CN105836733B - A kind of method of the graphene quality of direct growth on improvement nonmetallic substrate - Google Patents
A kind of method of the graphene quality of direct growth on improvement nonmetallic substrate Download PDFInfo
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- CN105836733B CN105836733B CN201610144523.2A CN201610144523A CN105836733B CN 105836733 B CN105836733 B CN 105836733B CN 201610144523 A CN201610144523 A CN 201610144523A CN 105836733 B CN105836733 B CN 105836733B
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- graphene
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- nonmetallic substrate
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
Abstract
The method of the graphene quality of direct growth, belongs to semiconductor material growing field on a kind of improvement nonmetallic substrate.A layer graphene film is grown on nonmetallic substrate first with chemical vapour deposition technique, one layer of thin metal layer is sputtered on graphene film again, the substrate that growth has thin metal layer is carried out to the CVD growth of graphene film again, surface graphene film and metal level are removed after the completion of growth.Present invention improves the quality of the graphene of direct growth on nonmetallic substrate, and after catalytic growth again, the quality and performance of graphene film are obviously improved.
Description
Technical field：
The present invention relates to a kind of method for improving the graphene quality of direct growth on nonmetallic substrate, belong to semiconductor material
Expect growing technology field.
Background technology：
2004, graphene was separated out by the scientist of Univ Manchester UK from graphite, before this, stone
Black alkene is considered as hypothetical structure always, can not be individually stabilized.Graphene be one kind by carbon atom with sp2 hydridization rails
The hexagon of road composition is in the flat film of honeycomb structure, is a kind of two dimension for there was only a carbon atom thickness (about 0.335nm)
Material.As most thin and most hard material, graphene have the premium properties that many other materials do not possess in the world at present：
Electron mobility is more than 15000cm at room temperature2/ VS, resistivity only have 10-6Ω cm are lower than copper or silver；Single-layer graphene
97.7% is reached to the transmissivity of visible ray, even if optical wavelength reaches several microns, its absorption to light wave is also very little
's；Thermal conductivity factor reaches 5300W/mk, higher than CNT (CNT) and diamond.Have these excellent just because of graphene
Good characteristic, in recent years by the very big concern of each area research personnel, the achievement in research related to graphene emerges in an endless stream, all
Such as had been achieved for well in transparency electrode, ultracapacitor, lithium ion battery, biological medicine etc., the application of graphene
Effect.
Application of the graphene in microelectronic component is a very valuable research field.Modern microelectronic devices chi
Very little minimum, precision is high, and this is just to proposing harsh requirement applied to the quality of graphene therein, therefore, how to prepare
Going out the graphene of high quality and it is completely transferred to target substrate becomes the significant challenge of area research personnel.Stone at present
The preparation method of black alkene mainly includes micromechanics stripping method, SiC epitaxys, chemical stripping method and CVD, prepared by wherein CVD
Graphene is simple to operate, and graphene quality height is made, and area is big, has become the main method for obtaining high-quality graphene.Mesh
The graphene of the preceding direct growth on nonmetallic substrate is second-rate, and this is due to that the C-H bond of carbonaceous gas is only urged in metal
It can be just broken under change effect, therefore only growth graphene just can guarantee that its quality is higher on the metallic substrate.If will growth
Graphene film on the metallic substrate is transferred on nonmetallic substrate, just inevitably introduces the unreasonablys such as impurity, broken hole
Factor is thought so as to reduce film quality.For this case, existing researcher uses plates thin metal layer on nonmetallic substrate
Method direct growth graphene and achieve good result, but make the graphene quality that grows in this way still with reality
The requirement of border application has larger gap.
