CN110429026B - Method for opening graphene band gap - Google Patents
Method for opening graphene band gap Download PDFInfo
- Publication number
- CN110429026B CN110429026B CN201910752677.3A CN201910752677A CN110429026B CN 110429026 B CN110429026 B CN 110429026B CN 201910752677 A CN201910752677 A CN 201910752677A CN 110429026 B CN110429026 B CN 110429026B
- Authority
- CN
- China
- Prior art keywords
- graphene
- gallium oxide
- substrate
- layer
- oxide layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/186—Preparation by chemical vapour deposition [CVD]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02115—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material being carbon, e.g. alpha-C, diamond or hydrogen doped carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
Abstract
The invention discloses a method for opening a graphene band gap, which belongs to the technical field of semiconductor electronics and comprises the following steps: respectively preparing a gallium oxide layer and a graphene layer; transferring the graphene layer to a gallium oxide layer, changing the electronic structure of graphene through charge transfer between gallium oxide and graphene, forming a gallium oxide/graphene heterojunction, and realizing opening of a graphene band gap; the method for opening the graphene band gap is simple in preparation process, clear in device structure, capable of effectively opening the graphene band gap to a large extent, and significant in application of graphene to the field of semiconductor electronic devices.
Description
Technical Field
The invention belongs to the technical field of semiconductor electronics, and particularly relates to a method for opening a graphene band gap.
Background
Graphene, a single-layer two-dimensional crystal, has excellent physical properties such as ultrahigh carrier mobility, monatomic layer thickness and ultrahigh mechanical strength and flexibility, has a very good potential application value in the future semiconductor field, and has attracted extensive attention of people. However, since graphene does not have a band gap, graphene cannot be directly applied to the field of semiconductor electronic devices, and in order to realize application of graphene in the field of semiconductor electronic devices, the problem of opening the band gap of graphene needs to be solved first. The current common method for opening the graphene band gap is to cut graphene into a nanobelt, so that the graphene band gap is opened. Although the band gap of the graphene can be opened by cutting the graphene into the nanobelts, and the narrower the width of the nanobelts, the larger the opened band gap is, the narrower the width of the nanobelts is, the smaller the carried driving current is, and the practical application of the graphene is greatly limited.
The published article "Tunable and foldable band gap of single-layer graphene sandwiched between two hexagonal boron nitride" (NPG Asia Materials (2012)4, e 16; doi: 10.1038/am.2012.29; published online 27April 2012) by Ruge Quhe et al suggests a sandwich structure of BN/graphene/BN, i.e. graphene is sandwiched between planar hexagonal BN sheets, and it was found that graphene can open a band gap of 0.16eV in a suitable stacking manner. If a vertical electric field is applied to the BN/graphene/BN composite structure, the band gap can be further increased to 0.34 eV. Although the band gap of the graphene is opened, the opened band gap value is small, and the method is not enough to be applied to electronic devices at room temperature, so that the wide application of the graphene is still greatly limited. Therefore, how to provide a simple and effective method to open the graphene band gap as much as possible is of great significance to the application of graphene in the field of semiconductors.
Disclosure of Invention
The invention aims to provide a method for opening a graphene band gap aiming at the defects in the prior art, which is simple to operate and can open the graphene band gap to a greater extent, so that the application of graphene in the field of semiconductor electronic devices is realized.
The invention aims to provide a method for opening a graphene band gap, which comprises the following steps: respectively preparing a gallium oxide layer and a graphene layer; and transferring the graphene layer to a gallium oxide layer, changing the electronic structure of the graphene through charge transfer between the gallium oxide and the graphene, forming a gallium oxide/graphene heterojunction, and opening the graphene band gap.
Preferably, the gallium oxide layer is prepared by the following steps:
and cleaning and pretreating the substrate, and growing a gallium oxide layer on the cleaned and pretreated substrate.
Preferably, the substrate is a sapphire substrate, a silicon substrate, or a quartz substrate.
Preferably, the gallium oxide layer is grown on the surface of the sapphire substrate by the following steps:
cleaning the sapphire substrate with acetone, absolute ethyl alcohol and deionized water in sequence to prepare a pretreated sapphire substrate; placing the pretreated sapphire substrate on a rotating tray, and controlling the pressure to be 10-1Pa, heating to 700 ℃; after the temperature rise is finished, introducing nitrogen, oxygen and Ga (C) carried in sequence2H5)3And (4) enabling the surface of the sapphire substrate to grow a gallium oxide layer.
