CN105296958B - A kind of three-dimensional non-catalytic base load graphene film structure and its preparation method at low ambient temperatures - Google Patents
A kind of three-dimensional non-catalytic base load graphene film structure and its preparation method at low ambient temperatures Download PDFInfo
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Abstract
The invention discloses a kind of three-dimensional non-catalytic base load graphene film structure, the structure includes non-catalytic substrate body, the three-dimensional structure etched on body surface, and is covered in the graphene film of whole surface.Invention also discloses the preparation method of the three-dimensional non-catalytic base load graphene film structure at low ambient temperatures.This method is easy to operate, and fabrication cycle is short, low manufacture cost, can directly on different materials, with the non-catalytic substrate with different surfaces three-dimensional structure the continuous uniform of the conformal covering high quality in full surface graphene film.Three-dimensional non-catalytic base load graphene film can be applied as the transparent electrode on surface on the devices such as photoelectric device, MEMS (MEMS), it can also be used to develop novel nano device.
Description
Technical field
The invention belongs to field of material technology, be related to a kind of three-dimensional non-catalytic base load graphene film structure and its
Preparation method at low ambient temperatures.
Background technology
Graphene is a kind of two dimensional crystal with hexangle type honeycomb lattice structure being made of single layer of carbon atom.Due to
With the big key that low-dimensional quantum characteristic and uniqueness sp2 hydridization are formed, free electron gas shows as two-dimentional massless dirac expense
Meter Zi Qi, thus graphene shows to absorb only 2.3% preferable translucency and up to 15,000cm2V- in visible region
The photoelectric characteristic of the superior electron mobility of 1s-1 etc..Meanwhile grapheme material also has high heat conductance and superpower mechanicalness
Can, these excellent characteristics make grapheme material be expected to become a kind of epoch-making transparent conductive film.
However in the application report of most photoelectric devices, graphene as transparent conductive film, is served as a contrast from catalytic
Bottom (such as：Copper foil, nickel foil etc.) surface, the target substrates such as semiconductor or insulator are transferred graphene to by transfer method and are obtained
Come, the residue glue which often brings to graphene surface, fold, tearing, the problems such as impurity, defect, to drop significantly
The low performance of graphene, and then influence the application of photoelectric device.Seek one kind directly graphene can be deposited to it is non-catalytic
Property substrate on graphene preparation method, be the key that solve problem above.
Plasma enhanced chemical vapor deposition method (PECVD) is a kind of key method of growth graphene.It is growing
The various actives such as during graphene, plasma is capable of providing high energy electron, is stimulated molecule and atom, free group
Substance, to which " PECVD " has lot of advantages when depositing nano structural material, for example, substrate growth temperature is low, sample life
Long rate is fast, and nanostructure sequence is easy to control etc..These advantages, it is a kind of direct to be doomed " PECVD ", quickly by graphite
Alkene is prepared into semiconductor, the appropriate method on the non-catalytics substrate such as insulator.Graphene is prepared using this method, avoids and turns
The harm that walk suddenly brings graphene, to widen graphene significantly in graphene-based MEMS (MEMS) device
With the application range of the field of photoelectric devices such as solar cell, ultracapacitor.
So far, using PECVD, the minority of graphene is prepared in the non-catalytics substrate such as semiconductor or insulator
In report, made in the plane non-catalytic substrate of a certain or few several materials under the higher temperature more than 650 DEG C
Standby, this results in that much there is the material compared with low melting point cannot directly be used to prepare graphene.Meanwhile saturating based on graphene
In the device application of bright conductive film, most devices of report are made of the optical element of various microstructures.So higher
At a temperature of, the graphene that is prepared in plane non-catalytic substrate, it is difficult to meet it in a variety of materials and various micromechanical devices
In application.Therefore the universality method for finding one kind " PECVD " conformal graphene growth is extremely urgent, this method is required to
Meet the non-catalytic substrate grown of different kind of material, and meets the non-catalytic base that surface has diverse microcosmic structure simultaneously
Bottom growth.
