CN110429026A - A method of opening graphene band gap - Google Patents
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Abstract
The invention discloses a kind of methods for opening graphene band gap, belong to semiconductor electronic technical field, comprising the following steps: prepare gallium oxide layer and graphene layer respectively；Graphene layer is transferred on gallium oxide layer, changes the electronic structure of graphene by the electric charge transfer between gallium oxide and graphene, forms gallium oxide/graphene hetero-junctions, realizes the opening of graphene band gap；The method provided by the invention for opening graphene band gap, preparation process is simple, and device architecture is clear, largely can effectively open graphene band gap, has great significance for graphene is applied to semi-conductor electronic device field.
Description
Technical field
The invention belongs to semiconductor electronic technical fields, and in particular to a method of open graphene band gap.
Background technique
Graphene, a kind of single layer two dimensional crystal have excellent physical property, such as the carrier mobility of superelevation, Dan Yuan
The mechanical strength and suppleness of molecular layers thick and superelevation have good potential using value in following semiconductor field, draw
The extensive concern of people is played.But since graphene itself is without band gap, it not can be used directly and led in semi-conductor electronic device
Domain, Yao Shixian graphene will solve the problems, such as to open graphene band gap first in the application in semi-conductor electronic device field.Mesh
Preceding common opening graphene band gap method is that graphene is cut into nanobelt, to realize the opening of graphene band gap.Although
Graphene, which is cut into nanobelt, can open the band gap of graphene, and the band gap of the narrower opening of width is bigger, but following
Have that width is narrower, the smaller problem of the driving current of carrying greatly limits the practical application of graphene.
Paper " the Tunable and sizable band gap of single- that Ruge Quhe etc. is delivered at it
layer graphene sandwiched between hexagonal boron nitride”(NPG Asia Materials
(2012)4,e16；doi:10.1038/am.2012.29；Published online 27April 2012) propose one kind
The sandwich structure of BN/graphene/BN is clipped in graphene between the hexagonal BN piece of plane, discovery is suitably stacking
Under mode, graphene can open the band gap of 0.16eV.If adding vertical electric field, band to BN/graphene/BN composite construction
Gap can be further improved 0.34eV.Although this method opens graphene band gap, but it is smaller to be open band gap magnitude, In
It is not enough to apply in electronic device at room temperature, so the extensive use to graphene still has very big limitation.Therefore, how
A kind of simple effective method, opening graphene band gap as bigger as possible, for graphene answering in semiconductor field are provided
With significant.
Summary of the invention
It is an object of the invention to, propose a kind of to open graphene band gap in view of the deficiency of the prior art
Method, it is easy to operate and can greatly open graphene band gap, realize graphene in semi-conductor electronic device field
Using.
It is an object of the present invention to provide a kind of methods for opening graphene band gap, comprising the following steps: prepares gallium oxide respectively
Layer and graphene layer；Graphene layer is transferred on gallium oxide layer, is changed by the electric charge transfer between gallium oxide and graphene
The electronic structure of graphene forms gallium oxide/graphene hetero-junctions, realizes the opening of graphene band gap.
Preferably, the gallium oxide layer is through the following steps that obtained:
Substrate is subjected to cleaning pretreatment, and grows gallium oxide layer on cleaning pretreated substrate.
Preferably, the substrate is Sapphire Substrate, silicon substrate or quartz substrate.
Preferably, the gallium oxide layer is grown in the sapphire substrate surface by following steps:
Sapphire Substrate successively passes through acetone, dehydrated alcohol and deionized water cleaning, and pretreated Sapphire Substrate is made；
The pretreated Sapphire Substrate is placed on the pallet of rotation, control pressure is 10-1Pa is warming up to 700 DEG C；It has heated up
Cheng Hou is successively passed through nitrogen, oxygen and carries Ga (C2H5)3Argon gas so that sapphire substrate surface grow gallium oxide layer.
Preferably, the temperature-rise period are as follows: keep the subsequent temperature of continuing rising of temperature-resistant 1min after every 50 DEG C of heating.