Preferably, the temperature raising process is as follows: keeping the temperature unchanged for 1min after heating to 50 ℃ every time, and then continuing heating.
Preferably, the gallium oxide layer is grown on the surface of the silicon substrate by the following steps:
s1: cleaning the silicon substrate with deionized water, acetone and alcohol in sequence to obtain a pretreated silicon substrate;
s2: placing the silicon substrate pretreated by the S1 into the mixed solution I, and growing for 1-3 h at the temperature of 80-98 ℃ to obtain a substrate with a gallium oxyhydroxide seed layer; the mixed solution I is a mixed water solution of gallium nitrate and hexamethylenetetramine, the concentration of the gallium nitrate in the mixed solution I is 0.1-0.6 mol/L, and the concentration of the hexamethylenetetramine in the mixed solution I is 0.5-1 mol/L;
s3: washing the substrate with the hydroxyl gallium oxide seed layer prepared in the step S2 with deionized water, drying, placing the substrate in a mixed solution II, carrying out hydrothermal reaction at the temperature of 120-180 ℃ for 2-6 h, and drying to prepare a hydroxyl gallium oxide nano array; the mixed solution II is a mixed water solution of gallium nitrate and hexamethylenetetramine, the concentration of the gallium nitrate in the mixed solution II is 0.05-1 mol/L, and the concentration of the hexamethylenetetramine in the mixed solution II is 0.1-0.3 mol/L;
s4: annealing the hydroxyl gallium oxide nano-array prepared in the step S3 at the annealing temperature of 650-900 ℃ for 2-4 h, and naturally cooling to room temperature to obtain a beta-gallium oxide nano-column array;
s5: preparing the beta-gallium oxide nano-pillar array prepared by the S4 by using a magnetron sputtering method to obtain an amorphous gallium oxide film; and annealing the amorphous gallium oxide film at 650-900 ℃ for 2-4 h, and naturally cooling to room temperature to obtain the gallium oxide layer.
Preferably, the gallium oxide layer is grown on the surface of the quartz substrate by a chemical vapor deposition method.
Preferably, the graphene layer is prepared by the following steps:
and (3) putting the substrate copper foil into a furnace, introducing hydrogen and inert gas for protection, heating to 1000 ℃, stabilizing the temperature, keeping for 20min, stopping introducing the protective gas, and introducing a carbon source gas for 30min to prepare the graphene layer on the copper foil.
Preferably, the graphene layer is transferred onto the gallium oxide layer by:
s1: spin-coating polymethyl methacrylate (PMMA) on the surface of the graphene layer, and drying to obtain a PMMA/graphene/copper foil junction;
s2: soaking the PMMA/graphene/copper foil knot in HCl: h2O2：H2Removing the copper foil in the mixed solution with the volume ratio of O being 2:1:20, and removing the residues of hydrochloric acid and hydrogen peroxide by using deionized water to prepare PMMA/graphene; and placing the gallium oxide layer below the PMMA/graphene, annealing at 120 ℃ for 20min to transfer the graphene layer onto the gallium oxide layer, removing the PMMA with acetone, washing with deionized water, and drying with nitrogen to obtain the gallium oxide/graphene heterojunction.
Compared with the prior art, the invention has the following beneficial effects:
firstly, compared with the traditional method for preparing graphene into a nanobelt open band gap, the method has the advantages that the graphene band gap is opened through strong charge transfer of a heterojunction interface, so that the prepared heterojunction has a clear structure and a simple process, and has good practicability in the field of semiconductor electronic devices;
secondly, compared with the method that the band gap obtained by graphene is opened by utilizing a BN/graphene/BN sandwich structure, the method is simpler in structure, the band gap value of the obtained graphene is larger and reaches 0.82eV, and the method has important significance for applying the graphene to the field of semiconductor electronic devices, regulating and controlling the band gap and remarkably improving the device performance and the current on-off ratio.
Drawings
Fig. 1 is a flow chart of a method for opening a graphene bandgap according to the present invention;
wherein (a) gallium oxide and graphene are respectively prepared; (b) spin-coating PMMA on the surface of graphene; (c) transferring graphene by PMMA; (d) a gallium oxide/graphene heterojunction;
fig. 2 is a spectrum of light absorption energy of graphene in a gallium oxide/graphene heterojunction.
Description of reference numerals:
1. the substrate of growing gallium oxide, 2 gallium oxide layers, 3 the substrate of growing graphite alkene, 4 graphene layers, 5, PMMA.