Invention content
In view of this, the purpose of the present invention is to provide a kind of three-dimensional non-catalytic base load graphene film structure and
Its preparation method at low ambient temperatures, the graphene film continuous uniform of the structure, and inhomogeneity can be used in its substrate
The material of type, and preparation method is easy to operate, and fabrication cycle is short, low manufacture cost, and can be in the condition of lower temperature
Under realization can be completed.
In order to achieve the above objectives, the present invention provides the following technical solutions：
1, a kind of three-dimensional non-catalytic base load graphene film structure, the structure includes non-catalytic substrate machine
Body, the three-dimensional structure etched on body surface, and it is covered in the graphene film of whole surface.
Preferably, the three-dimensional structure is in periodic arrangement or no periodic array, and the three-dimensional structure is grating, receives
Metre hole, nano wire, nanometer rods, one or more of pyramid, step structure.
2, the preparation method of the three-dimensional non-catalytic base load graphene film structure, which is characterized in that step is such as
Under：
A. three-dimensional structure is prepared in non-catalytic substrate by photoetching, ion etching or wet etching, and cleaned up
And it is dry；
B. it will be placed in the temperature control cavity of plasma enhanced chemical vapor deposition unit, drain by the substrate of step A
Air in cavity, then fills protective gas into cavity；
C., temperature control cavity after step B filling protective gas is evacuated to the vacuum state of growth, is then heated to
It 500-650 DEG C, is passed through carbon-source gas and plays the protective gas of current-carrying, open plasma enhances source, maintains air pressure in 1-
10Pa makes graphene film directly grow 60-120min in the non-catalytic substrate surface of three-dimensional structure；
D. after waiting for the growth of step C graphene films, plasma enhancing source is closed immediately, and stop to temperature control cavity
In be passed through carbon-source gas, by temperature control cavity, speed is cooled to 10-30 DEG C under protective gas and graphene film growth pressure, takes out
The non-catalytic substrate of three-dimensional structure, full surface are the graphene film for being covered with continuous uniform.
Preferably, the non-catalytic substrate is growth temperature of the fusing point less than graphene film and is given birth in graphene film
Stablize unvaporized inorganic material under long temperature condition.
Preferably, the non-catalytic substrate be silica, silicon, germanium, GaAs, indium phosphide, silicon nitride, silicon carbide,
Zinc oxide or aluminium oxide.
It is preferred, the protective gas be one kind in nitrogen, hydrogen, argon gas, helium, neon, Krypton and xenon or
Several mixing, the carbon-source gas are that one or more of methane, ethylene, acetylene, methanol, ethyl alcohol, benzene and toluene gas are mixed
It closes.
Preferably, cleaning way described in step A is as follows：By the non-catalytic substrate of three-dimensional structure set successively acetone,
Respectively it is cleaned by ultrasonic 10-15min in 95vol% ethyl alcohol, water, is then dried up with nitrogen.
Preferably, the method that air in temperature control cavity is drained in step B is as follows：Temperature control cavity is evacuated to 1-5Pa, so
Filling protective gas repeats the above-mentioned operation for vacuumizing, filling protective gas to 1atm afterwards, until the air in temperature control cavity
It drains；Or the air pressure in temperature control cavity is maintained at 1atm, the protective gas 10- of big flow is passed through into temperature control cavity
30min is rinsed, and the air in temperature control cavity is made to drain.
Preferably, the plasma enhancing source is radio frequency plasma source.
Preferably, RF plasma power 10-100W.
The beneficial effects of the present invention are：The present invention provides a kind of three-dimensional non-catalytic base load graphene film knots
Structure, the graphene film continuous uniform of structure, and different types of material can be used in its substrate.And the present invention provides one
The universality method of conformal growth graphene film in the non-catalytic substrate of three-dimensional structure under low temperature environment is planted, it is easy to operate,
Fabrication cycle is short, low manufacture cost, can be directly in different materials, with the non-catalytic substrate with different surfaces three-dimensional structure
The graphene film of the continuous uniform of the upper conformal covering high quality in full surface, which is polycrystalline film, the atom number of plies
It can be controlled by adjusting processes conditions such as the flow-rate ratio of carbon-source gas and protective gas, RF plasma powers, shape
At single-layer or multi-layer；Crystallinity, film resistor, translucency of graphene etc. can also pass through the flow of carbon-source gas and protective gas
It is controlled than adjusting processes conditions such as, RF plasma powers.Graphene in the non-catalytic substrate of three-dimensional structure
Film can be applied as the transparent electrode on surface on the devices such as photoelectric device, MEMS (MEMS), it is also possible to
In exploitation novel nano device.