Preferably, the gallium oxide layer is grown in the surface of silicon by following steps:
S1: silicon substrate successively passes through deionized water, acetone and alcohol washes, and pretreated silicon substrate is made；
S2: the pretreated silicon substrate of S1 is placed in mixed solution I, and 1~3h is grown at a temperature of 80~98 DEG C, is made
Substrate with gallium oxide hydroxide seed layer；The mixed solution I is gallium nitrate and hexa mixed aqueous solution, mixing
Gallium nitrate concentration described in solution I be 0.1~0.6mol/L, hexa concentration described in mixed solution I be 0.5~
1mol/L；
S3: the substrate deionized water for having gallium oxide hydroxide seed layer made from S2 is rinsed, drying, and be placed in mixed
It closes in solution II, 120~180 DEG C, is dried after 2~6h of hydro-thermal reaction, gallium oxide hydroxide nano-array is made；The mixed solution
II is gallium nitrate and hexa mixed aqueous solution, and gallium nitrate concentration described in mixed solution II is 0.05~1mol/L,
Hexa concentration described in mixed solution II is 0.1~0.3mol/L；
S4: gallium oxide hydroxide nano-array made from S3 is annealed, and 650~900 DEG C of annealing temperature, 2~4h of annealing time,
Room temperature is naturally cooled to, beta-gallium oxide nano column array is obtained；
S5: it is thin that unformed gallium oxide is prepared in beta-gallium oxide nano column array made from S4 using magnetically controlled sputter method
Film；By the unformed gallium oxide Thin-film anneal, 650~900 DEG C of annealing temperature, 2~4h of time naturally cools to room temperature, i.e.,
Obtain gallium oxide layer.
Preferably, the gallium oxide layer is grown in the quartz substrate surface by chemical vapour deposition technique.
Preferably, the graphene layer is through the following steps that be made:
Substrate copper foil is put into furnace, hydrogen is passed through and inert gas shielding is heated to 1000 DEG C, equilibrium temperature is kept
Stop being passed through protective gas after 20min, change and be passed through carbon-source gas 30min, the graphene layer on copper foil is made.
Preferably, graphene layer is transferred on gallium oxide layer by following steps:
S1: being spun to graphene layer surface for polymethyl methacrylate (PMMA), and PMMA/ graphene/copper is made in drying
Foil knot；
S2: PMMA/ graphene/copper foil knot is immersed in HCl:H2O2: H2O volume ratio is to go in the mixed solution of 2:1:20
Except PMMA/ graphene is made with the residual of deionized water removal hydrochloric acid and hydrogen peroxide in copper foil；Gallium oxide layer is placed into
The lower section of PMMA/ graphene, 120 DEG C of annealing 20min remove PMMA with acetone so that graphene layer is transferred on gallium oxide layer,
Deionized water cleaning, with being dried with nitrogen, obtains gallium oxide/graphene hetero-junctions.
Compared with prior art, the present invention has the following advantages:
First, graphene is made compared with nanobelt opens band gap with traditional, since the present invention is by hetero-junctions circle
The strong electric charge transfer in face opens graphene band gap to realize, the heterojunction structure of preparation is clear, simple process, in semi-conductor electricity
Sub- devices field has good practicability；
Second, it is compared to using the sandwich structure of BN/graphene/BN and opens the band gap that graphene obtains, this
Inventive structure is simpler, and obtained graphene band gap magnitude is bigger, reaches 0.82eV, this is for being applied to semiconductor for graphene
Field of electronic devices carries out band gap regulation, is obviously improved device performance and current on/off ratio, has great significance.
Detailed description of the invention
Fig. 1 is the flow chart of the method provided by the invention for opening graphene band gap；
Wherein, (a) is to prepare gallium oxide and graphene respectively；(b) PMMA is spun to graphene surface；(c) PMMA turns
Print graphene；(d) gallium oxide/graphene hetero-junctions；
Fig. 2 is the light absorption energy spectrum diagram of graphene in gallium oxide/graphene hetero-junctions.