Detailed Description
In order to make the technical solutions of the present invention better understood and implemented by those skilled in the art, the present invention is further described below with reference to the following specific embodiments and the accompanying drawings, but the embodiments are not meant to limit the present invention.
Example 1
Example 1 of the present invention is a process in which, as shown in fig. 1, gallium oxide is grown using a sapphire substrate technique, graphene is prepared using a chemical vapor deposition CVD method, and the graphene is transferred to a gallium oxide layer using a transfer method, thereby completing gallium oxide/graphene (Ga)2O3Graphene) heterojunction, and a graphene band gap is effectively opened.
(1) first, the cut pieces are cut into 1X 1cm2The sapphire substrate is placed in an acetone solution for ultrasonic cleaning for 10min to remove organic matters attached to the surface of the substrate;
(2) then, the cleaning solution is changed into absolute ethyl alcohol, and ultrasonic cleaning is carried out for 10min to remove the residual acetone solution on the substrate;
(3) finally, ultrasonic cleaning is carried out in deionized water for 10min, and residual ethanol and particles on the surface of the substrate are removed;
after the three steps are completed, the substrate needs to be blown dry by high-purity nitrogen as soon as possible, and the substrate is placed into a growth chamber in the shortest time, so that secondary pollution on the surface of the substrate is avoided to the maximum extent;
step 2, growing a gallium oxide layer;
(1) after the cleaned sapphire substrate is placed into a reaction chamber, opening a vacuum pump to vacuumize the reaction chamber;
(2) when the pressure in the reaction chamber is reduced to 10-1When the Pa magnitude is in an order of magnitude, a power supply of the variable-frequency speed regulator is turned on, so that the tray loaded with the substrate rotates at the speed of 10r/s, the rotation of the tray can enable the substrate to be heated uniformly, and the growth of a more smooth and uniform film is facilitated;
(3) turning on a power supply of the heating module while the tray rotates, starting to perform heat treatment on the substrate, wherein the temperature of the heat treatment is 700 ℃, and in order to ensure the heating balance of the heating resistance wire in the heating process, adopting a stepped heating mode, namely pausing for 1min every time when the temperature is increased by 50 ℃, and continuing to heat until the temperature reaches a preset value;
(4) after the temperature rise process is finished, introducing high-purity nitrogen into the reaction chamber, simultaneously opening a pressure controller of the reaction chamber, and controlling the pressure in the reaction chamber to be 3500Pa by matching with a spherical electromagnetic valve;
(5) opening the Ar gas control end, and adjusting Ga (C) according to set parameters2H5)3The carrier gas flow is led into the organic source bottle stably and is extracted through the auxiliary gas circuit, so that the flow of the organic source gas is stabilized to be 50sccm before growth;
(6) opening of O2The control end is used for introducing oxygen into the reaction chamber and adjusting the flow value to 50 sccm;
(7) ar gas carrying an organic source enters a reaction chamber through a spray gun, and the growth process is started and continues to grow for 60 min;
(8) cutting the organic source into a vacuum chamber after the organic source grows to the preset time, closing the gas circuit of the organic source, gradually reducing the temperature of the heating wire to the room temperature, stopping the rotation of the tray, and stopping introducing O2When the temperature is reduced to room temperature, closing the vacuum valve, introducing high-purity nitrogen until the pressure in the reaction chamber is kept level with the outside, and taking out the epitaxial wafer;
(1) putting the substrate copper foil into a furnace, introducing hydrogen and argon or nitrogen for protection, heating to 1000 ℃, stabilizing the temperature, and keeping the temperature for 20 min;
(2) then stopping introducing the protective gas, and introducing carbon source (such as methane) gas for 30min to complete the reaction;
(3) cutting off a power supply, closing methane gas, introducing protective gas to exhaust the methane gas, taking out the metal foil in the environment of the protective gas until the temperature of the pipe is cooled to room temperature, and obtaining graphene on the metal foil;
(4) spin-coating PMMA serving as a support and a carrier on the surface of the graphene by using a spin coater, heating at 100 ℃ for 5min, and drying the PMMA;
(5) soaking the PMMA/graphene/copper foil knot in HCl: h2O2：H2Removing the copper foil in a solution with the volume ratio of O being 2:1:20 for 10 min;
(6) removing residues of hydrochloric acid and hydrogen peroxide by using deionized water, flatly placing PMMA/graphene into acetone by using a PET sterile plastic sheet for soaking for 20min, then cleaning by using deionized water, and drying by using nitrogen;
(7) gently placing the substrate and the gallium oxide layer prepared in the step 2 below the PMMA/graphene, annealing at 120 ℃ for 20min to enable the graphene and the gallium oxide to be completely combined, removing the PMMA with acetone, finally cleaning with deionized water, and drying with nitrogen to obtain Ga2O3A/graphene heterojunction.