Description of the drawings
In order to keep the purpose of the present invention, technical solution and advantageous effect clearer, the present invention provides following attached drawing and carries out
Explanation：
Fig. 1 is the non-catalytic base load graphene film structure in grating three-dimensional structure；
Fig. 2 is the non-catalytic base load graphene film structure in variously-shaped three-dimensional structure；
Fig. 3 is the schematic diagram that " PECVD " prepares graphene film；
Fig. 4 is the non-catalytic base load graphene film structure that embodiment 1 is prepared under the conditions of different growth times
Light transmittance and film resistor tendency chart；
Fig. 5 is that the conformal covering graphene in non-catalytic substrate of the different materials from different three-dimensional structures of embodiment 2 is thin
Raman (Raman) spectrum after film.
Specific implementation mode
Below in conjunction with attached drawing, the preferred embodiment of the present invention is described in detail.
Test method without specific conditions in embodiment usually according to normal condition, or is built according to manufacturer
The condition of view.
Embodiment 1
One, the conformal method for covering graphene film in full surface on the quartz substrate of optical grating construction, includes the following steps：
A. it is prepared in the periodic optical grating construction of the surface etch of quartz substrate by the method for photoetching and ion etching
The quartz substrate of optical grating construction；
B. the quartz substrate of optical grating construction is set successively in acetone, 95vol% ethyl alcohol, pure water and is respectively cleaned by ultrasonic 10-
15min is dried up with nitrogen；
C. the quartz substrate of the optical grating construction after step B dryings is set into the tubular type PECVD system temperature control chamber that caliber is 30mm
In body, sealing temperature controlled cavity；Temperature control cavity after sealing is evacuated to 1Pa with vacuum pump, argon gas is filled extremely into vacuum cavity
1atm, then it is evacuated to 1Pa with vacuum pump, operating repeatedly three times drains the air in vacuum cavity, is then filled out into vacuum cavity
It is 10sccm to be flushed with hydrogen gas, and air pressure maintains 5Pa；
D. the vacuum cavity after step C filling hydrogen is warming up to 600 DEG C, methane gas is passed through into vacuum cavity
1.5sccm and hydrogen 1sccm opens radio frequency plasma enhancing source and is set as 50W, and air pressure maintains 5Pa, and graphene is made to give birth to
Long 60-120min (being spaced 10min, totally 7 samples), (schematic diagram that " PECVD " prepares graphene is as shown in Figure 3, wherein 1 is
PECVD diamond heating systems；2 enhance source for radio frequency plasma；3 be the temperature control cavity of PECVD tube furnaces；4 be graphene
Film；5 be the non-catalytic substrate of three-dimensional structure；6 be the vacuum pump of PECVD tube furnace systems, is furnished with vacuum meter)；
E. after waiting for step D graphene growths, closing radio frequency plasma immediately enhances source, and stops to temperature control cavity
In be passed through methane gas, by vacuum cavity, prompt drop warms to room temperature under 10sccm hydrogen and 5Pa pressure, takes out the stone of optical grating construction
English substrate, full surface are the graphene film for being covered with continuous uniform, and the atom number of plies is 2~5 layers.
Resulting structures are as shown in Figure 1a, wherein 1 represents quartz substrate, 2 represent the periodicity of the surface etch of quartz substrate
Optical grating construction, 3 represent the graphene film of the continuous uniform covered on full surface, resulting structures SEM (scanning electron microscope)
Shape appearance figure is as shown in topic 1b.
Two, the optical performance test of three-dimensional non-catalytic base load graphene film structure is as follows：
1, light transmittance is tested by " UV, visible light scene photometer " to 7 samples that step E is obtained, and to each sample
Light transmittance at a length of 550nm of visible light wave is compared, and the results are shown in Figure 4；Light transmittance with growth time increase
And reduce, this illustrates that it is a critical developmental factor for thickening graphene to extend the time；In the sample of gained, the life of 60min
Corresponding graphene light transmittance highest for a long time is 92.5%.