Description of symbols:
1, the substrate of gallium oxide, 2 gallium oxide layers, the substrate of 3 growth graphenes, 4 graphene layers, 5, PMMA are grown.
Specific embodiment
In order to enable those skilled in the art to more fully understand, technical solution of the present invention is practiced, below with reference to specific
The invention will be further described for embodiment and attached drawing, but illustrated embodiment is not as a limitation of the invention.
Embodiment 1
The embodiment of the present invention 1 refers to, as shown in Figure 1, using sapphire for the technology growth gallium oxide of substrate, using change
It learns vapor deposition CVD method and prepares graphene, then transfer graphene to gallium oxide layer with transfer method, complete gallium oxide/stone
Black alkene (Ga2O3/ graphene) hetero-junctions preparation, effectively open graphene band gap.
Step 1 pre-processes Sapphire Substrate；
(1) it will be cut into 1 × 1cm first2Sapphire Substrate be placed in acetone soln and be cleaned by ultrasonic 10min, to remove
The organic matter of substrate surface attachment；
(2) then cleaning solution is changed into dehydrated alcohol, the same 10min that is cleaned by ultrasonic is to remove remaining acetone on substrate
Solution；
It (3) finally will also ultrasound removes cleaning 10min, the remaining ethyl alcohol of removal substrate surface and particle in deionized water again；
After above three step is completed, need as early as possible to be dried up substrate with high pure nitrogen, and be put into life within the shortest time
Long room avoids the secondary pollution of substrate surface to greatest extent；
Step 2 grows gallium oxide layer；
(1) it after the Sapphire Substrate after cleaning being put into reaction chamber, opens vacuum pump and reaction chamber is vacuumized；
(2) when the indoor pressure of reaction drops to 10-1When the Pa order of magnitude, variable-frequency governor power supply is opened, makes to be loaded with substrate
Pallet is rotated with the speed of 10r/s, and the rotation of pallet can be such that substrate is heated evenly, and is also beneficial to growth more even uniform
Film；
(3) while pallet rotates, the power supply of heating module is opened, starts to be heat-treated substrate, heat treatment
Temperature is 700 DEG C, in order to guarantee resistive heater in temperature-rise period by thermal balance, using staged heating mode, i.e., every liter
50 DEG C of pause 1min of temperature, continue to heat up, later until temperature reaches predetermined value；
(4) after temperature-rise period is completed, it is passed through high-purity nitrogen into reaction chamber, opens chamber pressure control at the same time
Device processed, cooperation ball electromagnetic valve can will react indoor pressure control in 3500Pa；
(5) Ar gas control terminal is opened, Ga (C is regulated according to setup parameter2H5)3Carrier gas flux, make carrier gas stabilization be passed through
Organic bottle in a steady stream, and extracted out through auxiliary air passage, it is therefore an objective to stablize the flow 50sccm of organic source gas before growth；
(6) O is opened2Control terminal adjusts its flow value and reaches 50sccm to reaction chamber with oxygen is passed through；
(7) the Ar gas for carrying organic source is entered into reaction chamber by spray gun, growth course starts, continued propagation 60min；
(8) after growing into the predetermined time, organic source is cut out into vacuum chamber, closes organic source gas circuit, by heater strip temperature by
Step drops to room temperature, stops pallet rotation, and stopping is passed through O2, vacuum valve is closed after temperature drops to room temperature, it is straight to be passed through high pure nitrogen
When maintaining an equal level to reaction intraventricular pressure with the external world by force, epitaxial wafer is taken out；
Step 3 prepares graphene layer and is transferred to gallium oxide layer；
(1) substrate copper foil is put into furnace, is passed through hydrogen and argon gas or nitrogen protection is heated to 1000 DEG C, stablizes temperature
Degree keeps 20min；
(2) then stop being passed through protective gas, change and be passed through carbon source (such as methane) gas 30min, reaction is completed；
(3) it cuts off the power, closes methane gas, then be passed through protective gas and empty methane gas, in the environment of protective gas
Down until pipe is cooled to room temperature, metal foil is taken out, the graphene on metal foil is obtained；
(4) then use sol evenning machine that will be spun to graphene surface as the PMMA of support and carrier, then 100 DEG C of heating
5min dries PMMA；
(5) PMMA/ graphene/copper foil knot is immersed in HCl:H2O2: H2O volume ratio is 10min in the solution of 2:1:20,
Remove copper foil；
(6) residual of demineralizing acid and hydrogen peroxide is gone using deionized water, using PET aseptic plastic piece, it is smooth general
PMMA/ graphene, which is put into acetone, impregnates 20min, is then cleaned with deionized water, with being dried with nitrogen；
(7) substrate and gallium oxide layer that step 2 prepares gently are placed into the lower section of PMMA/ graphene, 120 DEG C of annealing
Then 20min removes PMMA with acetone, is finally cleaned up with deionized water so that graphene is completely combined with gallium oxide, use
It is dried with nitrogen, obtains Ga2O3/ graphene hetero-junctions.