Example 2
Example 2 of the present invention is a method of growing gallium oxide using a silicon substrate technique, preparing graphene using a chemical vapor deposition CVD method, transferring the graphene to a gallium oxide layer using a transfer method, and completing a heterojunction Ga2O3Preparation of graphene Ga obtainable by the preparation method of the invention2O3The/graphene heterojunction effectively opens the graphene band gap.
respectively putting the silicon substrate into a detergent, deionized water, acetone and an alcohol solution, and respectively ultrasonically cleaning for 20min to obtain a cleaned silicon substrate for later use;
step 2, growing a gallium oxide layer;
(1) preparing a GaOOH seed layer by a water bath method: preparing a mixed solution of gallium nitrate and hexamethylenetetramine by a water bath method, and placing the growth surface of the substrate downwards in the mixed solution for growth; wherein the concentration of gallium nitrate is 0.1mol/L, the concentration of hexamethylenetetramine is 0.5mol/L, the dosage of the mixed solution is based on the requirement of fully growing a GaOOH seed layer on the substrate, the total volume of the mixed solution is 30mL, and the growth time is 1h when the water bath temperature is 80 ℃;
(2) carrying out seed layer on the obtained product in the step (1)Washing the substrate with deionized water, drying in an oven at 150 ℃, then placing the substrate in a hydrothermal mixed solution for reaction, naturally cooling after the reaction, taking out the substrate, washing with deionized water, and drying in the oven at 150 ℃ to obtain the gallium oxyhydroxide nano-array, wherein in the hydrothermal mixed solution, Ga (NO) is in a mixed solution3)3The concentration is 0.05mol/L, the concentration of hexamethylenetetramine is 0.1mol/L, the volume is 30mL, the hydrothermal temperature is 120 ℃, and the hydrothermal time is 2 h;
(3) putting the hydroxyl gallium oxide nano-array obtained in the step (2) into an annealing furnace for annealing at the annealing temperature of 650 ℃ for 2 hours, and then naturally cooling to room temperature to obtain a beta-gallium oxide nano-column array;
(4) growing an amorphous gallium oxide film at room temperature: preparing an amorphous gallium oxide film on the beta-gallium oxide nano-pillar array obtained in the step (3) by using a magnetron sputtering method, wherein the used target is a gallium oxide target, the sputtering power is 160W, the sputtering pressure is 0.8Pa, the total gas flow is 40sccm, the oxygen flow is 2sccm, the substrate is not heated in the sputtering process, and the growth time is 2 hours;
(5) annealing at high temperature to obtain a beta-gallium oxide film: putting the amorphous gallium oxide film obtained in the step (4) into an annealing furnace for annealing at the annealing temperature of 650 ℃ for 2 hours, and then naturally cooling to room temperature to obtain a beta-gallium oxide film;
(1) putting the substrate copper foil into a furnace, introducing hydrogen and argon or nitrogen for protection, heating to 1000 ℃, stabilizing the temperature, and keeping the temperature for 20 min;
(2) then stopping introducing the protective gas, and introducing carbon source (such as methane) gas for 30min to complete the reaction;
(3) and cutting off a power supply, closing the methane gas, introducing protective gas to exhaust the methane gas, taking out the metal foil in the environment of the protective gas until the temperature of the pipe is cooled to the room temperature, and obtaining the graphene on the metal foil.
(4) Spin-coating PMMA serving as a support and a carrier on the surface of the graphene by using a spin coater, heating at 100 ℃ for 5 minutes, and drying the PMMA;
(5) soaking the PMMA/graphene/copper foil knot in HCl: h2O2：H2Removing the copper foil in a solution with the volume ratio of O being 2:1:20 for 10 min;
(6) removing residues of hydrochloric acid and hydrogen peroxide by using deionized water, flatly placing PMMA/graphene into acetone by using a PET sterile plastic sheet for soaking for 20min, then cleaning by using deionized water, and drying by using nitrogen;
(7) gently placing the substrate and the gallium oxide layer prepared in the second step below the PMMA/graphene, annealing at 120 ℃ for 20 minutes to enable the graphene and the gallium oxide to be completely combined, removing the PMMA with acetone, finally cleaning with deionized water, and drying with nitrogen to obtain Ga2O3A/graphene heterojunction.