2, method of 7 samples step E obtained by brushing silver paste with connecting silver wire, in the both ends system of each sample
Standby electrode, then utilizes " four-point probe ", tests the I-V curve figure of graphene film on each sample, and corresponding calculating
Go out the corresponding film resistor of each sample, as shown in figure 4, the graphene film thickened can increase the conductive capability of graphene, drop
The film resistor of low graphene, when growth time is 120min, the electric conductivity of graphene is best, and corresponding film resistor is
1200 Ou Fang；Compare the plane non-catalytic substrate of report, is prepared in the non-catalytic substrate of three-dimensional structure three-dimensional conformal
Graphene film is more difficult to control, especially the side of microscopic three-dimensional structural, and there are more uncontrollabilities for the attachment of graphene.But
It is that in contrast, the film resistor for the conformal graphene of three-dimensional that we prepare but reduces~500 Ou Fang, this just confirms me
The PECVD graphene growth methods reported be a kind of high-quality graphene growth method that low-resistance three-dimensional is conformal.
Embodiment 2
One, in the silicon chip of different base, including pyramid structure, the silicon chip of nano thread structure, the silicon chip of optical grating construction, light
The method of the complete conformal covering graphene film in surface on five kinds of substrates such as the quartz plate of grid structure and the germanium wafer of optical grating construction, including
Following steps：
A. periodical in the surface etch of silicon base, quartz substrate and germanium substrate by the method for photoetching and ion etching
Optical grating construction；By the method for wet etching no periodic pyramid and nano thread structure are prepared in silicon substrate surface；
B. the substrates of different of different structure is set successively respectively in acetone, 95vol% ethyl alcohol, pure water and is respectively cleaned by ultrasonic 10-
15min is dried up with nitrogen；
C. the substrates of different of the different structure after step B dryings is placed in the tubular type PECVD system that caliber is 30mm simultaneously
In temperature control cavity (as shown in Figure 3), sealing temperature controlled cavity；Temperature control cavity after sealing is evacuated to 1Pa with vacuum pump, to vacuum chamber
Argon gas is filled in body and is evacuated to 1Pa to 1atm, then with vacuum pump, and operating repeatedly three times drains the air in vacuum cavity, then
It is 10sccm that hydrogen is filled into vacuum cavity, and air pressure maintains 10Pa；
D. the vacuum cavity after step C filling hydrogen is warming up to 600 DEG C, ethylene gas is passed through into vacuum cavity
3sccm and hydrogen 2sccm opens radio frequency plasma enhancing source and is set as 30W, and air pressure maintains 8Pa, makes graphene growth
90min；
E. after waiting for step D graphene growths, closing radio frequency plasma immediately enhances source, and stops to temperature control cavity
In be passed through ethylene gas, by vacuum cavity, prompt drop warms to room temperature under 10sccm hydrogen and 5Pa pressure, takes out all different knots
The substrates of different of structure, full surface are 2-5 layers by the graphene film of conformal covering continuous uniform, the atom number of plies.
Resulting structures are as shown in Figure 2 a, and structure shown in wherein Fig. 2 a is the knot for concentrating in together various three-dimensional structures
Structure, it is in any three-dimensional structure that substrate etching can drop in expression, wherein 1 represents substrate, 2 represent the periodical light of substrate surface etching
Grid structure, 3 represent the graphene film of the continuous uniform covered on full surface, and Fig. 2 b indicate the SEM figures of pyramid structure structure
(scanning electron microscope).
Two, the optical performance test of three-dimensional non-catalytic base load graphene film structure is as follows：
The each conformal substrate for being covered with graphene film obtained in step E is once put into Raman spectrometer and is carried out
Raman characterization obtains the Raman spectrogram of each sample, as shown in figure 5, the graphene prepared in different base as seen from Figure 5
With similar raman spectrum feature.It follows that for the non-catalytic substrate of different type three-dimensional structure, with different materials
Non-catalytic substrate, PECVD is to obtain the universality growth method of conformal graphene.