The present invention using the nonmetallic materials after direct growth graphene film as sample, by way of magnetron sputtering
Graphenic surface sputters thin metal layer, then carries out the CVD catalytic growth of graphene in layer on surface of metal, is removed after the completion of growth
The graphene film and metal level of second secondary growth.During quadric catalysis grows graphene, metal level is secondary to first
Long graphene film (on nonmetallic substrate) equally serves certain catalytic action, gives birth to its catalysis carried out again
It is long.With in general on nonmetallic substrate compared with the method for direct growth graphene, the method in the present invention can be obviously improved
The quality of graphene film, it is significant for application of the graphene on nonmetallic substrate.
The content of the invention：
It is an object of the invention to provide a kind of method for improving the graphene quality of direct growth on nonmetallic substrate.
Direct growth graphene can eliminate the influence that shifting process is brought and can significantly improve contact interface characteristic on nonmetallic substrate,
But due to growth of the nonmetallic substrate to graphene does not have catalytic action, therefore the graphene grown on nonmetallic substrate
Film is often of low quality, and defect is more, does not reach using standard.It is contemplated that overcome these shortcomings.
A kind of method for improving direct growth graphene quality on nonmetallic substrate provided by the invention, the process of this method
As shown in Figure 1：Bottom is nonmetallic substrate material 100, and graphene 101 is grown directly upon nonmetallic substrate surface, in 101 tables
Face sputtering Cu layers 102, then catalytic growth graphene 103, finally remove 102 and 103；Before accompanying drawing 2 shows catalytic growth again
Raman spectrum comparison diagram afterwards；Accompanying drawing 3 is shown using the light transmittance of material and other techniques after present invention progress graphene growth
Comparison diagram；
Backing material can meet any semiconductor of technological level requirement or insulation in growth course in the present invention
Material
The invention provides a kind of method for improving direct growth graphene quality on nonmetallic substrate, it is characterised in that
Comprise the following steps that：
Step 1, the graphene film surface grown on nonmetallic substrate sputter a layer thickness for 500-600nm (preferably
Cu 550nm)；
Step 2, step 1 gained sample is put into the chemical vapor deposition regeneration for carrying out graphene in CVD reative cells again
It is long；
Step 3, the sample after step 3 growth graphene is taken out, the graphene on Cu surfaces is removed using oxygen plasma, so
After reuse FeCl3Solution corrosion falls Cu.
Thin metal layer carries out the growth of graphene from Cu in the present invention, and the metal material has good to graphene growth
Catalytic action.
The present invention sputters the catalyst layer of one layer of 4-5 nano thickness further preferably on nonmetallic substrate surface, then
Regrowth graphene film.
Chemical vapour deposition technique is used during the catalytic growth again that graphene is carried out in step 2 of the present invention, carbon-source gas use
Methane, reducibility gas use hydrogen, and protective gas uses argon gas
The temperature of chemical vapour deposition technique regrowth graphene is not cause substrate surface structure to destroy in step 2 of the present invention
And the maximum temperature for melting thin metal layer；
The graphene film after regrowth is removed using oxygen plasma etch in the present invention, uses FeCl3Solution removes
Copper plate.
Effect of the present invention：
1) there are some researches show can improve the matter of grown graphene by sputtering thin metal layer on nonmetallic substrate
Amount, but still have certain gap with application requirement by test, its actual mass.In order to further improve on nonmetallic substrate directly
The quality of graphene is grown, employs the method being catalyzed again to graphene film, the graphene after catalytic growth again lacks
Falling into density reduces, and quality significantly improves；
2) compared with other growth techniques, using method in the present invention carry out catalytic growth again graphene film have it is good
Good light transmittance, this is significant in the application of photoelectric field for graphene；
3) catalysis process is a kind of general method again for the graphene that provides in the present invention, no matter which kind of Grown
Graphene film, if again catalytic growth when reaction condition backing material is not damaged, can using this method come
Improve the quality of graphene film, there is very strong flexibility.
Brief description of the drawings：
Fig. 1：Graphene film catalytic growth flow chart again on nonmetallic substrate；
Fig. 2：Graphene Raman spectrum comparison diagram after catalytic growth again；
Fig. 3：Graphene light transmittance comparison diagram after catalytic growth again.
Embodiment：
The implementation of the present invention is described by following examples, but is not limited to following examples.
Embodiment 1：
Step 1, cleaning with batch two panels GaN base LED, using acetone ultrasound 5 minutes, successively with acetone, second
Alcohol, chloroazotic acid boil, and are cleaned with deionized water, nitrogen drying；
Step 2, in epitaxial wafer surface spin coating photoresist, ledge structure is formed using ICP lithographic techniques and exposes n-GaN
Layer；
Step 3, PECVD deposits SiO2, photoetching simultaneously corroded with BOE, forms SiO2Barrier layer；
Step 4, surface sputtering thickness be 4-5nm thin Ni layers as Catalytic Layer；
Step 5, epitaxial wafer is put into the graphene growth carried out in CVD reative cells under equal conditions, argon flow amount
960sccm, hydrogen flowing quantity 40sccm, methane flow 40sccm, 800 DEG C of growth temperature, growth time 5min；
Step 6, the Cu by magnetron sputtering growth 550nm on the epitaxial wafer for having graphene is grown；
Step 7, the catalytic growth again using growth conditions progress graphene film in step 5；
Step 8, the graphene using oxygen plasma removal surface, use FeCl3Solution corrosion Copper thin film；
Step 9, metal electrode evaporation (Ni/Au electrodes) is carried out, remove photoresist, stripping electrode；
Step 10, reducing thin of sapphire substrate to 150um, back side metallized reflective layer；
Step 11, scribing, sliver；
Using the method in the present invention in GaN base LED catalytic growth again, gained after direct growth graphene
Graphene film is to substitute traditional ITO nesa coating, respectively to GaN base LED after the completion of step 5 and step 8
Raman spectrum test is carried out, as a result as shown in Figure 2, it can be seen that the Raman spectrum of graphene has obtained obvious improvement.D
Peak relative intensity substantially reduces, and illustrates that defect is reduced in film；2D peaks strengthen, illustrate film from more unordered state be changed into compared with
For orderly state.So graphite of the catalysis process again proposed in the present invention for direct growth on improvement nonmetallic substrate
It is a kind of effective method for alkene quality.
Claims (4)
- A kind of 1. method for improving direct growth graphene quality on nonmetallic substrate, it is characterised in that walked including following technique Suddenly：Step 1, the graphene film surface grown on nonmetallic substrate sputter the Cu that a layer thickness is 500-600nm；Step 2, step 1 gained sample is put into the chemical vapor deposition regrowth for carrying out graphene in CVD reative cells again；Step 3, the sample after step 3 growth graphene is taken out, the graphene on Cu surfaces, Ran Houzai are removed using oxygen plasma Use FeCl3Solution corrosion falls Cu.
- 2. according to the method for direct growth graphene quality on a kind of improvement nonmetallic substrate described in claim 1, its feature It is, step 1 sputters the catalyst layer of one layer of 4-5 nano thickness on nonmetallic substrate surface, and then regrowth graphene is thin Film.
- 3. according to the method for direct growth graphene quality on a kind of improvement nonmetallic substrate described in claim 1, its feature It is, use chemical vapour deposition technique during the catalytic growth again of progress graphene in step 2, carbon-source gas use methane, reduction Property gas uses hydrogen, and protective gas uses argon gas.
- 4. according to the method for direct growth graphene quality on a kind of improvement nonmetallic substrate described in claim 1, its feature It is, the temperature of chemical vapour deposition technique regrowth graphene is not cause substrate surface structure to destroy and do not make in step 2 The maximum temperature of thin Ni metal layer fusing.
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| KR102071663B1 (en) * | 2018-06-15 | 2020-01-30 | 광주과학기술원 | Method of manufacturing graphene directly on a substrate without transfer process |
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