Example 3
The preparation method is the same as example 2, except that:
step 2, growing a gallium oxide layer
(1) The concentration of gallium nitrate is 0.6mol/L, the concentration of hexamethylenetetramine is 1mol/L, the total volume of the mixed solution is 30mL, and the growth time is 3h when the water bath temperature is 98 ℃;
(2)Ga(NO3)3the concentration is 1mol/L, the concentration of hexamethylenetetramine is 0.3mol/L, the volume is 30mL, the hydrothermal temperature is 180 ℃, and the hydrothermal time is 6 h;
(3) the annealing temperature is 900 ℃, and the annealing time is 4 hours;
(4) the sputtering power is 220W, the sputtering pressure is 1.6Pa, the total gas flow is 42sccm, the oxygen flow is 5sccm, the substrate is not heated in the sputtering process, and the growth time is 4 h;
(5) the annealing temperature is 900 ℃ and the time is 4 h.
Example 4
The preparation method is the same as example 2, except that:
step 2, growing a gallium oxide layer
(1) The concentration of gallium nitrate is 0.4mol/L, the concentration of hexamethylenetetramine is 0.7mol/L, the total volume of the mixed solution is 30mL, and the growth time is 2h when the water bath temperature is 90 ℃;
(2)Ga(NO3)3the concentration is 0.07molThe concentration of the hexamethylenetetramine is 0.2mol/L, the volume is 30mL, the hydrothermal temperature is 150 ℃, and the hydrothermal time is 4 h;
(3) the annealing temperature is 700 ℃, and the annealing time is 3 h;
(4) the sputtering power is 180W, the sputtering pressure is 1.2Pa, the total gas flow is 41sccm, the oxygen flow is 3sccm, the substrate is not heated in the sputtering process, and the growth time is 3 h;
(5) the annealing temperature is 750 ℃ and the time is 3 h.
Example 5
Example 3 of the present invention is a method of preparing gallium oxide using a quartz substrate, preparing graphene using a CVD method, transferring the graphene to a gallium oxide layer using a transfer method, and completing a heterojunction Ga2O3Preparation of graphene Ga obtainable by the preparation method of the invention2O3The/graphene heterojunction effectively opens the graphene band gap.
cleaning the quartz substrate, and drying by using nitrogen;
step 2, growing a gallium oxide layer;
(1) placing the quartz substrate on a quartz boat, placing the quartz boat at a proper position in a reaction chamber of the chemical vapor deposition equipment, and closing a valve of the reaction chamber;
(2) placing gallium oxide powder between the quartz boat and an air inlet port of a reaction chamber of the chemical vapor deposition equipment, wherein the distance between the gallium oxide powder and the quartz boat is 8-12 cm;
(3) opening the gas path, and continuously introducing the mixed gas of inert gas and oxygen into the reaction chamber to grow the gallium oxide film on the quartz substrate;
(1) putting the substrate copper foil into a furnace, introducing hydrogen and argon or nitrogen for protection, heating to 1000 ℃, stabilizing the temperature, and keeping the temperature for 20 min;
(2) then stopping introducing the protective gas, and introducing carbon source (such as methane) gas for 30min to complete the reaction;
(3) cutting off a power supply, closing methane gas, introducing protective gas to exhaust the methane gas, taking out the metal foil in the environment of the protective gas until the temperature of the pipe is cooled to room temperature, and obtaining graphene on the metal foil;
(4) spin-coating PMMA serving as a support and a carrier on the surface of the graphene by using a spin coater, heating at 100 ℃ for 5min, and drying the PMMA;
(5) soaking the PMMA/graphene/copper foil knot in HCl: h2O2：H2Removing the copper foil in a solution with the volume ratio of O being 2:1:20 for 10 minutes;
(6) removing residues of hydrochloric acid and hydrogen peroxide by using deionized water, flatly placing PMMA/graphene into acetone by using a PET sterile plastic sheet for soaking for 20min, then cleaning by using deionized water, and drying by using nitrogen;
(7) gently placing the substrate and the gallium oxide layer prepared in the step 2 below the PMMA/graphene, annealing at 120 ℃ for 20min to enable the graphene and the gallium oxide to be completely combined, removing the PMMA with acetone, finally cleaning with deionized water, and drying with nitrogen to obtain Ga2O3A/graphene heterojunction.