Embodiment 3
The method of the complete conformal covering graphene film in surface, includes the following steps in the silicon base of club shaped structure：
A. by the method for the wet etching in alkaline solution, show that no preiodic type is three-dimensional in the surface etch of silicon base
Rodlike knot prepares the silicon chip of club shaped structure；
B. the silicon chip of club shaped structure is set successively in acetone, 95vol% ethyl alcohol, pure water and is respectively cleaned by ultrasonic 10-15min,
It is dried up with nitrogen；
C. the silicon chip of the club shaped structure after step B dryings is set into the tubular type PECVD system temperature control cavity that caliber is 30mm
In, sealing temperature controlled cavity；Temperature control cavity after sealing is evacuated to 1Pa with vacuum pump, argon gas is filled into vacuum cavity to 1atm,
It is evacuated to 1Pa with vacuum pump again, operating repeatedly three times drains the air in vacuum cavity, and hydrogen is then filled into vacuum cavity
For 20sccm, air pressure maintains 10Pa；
D. the vacuum cavity after step C filling hydrogen is warming up to 650 DEG C, acetylene gas is passed through into vacuum cavity
3sccm and hydrogen 2sccm opens radio frequency plasma enhancing source and is set as 30W, and air pressure maintains 10Pa, and graphene is made to give birth to
Long 60min；
E. after waiting for step D graphene growths, closing radio frequency plasma immediately enhances source, and stops to temperature control cavity
In be passed through acetylene gas, by vacuum cavity, prompt drop warms to room temperature under 20sccm hydrogen and 10Pa pressure, takes out club shaped structure
Silicon chip, the conformal graphene film for being covered with continuous uniform in full surface, the atom number of plies are 1-3 layers；
Embodiment 4
The method of the complete conformal covering graphene film in surface in the non-polished silicon base of arbitrary structures, including following step
Suddenly：
A. the non-polished silicon chip of purchase is set successively in acetone, 95vol% ethyl alcohol, pure water and is respectively cleaned by ultrasonic 10-
15min is dried up with nitrogen；
C. the non-polished silicon base after step B dryings is set in the tubular type PECVD system temperature control cavity that caliber is 30mm,
Sealing temperature controlled cavity；Temperature control cavity after sealing is evacuated to 1Pa with vacuum pump, argon gas is filled into vacuum cavity to 1atm, then
It is evacuated to 1Pa with vacuum pump, operating repeatedly three times drains the air in vacuum cavity, and hydrogen is then filled into vacuum cavity is
10sccm, air pressure maintain 5Pa；
D. the vacuum cavity after step C filling hydrogen is warming up to 650 DEG C, acetylene gas is passed through into vacuum cavity
1.5sccm and hydrogen 1sccm opens radio frequency plasma enhancing source and is set as 10W, and air pressure maintains 5Pa, and graphene is made to give birth to
Long 60min；
E. after waiting for step D graphene growths, closing radio frequency plasma immediately enhances source, and stops to temperature control cavity
In be passed through methane gas, by vacuum cavity, prompt drop warms to room temperature under 10sccm hydrogen and 5Pa pressure, takes out non-polished silicon substrate
Bottom, the full surface, that is, conformal graphene film for being covered with continuous uniform, the atom number of plies are 1-2 layers；
Embodiment 5
The method of the complete conformal covering graphene film in surface, includes the following steps on the indium phosphide bottom of step structure：
A. by the method for high annealing substrate, acyclic step structure is prepared on the surface at indium phosphide bottom, is obtained
To the indium phosphide bottom of step structure；
B. the indium phosphide bottom of step structure is set successively in acetone, 95vol% ethyl alcohol, pure water and is respectively cleaned by ultrasonic 10-
15min is dried up with nitrogen；
C. the tubular type PECVD system temperature control that caliber is 30mm is set at the indium phosphide bottom of the step structure after step B dryings
In cavity (as shown in Figure 2), sealing temperature controlled cavity；Temperature control cavity after sealing is evacuated to 1Pa with vacuum pump, into vacuum cavity
Filling argon gas is evacuated to 1Pa to 1atm, then with vacuum pump, and operating repeatedly three times drains the air in vacuum cavity, then to true
It is 20sccm that hydrogen is filled in cavity body, and air pressure maintains 10Pa；
D. the vacuum cavity after step C filling hydrogen is warming up to 650 DEG C, acetylene gas is passed through into vacuum cavity