Embodiment 2
The embodiment of the present invention 2 refers to, using silicon substrate technology growth gallium oxide, using chemical vapor deposition CVD method
Graphene is prepared, then transfers graphene to gallium oxide layer with transfer method, completes hetero-junctions Ga2O3The preparation of/graphene,
Utilize the available Ga of preparation method of the invention2O3/ graphene hetero-junctions effectively opens graphene band gap.
Step 1 pre-processes silicon substrate；
Silicon substrate is respectively put into detergent, deionized water, acetone, in alcoholic solution, is cleaned by ultrasonic 20min respectively,
Cleaned silicon substrate is obtained, for use；
Step 2 grows gallium oxide layer；
(1) immersion method prepares GaOOH seed layer: immersion method configures gallium nitrate and hexa mixed solution, by institute
It is placed in mixed solution and is grown downwards with substrate growth；Wherein, gallium nitrate concentration is 0.1mol/L, hexa-methylene four
Amine concentration is 0.5mol/L, and mixed solution dosage is on the basis of meeting substrate and sufficiently grow GaOOH seed layer, mixed solution herein
Total volume is 30mL, and bath temperature is that 80 DEG C of growth times are 1h；
(2) substrate with seed layer for obtaining step (1) after being rinsed with deionized water, is put into baking oven in 150 DEG C of temperature
The lower drying of degree, is then placed in hydro-thermal mixed solution and reacts, and Temperature fall after reaction takes out substrate, and deionized water is rinsed, and puts
Enter 150 DEG C of baking oven drying, obtains gallium oxide hydroxide nano-array, wherein in hydro-thermal mixed solution, Ga (NO3)3Concentration is
0.05mol/L, hexa concentration be 0.1mol/L, volume 30mL, 120 DEG C of hydro-thermal temperature, hydro-thermal time 2h；
(3) the gallium oxide hydroxide nano-array for obtaining step (2), is put into annealing furnace and anneals, and 650 DEG C of annealing temperature,
Annealing time 2h, then naturally cools to room temperature, obtains beta-gallium oxide nano column array；
(4) it the unformed gallium oxide film of room temperature growth: is utilized on the beta-gallium oxide nano column array obtained in step (3)
Magnetically controlled sputter method prepares unformed gallium oxide film, and target used is gallium oxide target, sputtering power 160W, sputtering pressure
For 0.8Pa, total gas flow rate 40sccm, wherein oxygen flow is 2sccm, and substrate does not heat in sputtering process, growth time
For 2h；
(5) high annealing obtains beta-gallium oxide film: the unformed gallium oxide film that step (4) is obtained is put into annealing
Furnace annealing, naturally cools to room temperature then to get beta-gallium oxide film is arrived by 650 DEG C of annealing temperature, time 2h；
Step 3 prepares graphene layer and is transferred to gallium oxide layer；
(1) substrate copper foil is put into furnace, is passed through hydrogen and argon gas or nitrogen protection is heated to 1000 DEG C, stablizes temperature
Degree keeps 20min；
(2) then stop being passed through protective gas, change and be passed through carbon source (such as methane) gas 30min, reaction is completed；
(3) it cuts off the power, closes methane gas, then be passed through protective gas and empty methane gas, in the environment of protective gas
Down until pipe is cooled to room temperature, metal foil is taken out, the graphene on metal foil is obtained.
(4) then use sol evenning machine that will be spun to graphene surface as the PMMA of support and carrier, then 100 DEG C of heating 5
Minute, dry PMMA；
(5) PMMA/ graphene/copper foil knot is immersed in HCl:H2O2: H2O volume ratio is 10min in the solution of 2:1:20,
Remove copper foil；
(6) residual of demineralizing acid and hydrogen peroxide is gone using deionized water, using PET aseptic plastic piece, it is smooth general
PMMA/ graphene, which is put into acetone, impregnates 20min, is then cleaned with deionized water, with being dried with nitrogen；
(7) substrate and gallium oxide layer that step 2 prepares gently are placed into the lower section of PMMA/ graphene, 120 DEG C are moved back
Then fire 20 minutes removes PMMA with acetone so that graphene is completely combined with gallium oxide, finally cleaned with deionized water dry
Only, with being dried with nitrogen, Ga is obtained2O3/ graphene hetero-junctions.
Embodiment 3
Preparation method with embodiment 2, the difference is that:
Step 2 grows gallium oxide layer
(1) gallium nitrate concentration is 0.6mol/L, and hexa concentration is 1mol/L, and mixed solution total volume is
30mL, bath temperature are that 98 DEG C of growth times are 3h；
(2)Ga(NO3)3Concentration is 1mol/L, and hexa concentration is 0.3mol/L, volume 30mL, hydro-thermal temperature
180 DEG C, hydro-thermal time 6h；
(3) 900 DEG C of annealing temperature, annealing time 4h；
(4) sputtering power be 220W, sputtering pressure 1.6Pa, total gas flow rate 42sccm, wherein oxygen flow be
5sccm, substrate does not heat in sputtering process, growth time 4h；
(5) 900 DEG C of annealing temperature, time 4h.
Embodiment 4
Preparation method with embodiment 2, the difference is that:
Step 2 grows gallium oxide layer
(1) gallium nitrate concentration is 0.4mol/L, and hexa concentration is 0.7mol/L, and mixed solution total volume is
30mL, bath temperature are that 90 DEG C of growth times are 2h；
(2)Ga(NO3)3Concentration is 0.07mol/L, and hexa concentration is 0.2mol/L, volume 30mL, hydro-thermal
150 DEG C of temperature, hydro-thermal time 4h；
(3) 700 DEG C of annealing temperature, annealing time 3h；
(4) sputtering power be 180W, sputtering pressure 1.2Pa, total gas flow rate 41sccm, wherein oxygen flow be
3sccm, substrate does not heat in sputtering process, growth time 3h；
(5) 750 DEG C of annealing temperature, time 3h.
Embodiment 5
The embodiment of the present invention 3 refers to, uses quartz to prepare gallium oxide for the technology of substrate, using chemical vapor deposition
CVD method prepares graphene, then transfers graphene to gallium oxide layer with transfer method, completes hetero-junctions Ga2O3/graphene
Preparation, utilize the available Ga of preparation method of the invention2O3/ graphene hetero-junctions effectively opens graphene band gap.
Step 1 pre-processes quartz substrate；
Quartz substrate is cleaned, and use is dried with nitrogen；
Step 2 grows gallium oxide layer；
(1) quartz substrate is placed on quartz boat, the quartz boat is placed in the chemical vapor depsotition equipment
In reaction chamber at suitable position, the reaction chamber valve is closed；
(2) by gallium oxide powder be placed in the quartz boat and the chemical vapor depsotition equipment reaction chamber air inlet port it
Between, and at 8~12cm of quartz boat；
(3) gas circuit is opened, so that the mixed gas of inert gas and oxygen is continually fed into the reaction chamber, makes gallium oxide film
It is grown in quartz substrate；
Step 3 prepares graphene layer and is transferred to gallium oxide layer；
(1) substrate copper foil is put into furnace, is passed through hydrogen and argon gas or nitrogen protection is heated to 1000 DEG C, stablizes temperature
Degree keeps 20min；
(2) then stop being passed through protective gas, change and be passed through carbon source (such as methane) gas 30min, reaction is completed；
(3) it cuts off the power, closes methane gas, then be passed through protective gas and empty methane gas, in the environment of protective gas
Down until pipe is cooled to room temperature, metal foil is taken out, the graphene on metal foil is obtained；
(4) then use sol evenning machine that will be spun to graphene surface as the PMMA of support and carrier, then 100 DEG C of heating
5min dries PMMA；
(5) PMMA/ graphene/copper foil knot is immersed in HCl:H2O2: H2O volume ratio is 10 minutes in the solution of 2:1:20,
Remove copper foil；
(6) residual of demineralizing acid and hydrogen peroxide is gone using deionized water, using PET aseptic plastic piece, it is smooth general
PMMA/ graphene, which is put into acetone, impregnates 20min, is then cleaned with deionized water, with being dried with nitrogen；
(7) substrate and gallium oxide layer that step 2 prepares gently are placed into the lower section of PMMA/ graphene, 120 DEG C of annealing
Then 20min removes PMMA with acetone, is finally cleaned up with deionized water so that graphene is completely combined with gallium oxide, use
It is dried with nitrogen, obtains Ga2O3/ graphene hetero-junctions.
Ga prepared by above-described embodiment 1~52O3/ graphene hetero-junctions performance is approximate, provided by the invention in order to prove
The method for opening graphene band gap can obtain biggish graphene band gap magnitude, below by taking above-described embodiment 1 as an example, carry out band gap
Value measurement, the specific test method is as follows: spectrophotometer runs software opened, spectral scanning range is set as 190~700nm,
Scanning step is 1nm, and scanning mode is transmissivity；The Ga that embodiment 1 is prepared2O3/ graphene hetero-junctions substrate is placed
In sample cell, baseline scan is first done.Then to Ga2O3The plating waxing of/graphene hetero-junctions substrate, then it is placed in sample cell, it carries out
Spectral scan, to obtain transmitted spectrum；Transmissivity is converted into absorbance by the function that software carries；By absorbance with
The proportional relation and absorption coefficient of absorption coefficient and the relationship of photon energy, fit the optical band gap of sample, specific to detect
As a result as shown in Fig. 2, the band gap being calculated is 0.82eV.
Graphene is made compared with nanobelt opens band gap with traditional, since the present invention is strong by heterojunction boundary
Electric charge transfer come realize open graphene band gap, the heterojunction structure of preparation is clear, simple process, in semi-conductor electronic device
There is good practicability in field；It is compared to and is obtained to open graphene using the sandwich structure of BN/graphene/BN
Band gap (graphene band gap magnitude 0.16eV), structure of the invention is simpler, and obtained graphene band gap magnitude is bigger, reaches
0.82eV, this carries out band gap regulation for graphene is applied to semi-conductor electronic device field, be obviously improved device performance and
Current on/off ratio has great significance.
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by those skilled in the art
Mind and range.In this way, if these modifications and changes of the present invention belongs to the range of the claims in the present invention and its equivalent technologies
Within be also intended to include these modifications and variations.
Claims (9)
1. a kind of method for opening graphene band gap, which comprises the following steps: prepare gallium oxide layer and graphite respectively
Alkene layer；Graphene layer is transferred on gallium oxide layer, graphene is changed by the electric charge transfer between gallium oxide and graphene
Electronic structure forms gallium oxide/graphene hetero-junctions, realizes the opening of graphene band gap.
2. it is according to claim 1 open graphene band gap method, which is characterized in that the gallium oxide layer be by with
Made from lower step:
Substrate is subjected to cleaning pretreatment, and grows gallium oxide layer on cleaning pretreated substrate.
3. the method according to claim 2 for opening graphene band gap, which is characterized in that the substrate is sapphire lining
Bottom, silicon substrate or quartz substrate.