Ga prepared in examples 1 to 52O3The performance of the graphene heterojunction is approximate, and in order to prove that the method for opening the bandgap of the graphene provided by the invention can obtain a larger bandgap value of the graphene, the bandgap value is measured by taking the above example 1 as an example, and the specific test method is as follows: opening spectrophotometer operation software, setting the spectrum scanning range to be 190-700 nm, the scanning step length to be 1nm, and the scanning mode to be transmissivity; ga prepared in example 12O3The/graphene heterojunction substrate is placed in a sample cell, and baseline scanning is firstly carried out. Then to Ga2O3Coating wax on a graphene heterojunction substrate, placing the substrate in a sample cell, and performing spectral scanning to obtain a transmission spectrum; converting the transmittance into absorbance through the self-carried function of software; the optical band gap of the sample is fitted through the proportional relation between the absorbance and the absorption coefficient and the relation between the absorption coefficient and the photon energy, the specific detection result is shown in fig. 2, and the calculated band gap is 0.82 eV.
Compared with the traditional method for manufacturing the graphene into the nanobelt open band gap, the method has the advantages that the open of the graphene band gap is realized through the strong charge transfer of the heterojunction interface, the prepared heterojunction has a clear structure and a simple process, and the method has good practicability in the field of semiconductor electronic devices; compared with the band gap (the graphene band gap value is 0.16eV) obtained by opening the graphene by utilizing the BN/graphene/BN sandwich structure, the structure is simpler, the obtained graphene band gap value is larger and reaches 0.82eV, and the method has important significance for applying the graphene to the field of semiconductor electronic devices, regulating the band gap and remarkably improving the device performance and the current on-off ratio.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, it is intended that such changes and modifications be included within the scope of the appended claims and their equivalents.
Claims (4)
1. A method for opening a graphene band gap is characterized by comprising the following steps: respectively preparing a gallium oxide layer and a graphene layer; transferring the graphene layer to a gallium oxide layer, changing the electronic structure of graphene through charge transfer between gallium oxide and graphene, forming a gallium oxide/graphene heterojunction, and realizing opening of a graphene band gap;
the graphene layer is transferred onto the gallium oxide layer by:
s1: spin-coating polymethyl methacrylate on the surface of the graphene layer, and drying to obtain a polymethyl methacrylate/graphene/copper foil junction;
s2: soaking the polymethyl methacrylate/graphene/copper foil junction in HCl: h2O2：H2Removing the copper foil in the mixed solution with the volume ratio of O being 2:1:20, and removing the residues of hydrochloric acid and hydrogen peroxide by using deionized water to prepare polymethyl methacrylate/graphene; placing the gallium oxide layer below the polymethyl methacrylate/graphene, annealing at 120 ℃ for 20min to transfer the graphene layer to the gallium oxide layer, and removing the polymethyl methacrylate layer by using acetoneWashing methyl acrylate with deionized water, and drying by using nitrogen gas to obtain a gallium oxide/graphene heterojunction;
the gallium oxide layer is prepared by the following steps:
cleaning and pretreating a substrate, and growing a gallium oxide layer on the substrate after cleaning and pretreating;
the gallium oxide layer is grown on the surface of the substrate by the following steps:
cleaning the substrate by acetone, absolute ethyl alcohol and deionized water in sequence to prepare a pretreated substrate; placing the pretreated substrate on a rotating tray, controlling the pressure to 10-1Pa, heating to 700 ℃; after the temperature rise is finished, introducing nitrogen, oxygen and Ga (C) carried in sequence2H5)3The argon gas makes the surface of the substrate grow a gallium oxide layer;
the gallium oxide layer grows on the surface of the substrate through a chemical vapor deposition method;
the temperature rise process comprises the following steps: keeping the temperature unchanged for 1min after heating to 50 ℃ every time, and then continuing heating.
2. The method for opening the graphene bandgap according to claim 1, wherein the substrate is a sapphire substrate, a silicon substrate or a quartz substrate.