3sccm and hydrogen 2sccm opens radio frequency plasma enhancing source and is set as 50W, and air pressure maintains 10Pa, and graphene is made to give birth to
Long 30min；
E. after waiting for step D graphene growths, closing radio frequency plasma immediately enhances source, and stops to temperature control cavity
In be passed through methane gas, by vacuum cavity, prompt drop warms to room temperature under 20sccm hydrogen and 10Pa pressure, takes out step structure
Indium phosphide bottom, the full surface, that is, conformal graphene film for being covered with continuous uniform, the atom number of plies are layer 2-3；
Embodiment 6
The method of the complete conformal covering graphene film in surface in the non-polished germanium substrate that surface has arbitrary structures, including
Following steps：
A. the non-polished germanium substrate of purchase is set successively in acetone, 95vol% ethyl alcohol, pure water and is respectively cleaned by ultrasonic 10-
15min is dried up with nitrogen；
B. the non-polished germanium substrate after step A dryings is set in the tubular type PECVD system temperature control cavity that caliber is 30mm, it is close
Sealed temperature cavity；Temperature control cavity after sealing is evacuated to 1Pa with vacuum pump, argon gas is filled into vacuum cavity to 1atm, then use
Vacuum pump is evacuated to 1Pa, and operating repeatedly three times drains the air in vacuum cavity, and hydrogen is then filled into vacuum cavity is
10sccm, air pressure maintain 5Pa；
C. the vacuum cavity after step B filling hydrogen is warming up to 550 DEG C, methane gas is passed through into vacuum cavity
1.5sccm and hydrogen 1sccm opens radio frequency plasma enhancing source and is set as 10W, and air pressure maintains 2Pa, and graphene is made to give birth to
Long 60min；
D. after waiting for step C graphene growths, closing radio frequency plasma immediately enhances source, and stops to temperature control cavity
In be passed through methane gas, by vacuum cavity, prompt drop warms to room temperature under 10sccm hydrogen and 5Pa pressure, takes out non-polished germanium base
Bottom, the full surface, that is, conformal graphene film for being covered with continuous uniform, the atom number of plies are single layer；
Finally illustrate, preferred embodiment above is merely illustrative of the technical solution of the present invention and unrestricted, although logical
It crosses above preferred embodiment the present invention is described in detail, however, those skilled in the art should understand that, can be
Various changes are made to it in form and in details, without departing from claims of the present invention limited range.
Claims (9)
1. a kind of three-dimensional non-catalytic base load graphene film structure, which is characterized in that the structure includes non-catalytic
Substrate body, the three-dimensional structure etched on body surface, and it is covered in the graphene film of whole surface；
The preparation method of the three-dimensional non-catalytic base load graphene film structure, steps are as follows：
A. three-dimensional structure is prepared in non-catalytic substrate by photoetching, ion etching or wet etching, and cleans up and does
It is dry；
B. it will be placed in the temperature control cavity of plasma enhanced chemical vapor deposition unit by the substrate of step A, drain cavity
Interior air, then fills protective gas into cavity；
C., temperature control cavity after step B filling protective gas is evacuated to the vacuum state of growth, then heats to 500-
650 DEG C, be passed through carbon-source gas and play the protective gas of current-carrying, open plasma enhancing source, maintenance air pressure in 1-10Pa,
Graphene film is set directly to grow 60-120min in the non-catalytic substrate surface of three-dimensional structure, RF plasma power is
10-100W；
D. after waiting for the growth of step C graphene films, plasma enhancing source is closed immediately, and stop into temperature control cavity
It is passed through carbon-source gas, speed is cooled to 10-30 DEG C under protective gas and graphene film growth pressure by temperature control cavity, takes out three
The non-catalytic substrate of structure is tieed up, full surface is the graphene film for being covered with continuous uniform.
2. a kind of three-dimensional non-catalytic base load graphene film structure according to claim 1, which is characterized in that described
Three-dimensional structure be in periodic arrangement or no periodic array, the three-dimensional structure be grating, nano-pore, nano wire, nanometer rods,
One or more of pyramid, step structure.