4. the method according to claim 3 for opening graphene band gap, which is characterized in that the gallium oxide layer passes through following
Step is grown in the sapphire substrate surface:
Sapphire Substrate successively passes through acetone, dehydrated alcohol and deionized water cleaning, and pretreated Sapphire Substrate is made；By institute
It states pretreated Sapphire Substrate to be placed on the pallet of rotation, control pressure is 10-1Pa is warming up to 700 DEG C；Heating is completed
Afterwards, nitrogen, oxygen are successively passed through and carries Ga (C2H5)3Argon gas so that sapphire substrate surface grow gallium oxide layer.
5. the method according to claim 4 for opening graphene band gap, which is characterized in that the temperature-rise period are as follows: every liter
The subsequent temperature of continuing rising of temperature-resistant 1min is kept after 50 DEG C of temperature.
6. the method according to claim 3 for opening graphene band gap, which is characterized in that the gallium oxide layer passes through following
Step is grown in the surface of silicon:
S1: silicon substrate successively passes through deionized water, acetone and alcohol washes, and pretreated silicon substrate is made；
S2: the pretreated silicon substrate of S1 is placed in mixed solution I, and 1~3h is grown at a temperature of 80~98 DEG C, is made and is had
The substrate of gallium oxide hydroxide seed layer；The mixed solution I is gallium nitrate and hexa mixed aqueous solution, mixed solution
Gallium nitrate concentration described in I is 0.1~0.6mol/L, and hexa concentration described in mixed solution I is 0.5~1mol/
L；
S3: the substrate deionized water that gallium oxide hydroxide seed layer is had made from S2 is rinsed, drying, and it is molten to be placed in mixing
In liquid II, 120~180 DEG C, dries after 2~6h of hydro-thermal reaction, gallium oxide hydroxide nano-array is made；The mixed solution II is
Gallium nitrate and hexa mixed aqueous solution, gallium nitrate concentration described in mixed solution II are 0.05~1mol/L, mixing
Hexa concentration described in solution II is 0.1~0.3mol/L；
S4: gallium oxide hydroxide nano-array made from S3 is annealed, 650~900 DEG C of annealing temperature, 2~4h of annealing time, natural
It is cooled to room temperature, obtains beta-gallium oxide nano column array；
S5: unformed gallium oxide film is prepared in beta-gallium oxide nano column array made from S4 using magnetically controlled sputter method；
By the unformed gallium oxide Thin-film anneal, 650~900 DEG C of annealing temperature, 2~4h of time naturally cools to room temperature to get arriving
Gallium oxide layer.
7. the method according to claim 3 for opening graphene band gap, which is characterized in that the gallium oxide layer passes through chemistry
Vapour deposition process is grown in the quartz substrate surface.
8. it is according to claim 1 open graphene band gap method, which is characterized in that the graphene layer be by with
Lower step is made:
Substrate copper foil is put into furnace, hydrogen is passed through and inert gas shielding is heated to 1000 DEG C, equilibrium temperature is kept
Stop being passed through protective gas after 20min, change and be passed through carbon-source gas 30min, the graphene layer on copper foil is made.
9. the method according to claim 1 for opening graphene band gap, which is characterized in that graphene layer passes through following steps
It is transferred on gallium oxide layer:
S1: being spun to graphene layer surface for polymethyl methacrylate, drying, and obtained polymethyl methacrylate/graphene/
Copper foil knot；
S2: polymethyl methacrylate/graphene/copper foil knot is immersed in HCl:H2O2: H2O volume ratio is the mixing of 2:1:20
In solution, copper foil is removed, with the residual of deionized water removal hydrochloric acid and hydrogen peroxide, polymethyl methacrylate/graphite is made
Alkene；Gallium oxide layer is placed into polymethyl methacrylate/graphene lower section, 120 DEG C of annealing 20min, so that graphene layer
It is transferred on gallium oxide layer, removes polymethyl methacrylate with acetone, deionized water cleaning with being dried with nitrogen, is aoxidized
Gallium/graphene hetero-junctions.
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