3. The method for opening the graphene bandgap according to claim 2, wherein the gallium oxide layer is grown on the surface of the silicon substrate by:
s1: cleaning the silicon substrate with deionized water, acetone and alcohol in sequence to obtain a pretreated silicon substrate;
s2: placing the silicon substrate pretreated by the S1 into the mixed solution I, and growing for 1-3 h at the temperature of 80-98 ℃ to obtain a substrate with a gallium oxyhydroxide seed layer; the mixed solution I is a mixed water solution of gallium nitrate and hexamethylenetetramine, the concentration of the gallium nitrate in the mixed solution I is 0.1-0.6 mol/L, and the concentration of the hexamethylenetetramine in the mixed solution I is 0.5-1 mol/L;
s3: washing the substrate with the hydroxyl gallium oxide seed layer prepared in the step S2 with deionized water, drying, placing the substrate in a mixed solution II, carrying out hydrothermal reaction at the temperature of 120-180 ℃ for 2-6 h, and drying to prepare a hydroxyl gallium oxide nano array; the mixed solution II is a mixed water solution of gallium nitrate and hexamethylenetetramine, the concentration of the gallium nitrate in the mixed solution II is 0.05-1 mol/L, and the concentration of the hexamethylenetetramine in the mixed solution II is 0.1-0.3 mol/L;
s4: annealing the hydroxyl gallium oxide nano-array prepared in the step S3 at the annealing temperature of 650-900 ℃ for 2-4 h, and naturally cooling to room temperature to obtain a beta-gallium oxide nano-column array;
s5: preparing the beta-gallium oxide nano-pillar array prepared by the S4 by using a magnetron sputtering method to obtain an amorphous gallium oxide film; and annealing the amorphous gallium oxide film at 650-900 ℃ for 2-4 h, and naturally cooling to room temperature to obtain the gallium oxide layer.
4. The method for opening the graphene band gap according to claim 1, wherein the graphene layer is prepared by the following steps:
and (3) putting the substrate copper foil into a furnace, introducing hydrogen and inert gas for protection, heating to 1000 ℃, stabilizing the temperature, keeping for 20min, stopping introducing the protective gas, and introducing carbon source gas for 30min to obtain the graphene layer on the copper foil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910752677.3A CN110429026B (en) | 2019-08-15 | 2019-08-15 | Method for opening graphene band gap |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910752677.3A CN110429026B (en) | 2019-08-15 | 2019-08-15 | Method for opening graphene band gap |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110429026A CN110429026A (en) | 2019-11-08 |
| CN110429026B true CN110429026B (en) | 2022-05-06 |
Family
ID=68416294
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910752677.3A Active CN110429026B (en) | 2019-08-15 | 2019-08-15 | Method for opening graphene band gap |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110429026B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112875688A (en) * | 2021-03-18 | 2021-06-01 | 中国矿业大学(北京) | Method for adjusting forbidden band width of graphene, graphene semiconductor element, semiconductor and application |
| CN114497277A (en) * | 2021-12-30 | 2022-05-13 | 昆明物理研究所 | Diode based on graphene/gallium oxide heterojunction and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012174040A1 (en) * | 2011-06-17 | 2012-12-20 | University Of North Texas | Direct graphene growth on mgo (111) by physical vapor deposition: interfacial chemistry and band gap formation |
| CN103606514A (en) * | 2013-12-03 | 2014-02-26 | 西安电子科技大学 | Chemical corrosion transfer method based on GaN substrate CVD epitaxial growth graphene |
| CN105460930A (en) * | 2016-01-04 | 2016-04-06 | 河南工程学院 | Method and device for controlling and representing graphene band gap |
| CN106783997A (en) * | 2016-12-05 | 2017-05-31 | 北京大学 | A kind of high mobility transistor and preparation method thereof |
| CN109920875A (en) * | 2017-12-12 | 2019-06-21 | 中国科学院苏州纳米技术与纳米仿生研究所 | Solar blind ultraviolet detector, its production method and application |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103489967B (en) * | 2013-09-05 | 2016-07-13 | 大连理工大学 | The preparation method of a kind of gallium oxide epitaxial film and gallium oxide epitaxial film |
| CN103469173B (en) * | 2013-09-12 | 2015-10-28 | 大连理工大学 | The preparation method of hole conducting properties gallium oxide film and hole conducting properties gallium oxide film |
| CN103833030B (en) * | 2014-01-16 | 2016-01-06 | 中国科学院青岛生物能源与过程研究所 | A kind of method of big area transfer CVD graphene film |