3. the preparation method of any one of the claim 1 ~ 2 three-dimensional non-catalytic base load graphene film structure, special
Sign is that steps are as follows：
A. three-dimensional structure is prepared in non-catalytic substrate by photoetching, ion etching or wet etching, and cleans up and does
It is dry；
B. it will be placed in the temperature control cavity of plasma enhanced chemical vapor deposition unit by the substrate of step A, drain cavity
Interior air, then fills protective gas into cavity；
C., temperature control cavity after step B filling protective gas is evacuated to the vacuum state of growth, then heats to 500-
650 DEG C, be passed through carbon-source gas and play the protective gas of current-carrying, open plasma enhancing source, maintenance air pressure in 1-10Pa,
Graphene film is set directly to grow 60-120min in the non-catalytic substrate surface of three-dimensional structure, RF plasma power is
10-100W；
D. after waiting for the growth of step C graphene films, plasma enhancing source is closed immediately, and stop into temperature control cavity
It is passed through carbon-source gas, speed is cooled to 10-30 DEG C under protective gas and graphene film growth pressure by temperature control cavity, takes out three
The non-catalytic substrate of structure is tieed up, full surface is the graphene film for being covered with continuous uniform.
4. the preparation method of three-dimensional non-catalytic base load graphene film structure, feature exist according to claim 3
In the non-catalytic substrate is that fusing point is less than the growth temperature of graphene film and under the conditions of graphene film growth temperature
Stablize unvaporized inorganic material.
5. the preparation method of three-dimensional non-catalytic base load graphene film structure, feature exist according to claim 4
In the non-catalytic substrate is silica, silicon, germanium, GaAs, indium phosphide, silicon nitride, silicon carbide, zinc oxide or oxidation
Aluminium.
6. the preparation method of three-dimensional non-catalytic base load graphene film structure, feature exist according to claim 3
In the protective gas is the mixing of one or more of nitrogen, hydrogen, argon gas, helium, neon, Krypton and xenon, the carbon
Source gas is the mixing of one or more of methane, ethylene, acetylene, methanol, ethyl alcohol, benzene and toluene gas.
7. the preparation method of three-dimensional non-catalytic base load graphene film structure, feature exist according to claim 3
In cleaning way is as follows described in step A：The non-catalytic substrate of three-dimensional structure is set successively each in acetone, 95vol% ethyl alcohol, water
It is cleaned by ultrasonic 10-15min, is then dried up with nitrogen.
8. the preparation method of three-dimensional non-catalytic base load graphene film structure, feature exist according to claim 3
In the method for draining air in temperature control cavity in step B is as follows：Temperature control cavity is evacuated to 1-5Pa, is subsequently filled protection gas
Body repeats the above-mentioned operation for vacuumizing, filling protective gas to 1atm, until the air in temperature control cavity drains；Or it will
Air pressure in temperature control cavity is maintained at 1atm, and the protective gas 10-30min that big flow is passed through into temperature control cavity is rinsed,
The air in temperature control cavity is set to drain.
9. the preparation method of three-dimensional non-catalytic base load graphene film structure, feature exist according to claim 3
In the plasma enhancing source is radio frequency plasma source.
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| CN102260858A (en) * | 2010-05-26 | 2011-11-30 | 中国科学院物理研究所 | Method for directly growing graphine on various substrates |
| CN103193224A (en) * | 2013-04-17 | 2013-07-10 | 苏州大学 | Method for preparing graphene film on nonmetallic substrate at low temperature |
| CN104018136A (en) * | 2014-04-30 | 2014-09-03 | 中国科学院重庆绿色智能技术研究院 | Method for directly and conformally covering graphene film on full surface of substrate with three-dimensional structure |
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| CN102260858A (en) * | 2010-05-26 | 2011-11-30 | 中国科学院物理研究所 | Method for directly growing graphine on various substrates |
| CN103193224A (en) * | 2013-04-17 | 2013-07-10 | 苏州大学 | Method for preparing graphene film on nonmetallic substrate at low temperature |
| CN104018136A (en) * | 2014-04-30 | 2014-09-03 | 中国科学院重庆绿色智能技术研究院 | Method for directly and conformally covering graphene film on full surface of substrate with three-dimensional structure |
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