrees celsius/minutes.
Step 4), 1000sccm argon gas, 20sccm hydrogen, 0.1sccm methane mixed gas protection under fast cooling extremely
Room temperature, the speed of cooling are selected as 10 degrees celsius/minutes.
Step 5) obtains being transferred to the graphene in Sapphire Substrate.The stone in Sapphire Substrate that the present embodiment obtains
The light microscopic figure of black alkene is as shown in figure 9, lower left is graphene, and upper right side is sapphire substrate surface, and arrow meaning is graphene
With the boundary of substrate, it can be seen that result of the invention does not have glue residua, and surface is cleaner.
As described above, the method that dry method of the invention shifts graphene in metal substrate, has the advantages that
1) method of the invention repeatability is high, simple and easy, for microelectronics and optoelectronic areas high-quality graphene
Scale batch shift；
2) transfer process of the present invention belongs to physical process and assists without other liquid or solid state reagents, and transfer process is not
Other impurities can be introduced, can effectively avoid unintentional doping, reduce influence of the transfer process to graphene electric property.
So the present invention effectively overcomes various shortcoming in the prior art and has high industrial utilization value.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (7)
1. a kind of method of graphene in dry method transfer metal substrate, which is characterized in that comprising steps of
Metal substrate with graphene is placed in target substrate by step 1), and by the graphene face towards target substrate,
In, it is not infiltrated after the metal substrate fusing with graphene, the material of the metal substrate includes one kind of copper, nickel, cobalt and ruthenium
Or two or more alloy；
Step 2), will place metal substrate with graphene and target substrate is put into reactor, under the protective atmosphere,
It is warming up to metal substrate fusion temperature or more, the metal substrate fusing is made to be shrunk to prill, the graphene attachment
Room temperature is dropped in protective atmosphere after in target substrate, keeping the temperature preset time, the graphene is transferred to target substrate
On, target substrate is tilted a certain angle placement, so that the prill after fusing is rolled into graphite under the effect of gravity
Region other than alkene, either by removing the prill with the method for mechanical external force or chemical attack.
2. the method for graphene in dry method transfer metal substrate according to claim 1, it is characterised in that: the graphite
Alkene includes one or two kinds of combinations of graphene separation domain and graphene continuous film.
3. the method for graphene in dry method transfer metal substrate according to claim 1, it is characterised in that: the target lining
The fusing point at bottom is higher than the fusing point of corresponding metal substrate, has silicon substrate, silicon substrate and the sapphire of silica including surface
One of substrate.
4. the method for graphene in dry method transfer metal substrate according to claim 1, it is characterised in that: in step 1),
If the metal substrate back side also has graphene, first the graphene at the back side is removed with oxygen plasma lithographic method.
5. the method for graphene in dry method transfer metal substrate according to claim 1, it is characterised in that: the target lining
The placement direction at bottom can be horizontal to vertical any angle.
6. the method for graphene in dry method transfer metal substrate according to claim 1, it is characterised in that: the protection gas
Atmosphere is the mixing of a kind of gas or two or more gases that avoid graphene from etching in the high temperature environment.
7. the method for graphene in dry method transfer metal substrate according to claim 1, it is characterised in that: in step 2)
Heating and cooling rate are 0.01~1000 degrees celsius/minute.
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| CN108516541B (en) * | 2018-04-02 | 2021-06-04 | 西安工程大学 | CVD graphene dry transfer method |
| CN109142408B (en) * | 2018-08-06 | 2021-02-26 | 华东师范大学 | Method for preparing TEM sample of two-dimensional material by dry method |
| CN110184585B (en) * | 2019-06-25 | 2023-04-18 | 福建闽烯科技有限公司 | Preparation method and device of graphene copper powder |
| CN111845003B (en) * | 2020-06-18 | 2021-07-27 | 华中科技大学 | Controllable hot-pressing implementation method of nano material |
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