| KR101712003B1 (en) * | 2015-07-31 | 2017-03-03 | 한국과학기술연구원 | 2-Dimensional laminated composite structured bistable non-volatile memory device and methods of manufacturing the same |
| CN105576073B (en) * | 2016-02-02 | 2017-04-12 | 合肥工业大学 | Graphene/beta-Ga＜2＞O＜3＞-based schottky junction deep ultraviolet photodetector and preparation method thereof |
| CN107785241B (en) * | 2017-10-09 | 2019-08-02 | 哈尔滨工业大学 | A method of preparing beta-gallium oxide film on a silicon substrate |
| CN108615672B (en) * | 2018-04-17 | 2020-09-04 | 中山大学 | Preparation method of semiconductor crystalline film and semiconductor crystalline film |
| CN109461790B (en) * | 2018-09-26 | 2020-08-14 | 北京镓族科技有限公司 | Gallium oxide/graphene heterojunction zero-power-consumption photoelectric detector and manufacturing method thereof |
-
2019
- 2019-08-15 CN CN201910752677.3A patent/CN110429026B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012174040A1 (en) * | 2011-06-17 | 2012-12-20 | University Of North Texas | Direct graphene growth on mgo (111) by physical vapor deposition: interfacial chemistry and band gap formation |
| CN103606514A (en) * | 2013-12-03 | 2014-02-26 | 西安电子科技大学 | Chemical corrosion transfer method based on GaN substrate CVD epitaxial growth graphene |
| CN105460930A (en) * | 2016-01-04 | 2016-04-06 | 河南工程学院 | Method and device for controlling and representing graphene band gap |
| CN106783997A (en) * | 2016-12-05 | 2017-05-31 | 北京大学 | A kind of high mobility transistor and preparation method thereof |
| CN109920875A (en) * | 2017-12-12 | 2019-06-21 | 中国科学院苏州纳米技术与纳米仿生研究所 | Solar blind ultraviolet detector, its production method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110429026A (en) | 2019-11-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103489967B (en) | The preparation method of a kind of gallium oxide epitaxial film and gallium oxide epitaxial film | |
| CN103952682A (en) | Method for growing single-layer molybdenum disulfide by chemical vapor deposition | |
| CN111081808B (en) | Based on MoS2/Ga2O3Heterojunction photoelectric detector, preparation method and application | |
| CN110429026B (en) | Method for opening graphene band gap | |
| CN110854013B (en) | Large-area continuous ultrathin two-dimensional Ga 2 O 3 Preparation method and application of amorphous film | |
| Yoshino et al. | Low-temperature growth of ZnO films by spray pyrolysis | |
| GB2592513A (en) | Method for efficiently eliminating graphene wrinkles formed by chemical vapor deposition | |
| CN111933519B (en) | Preparation method of non-layered two-dimensional gallium oxide film | |
| WO2023082540A1 (en) | Light-emitting device, aluminum nitride product, aluminum nitride single crystal, and manufacturing method therefor and use thereof | |
| CN111986987A (en) | P-type doping-based hexagonal boron nitride epitaxial film preparation method | |
| CN110055589B (en) | Large-size single-layer hexagonal boron nitride single crystal or film and preparation method thereof | |
| CN112103177B (en) | Preparation method of amorphous indium-aluminum-tin oxide semiconductor film | |
| Hu et al. | Effects of hydrogen surface pretreatment of silicon dioxide on the nucleation and surface roughness of polycrystalline silicon films prepared by rapid thermal chemical vapor deposition | |
| Shu-Wen | A Study of annealing time effects on the properties of Al: ZnO | |
| CN110724922B (en) | Epitaxial AZO film with controllable crystal orientation and polarity on flexible substrate and preparation method thereof | |
| CN105331950A (en) | Manufacturing method of two-dimensional perovskite film | |
| CN110172733B (en) | High-quality zinc stannate single crystal film and preparation method thereof | |
| CN108060458B (en) | A kind of preparation facilities and method of nonpolarity indium nitride nano-crystal film | |
| CN110993752A (en) | LED epitaxial growth method taking graphene as buffer layer | |
| CN113322522B (en) | Preparation method of large-single-domain large-area single-layer tungsten disulfide film by epitaxy | |
| Erdoğan et al. | Influence of substrate and substrate temperature on the structural, optical and surface properties of InGaN thin films prepared by RFMS method | |
| CN107731959A (en) | A kind of crystal silicon solar batteries processing method | |
| CN101928933A (en) | Method for preparing silicon carbide film | |
| Ali | Mechanisms of the growth of nanocrystalline Si: H films deposited by PECVD | |
| Yoshino et al. | Growth of spin-coated ZnO films using diethylzinc solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |