CN108428618B - Gallium nitride growth method based on graphene insertion layer structure - Google Patents
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Abstract
The invention relates to a gallium nitride growth method based on a graphene insertion layer structure, which comprises the following steps of (1) carrying out magnetron sputtering of an aluminum nitride film on a sapphire substrate with α planes, (2) transferring graphene onto the magnetron sputtering aluminum nitride film through a transfer technology of the graphene on the metal substrate, (3) carrying out heat treatment on a substrate covered with the graphene, (4) using a pulse Metal Organic Chemical Vapor Deposition (MOCVD) method to carry out epitaxial aluminum nitride as a transition layer, and (5) putting a sample into the MOCVD method to carry out epitaxial growth of a low-temperature GaN epitaxial layer and a high-temperature GaN epitaxial layer in sequence.
Description
Technical Field
The invention belongs to the technical field of electronics, and further relates to a gallium nitride growth method based on a graphene insertion layer structure in the technical field of microelectronic materials. The invention can grow gallium nitride on the graphene insertion layer, and the obtained gallium nitride can be further used for manufacturing gallium nitride electronic devices.
Background
Third generation wide bandgap semiconductor materials represented by gallium nitride have been widely used in the fields of optoelectronic devices and electronic devices due to their advantages of large bandgap, high electron mobility, large breakdown field, etc.
Due to the fact that large lattice mismatch and thermal mismatch exist between the gallium nitride epitaxial material and the substrate, gallium nitride obtained by heteroepitaxy is prone to generate large stress and form high-density dislocations in the growing process, and the dislocations have serious influences on the performance and reliability of the gallium nitride-based device.
Reducing dislocation density of gallium nitride material growth has been a key issue in gallium nitride research, and growing high quality gallium nitride has been a key issue in fabricating high quality gallium nitride electronic devices.
Liu Shi bin in the patent document "a gallium nitride film and a preparation method thereof and a graphene film and a preparation method thereof" of its application (application No. 201710192463.6, application publication No. CN106960781A) disclose a gallium nitride film and a preparation method of a graphene film. The preparation method comprises the steps of firstly growing a gallium nitride buffer layer on a semiconductor substrate, then forming a graphene catalyst layer with a pore structure on the gallium nitride buffer layer, then forming a graphene mask layer with the same pore structure as the graphene catalyst layer on the graphene catalyst layer, and finally growing a gallium nitride layer on the graphene mask layer. According to the method, the graphene mask layer with the pore structure is used as the mask to epitaxially grow the gallium nitride layer, so that the defect formed by the contact part of the gallium nitride epitaxial layer and the graphene mask layer can be effectively reduced, the formed gallium nitride film can be uniformly distributed and has a good crystalline phase structure, and high-quality gallium nitride is obtained. However, the method still has the following defects: firstly, the method needs to firstly extend the gallium nitride buffer layer, then a graphene catalyst layer and a graphene mask layer are formed on the gallium nitride buffer layer, and finally gallium nitride epitaxial growth is carried out, so that the method has multiple process steps and high cost. Secondly, because the method needs to form the graphene catalyst layer and the graphene mask layer with the same pore structure, the process is difficult to ensure that the same graphene catalyst layer and the same graphene mask layer are formed every time, and the process repeatability is poor.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a Metal Organic Chemical Vapor Deposition (MOCVD) growth method of gallium nitride on a sapphire substrate based on a graphene insertion layer structure, so as to reduce dislocation of gallium nitride growth and improve the quality of the gallium nitride.
In order to improve the quality of the gallium nitride, the specific idea of the invention is as follows: firstly, magnetron sputtering a layer of aluminum nitride film on a sapphire substrate to relieve stress generated between the substrate and gallium nitride due to lattice mismatch; then transferring the single-layer graphene to a sapphire substrate on which an aluminum nitride film is sputtered, and finally putting the sample into a metal organic chemical vapor deposition system to sequentially epitaxially form a pulse aluminum nitride transition layer, a low-temperature gallium nitride epitaxial layer and a high-temperature gallium nitride epitaxial layer.
The method is characterized in that an aluminum nitride nucleating layer, a graphene insertion layer and a pulse aluminum nitride transition layer are formed by magnetron sputtering, an aluminum nitride film is formed by magnetron sputtering on a sapphire substrate with the surface of α through a mode of extending the pulse aluminum nitride transition layer by a pulse metal organic chemical vapor deposition method, then the graphene insertion layer is transferred, finally pulse aluminum nitride and low-temperature gallium nitride epitaxial layers and high-temperature gallium nitride epitaxial layers are formed by metal organic chemical vapor deposition MOCVD, and a crystal lattice structure is optimized by adjusting growth conditions of the epitaxial layers, wherein the growth conditions mainly comprise reaction chamber pressure, temperature, metal source flow and the like, so that dislocation generation is reduced, and the quality of gallium nitride is improved.
The method comprises the following specific steps:
carrying out magnetron sputtering on an α -plane sapphire substrate to form an aluminum nitride film, transferring graphene on the magnetron sputtering aluminum nitride film, and sequentially extending pulsed aluminum nitride, low-temperature gallium nitride and high-temperature gallium nitride on the graphene by adopting a metal organic chemical vapor deposition method, wherein the method specifically comprises the following steps:
(1) magnetron sputtering of aluminum nitride:
(1a) placing the sapphire substrate with the α surface in a magnetron sputtering system, introducing nitrogen and argon for 5min under the pressure of 1Pa in a reaction chamber to obtain a processed sapphire substrate with the α surface;
(1b) performing magnetron sputtering on the treated α -plane sapphire substrate by using 99.999% purity aluminum as a target material by adopting a magnetron sputtering method to obtain a magnetron sputtering aluminum nitride substrate;
(2) transferring graphene:
(2a) growing graphene on a metal substrate by adopting a chemical vapor deposition method;
(2b) placing the metal substrate for growing the graphene in a mixed solution of 1mol/L ferric chloride and 2mol/L hydrochloric acid for 12 hours to remove the metal substrate, and obtaining the graphene with the metal substrate removed;
(2c) transferring the graphene with the metal substrate removed onto a magnetron sputtering aluminum nitride substrate to obtain a substrate covering the graphene;
(3) carrying out heat treatment on the substrate:
(3a) placing the substrate covered with the graphene in a metal organic chemical vapor deposition reaction chamber, introducing hydrogen and ammonia gas into the reaction chamber for 4min, and treating the substrate covered with the graphene to obtain a substrate covered with the graphene after gas treatment;
(3b) after the temperature of the reaction chamber is raised to 620 ℃, carrying out heat treatment on the substrate which is subjected to gas treatment and covered with the graphene to obtain a heat-treated substrate;
(4) growing pulse aluminum nitride:
adjusting the pressure of the reaction chamber to 40Torr, raising the temperature to 1060 ℃, introducing hydrogen, ammonia gas and an aluminum source, wherein the flow rate of the hydrogen is 800-1000sccm, the flow rate of the ammonia gas is 2000-3000sccm, the flow rate of the aluminum source is 6-20 mu mol/L, and growing pulse aluminum nitride on the substrate after heat treatment by adopting a pulse metal organic chemical vapor deposition method to obtain a pulse aluminum nitride substrate;
(5) growing low-temperature gallium nitride:
keeping the pressure of the reaction chamber unchanged, reducing the temperature to 900 ℃, introducing hydrogen, ammonia gas and a gallium source, wherein the hydrogen flow is 800-1000sccm, the ammonia flow is 2000-3000sccm, and the gallium source flow is 60-120 mu mol/L, and growing low-temperature gallium nitride on a pulse aluminum nitride substrate by adopting a metal organic chemical vapor deposition method to obtain a low-temperature gallium nitride substrate;
(6) growing high-temperature gallium nitride:
(6a) keeping the pressure of the reaction chamber unchanged, raising the temperature to 950 ℃, introducing hydrogen, ammonia gas and a gallium source, wherein the flow rate of the hydrogen is 800-1000sccm, the flow rate of the ammonia gas is 2000-3000sccm, the flow rate of the gallium source is 60-120 mu mol/L, and growing high-temperature gallium nitride on a low-temperature gallium nitride substrate by adopting a metal organic chemical vapor deposition method;
(6b) and cooling the temperature of the reaction chamber to room temperature, and taking out the sample to obtain the gallium nitride based on the graphene insertion layer structure.
Compared with the prior art, the invention has the following advantages:
firstly, the sputtering aluminum nitride substrate is obtained by sputtering an aluminum nitride film with the thickness of 10-100nm on a processed α -surface sapphire substrate, and the aluminum nitride film is grown on the sputtering aluminum nitride substrate, so that the problems of more process steps and higher cost caused by the need of firstly extending a gallium nitride buffer layer in the prior art are solved, and the method has the advantages of less process steps and low cost.
Secondly, the graphene layer with the metal substrate removed is transferred to the substrate sputtered with aluminum nitride to obtain the substrate covered with graphene, and the substrate is grown on the substrate covered with graphene, so that the problems that in the prior art, a graphene catalyst layer and a graphene mask layer with the same pore structure need to be formed, the same graphene catalyst layer and same graphene mask layer are difficult to form each time in the process, and the process repeatability is poor are solved, and the method has the advantage of good process repeatability.
Drawings
FIG. 1 is a flow chart of the present invention;
fig. 2 is a schematic cross-sectional structure of the present invention.
Detailed Description
The technical solution and effect of the present invention will be further described with reference to the embodiment of fig. 1.
The implementation steps of the present invention are further described with reference to fig. 1.
Step 1, magnetron sputtering aluminum nitride.
The method comprises the steps of placing a sapphire substrate with α surfaces in a magnetron sputtering system, introducing nitrogen and argon for 5min, and treating the sapphire substrate with α surfaces to obtain a treated sapphire substrate with α surfaces, wherein the nitrogen flow is 20-100sccm, the argon flow is 40-200sccm, a radio frequency magnetron sputtering method is adopted, aluminum with 99.999% purity is used as a target material, aluminum nitride is sputtered on the treated sapphire substrate with α surfaces, the sputtered aluminum nitride with good crystalline quality can relieve stress between the substrate and gallium nitride due to lattice mismatch, and the sputtered aluminum nitride substrate is obtained, and the thickness of the sputtered aluminum nitride is 10-100 nm.
And 2, transferring the graphene.
And growing graphene on the metal substrate by adopting a chemical vapor deposition method. The thickness of the graphene is 0.34-3.4 nm. And (3) placing the metal substrate for growing the graphene in a mixed solution of 1mol/L ferric chloride and 2mol/L hydrochloric acid for 12 hours to remove the metal substrate, so as to obtain the graphene with the metal substrate removed. And transferring the graphene with the metal substrate removed onto a substrate sputtered with aluminum nitride, wherein the subsequent growth temperature depends on the temperature of the sapphire substrate due to the good heat conduction characteristic of the graphene, so that the substrate covered with the graphene is obtained.
And 3, carrying out heat treatment on the substrate.
And placing the substrate covered with the graphene in a metal organic chemical vapor deposition reaction chamber, introducing hydrogen and ammonia gas into the reaction chamber for 4min, treating the substrate covered with the graphene, and using the hydrogen as a carrier gas to enable the substrate covered with the graphene to be in an ammonia gas environment to obtain the substrate covered with the graphene after gas treatment. The hydrogen flow is 800sccm, and the ammonia flow is 3000 sccm. And (3) heating the reaction chamber to 620 ℃, then carrying out heat treatment on the treated substrate covered with the graphene, removing impurities and chemical bonds on the surface of the substrate covered with the graphene, and optimizing the surface of the substrate covered with the graphene to obtain the substrate after heat treatment. The time of the heat treatment is 15-30 min.
And 4, growing the pulse aluminum nitride.
And adjusting the pressure of the reaction chamber to 40Torr, raising the temperature to 1060 ℃, introducing hydrogen, ammonia gas and an aluminum source, wherein the flow rate of the hydrogen is 800-1000sccm, the flow rate of the ammonia gas is 2000-3000sccm, and the flow rate of the aluminum source is 6-20 mu mol/L, and growing pulse aluminum nitride on the substrate after heat treatment by adopting a pulse metal organic chemical vapor deposition method to obtain the pulse aluminum nitride substrate. The pulse aluminum nitride is used as a transition layer to improve the crystallization quality of the material. The above-mentionedThe pulse metal organic chemical vapor deposition method refers to that in a pulse period T1+T2Within, at T1Introducing ammonia gas at T2Ammonia gas is not introduced during the time; the T is1Time is set to 12s, T2The time is set to 6s, the number of pulse period repetition is 80-200, and the thickness of the pulse aluminum nitride is 10-40 nm.
And 5, growing low-temperature gallium nitride.
Keeping the pressure of the reaction chamber unchanged, reducing the temperature to 900 ℃, introducing hydrogen, ammonia gas and a gallium source, wherein the flow rate of the hydrogen is 800-1000sccm, the flow rate of the ammonia is 2000-3000sccm, and the flow rate of the gallium source is 60-120 mu mol/L, and growing low-temperature gallium nitride on a pulse aluminum nitride substrate by adopting a metal organic chemical vapor deposition method so as to prevent graphene from being decomposed due to high temperature and obtain a low-temperature gallium nitride substrate. The thickness of the low-temperature gallium nitride is 20-500 nm.
And 6, growing high-temperature gallium nitride.
Keeping the pressure of the reaction chamber unchanged, raising the temperature to 950 ℃, introducing hydrogen, ammonia gas and a gallium source, wherein the flow rate of the hydrogen is 800-1000sccm, the flow rate of the ammonia is 2000-3000sccm, and the flow rate of the gallium source is 60-120 mu mol/L, and growing high-temperature gallium nitride on a low-temperature gallium nitride substrate by adopting a metal organic chemical vapor deposition method so that the gallium nitride grows at a proper growth temperature. The thickness of the gallium nitride is 600-2000 nm. And cooling the temperature of the reaction chamber to room temperature, and taking out the sample to obtain the gallium nitride based on the graphene insertion layer structure.
The cross-sectional layer structure of gallium nitride based on the graphene insertion layer structure obtained by the present invention is further described with reference to fig. 2.
The profile layer structure of the gallium nitride based on the graphene insertion layer structure obtained by the invention sequentially comprises an α -surface sapphire substrate, a magnetron sputtering aluminum nitride layer, a graphene layer, a pulse aluminum nitride transition layer, a low-temperature gallium nitride layer and a high-temperature gallium nitride layer from bottom to top.
The present invention is further described below by three examples of growing gallium nitride on the graphene insertion layer and the pulsed aluminum nitride transition layer structure, growing gallium nitride on the graphene insertion layer and the direct method aluminum nitride transition layer structure, and growing gallium nitride on the graphene insertion layer structure.
Example 1: and growing gallium nitride on the graphene insertion layer and the pulse aluminum nitride transition layer structure.
Step one, magnetron sputtering aluminum nitride.
The method comprises the steps of placing a sapphire substrate with α surfaces in a magnetron sputtering system, introducing nitrogen and argon for 5min, and treating the sapphire substrate with α surfaces to obtain a treated sapphire substrate with α surfaces, wherein the nitrogen flow is 20-100sccm, the argon flow is 40-200sccm, a radio frequency magnetron sputtering method is adopted, aluminum with 99.999% purity is used as a target material, aluminum nitride is sputtered on the treated sapphire substrate with α surfaces, the sputtered aluminum nitride with good crystalline quality can relieve stress between the substrate and gallium nitride due to lattice mismatch, and the sputtered aluminum nitride substrate is obtained, and the thickness of the sputtered aluminum nitride is 10-100 nm.
And step two, transferring the graphene.
And growing graphene on the metal substrate by adopting a chemical vapor deposition method. The thickness of the graphene is 0.34-3.4 nm. And (3) placing the metal substrate for growing the graphene in a mixed solution of 1mol/L ferric chloride and 2mol/L hydrochloric acid for 12 hours to remove the metal substrate, so as to obtain the graphene with the metal substrate removed. And transferring the graphene with the metal substrate removed onto a substrate sputtered with aluminum nitride, wherein the subsequent growth temperature depends on the temperature of the sapphire substrate due to the good heat conduction characteristic of the graphene, so that the substrate covered with the graphene is obtained.
And step three, carrying out heat treatment on the substrate.
And placing the substrate covered with the graphene in a metal organic chemical vapor deposition reaction chamber, introducing hydrogen and ammonia gas into the reaction chamber for 4min, treating the substrate covered with the graphene, and using the hydrogen as a carrier gas to enable the substrate covered with the graphene to be in an ammonia gas environment to obtain the substrate covered with the graphene after gas treatment. The hydrogen flow is 800sccm, and the ammonia flow is 3000 sccm. And (3) heating the reaction chamber to 620 ℃, then carrying out heat treatment on the treated substrate covered with the graphene, removing impurities and chemical bonds on the surface of the substrate covered with the graphene, and optimizing the surface of the substrate covered with the graphene to obtain the substrate after heat treatment. The time of the heat treatment is 15-30 min.
And step four, growing the pulse aluminum nitride.
And adjusting the pressure of the reaction chamber to 40Torr, raising the temperature to 1060 ℃, introducing hydrogen, ammonia gas and an aluminum source, wherein the flow rate of the hydrogen is 800-1000sccm, the flow rate of the ammonia gas is 2000-3000sccm, and the flow rate of the aluminum source is 6-20 mu mol/L, and growing pulse aluminum nitride on the substrate after heat treatment by adopting a pulse metal organic chemical vapor deposition method to obtain the pulse aluminum nitride substrate. The pulse aluminum nitride is used as a transition layer to improve the crystallization quality of the material. The pulse metal organic chemical vapor deposition method is that in one pulse period T1+T2Within, at T1Introducing ammonia gas at T2Ammonia gas is not introduced during the time; the T is1Time is set to 12s, T2The time is set to 6s, the number of pulse period repetition is 80-200, and the thickness of the pulse aluminum nitride is 10-40 nm.
And step five, growing the low-temperature gallium nitride.
Keeping the pressure of the reaction chamber unchanged, reducing the temperature to 900 ℃, introducing hydrogen, ammonia gas and a gallium source, wherein the flow rate of the hydrogen is 800-1000sccm, the flow rate of the ammonia is 2000-3000sccm, and the flow rate of the gallium source is 60-120 mu mol/L, and growing low-temperature gallium nitride on a pulse aluminum nitride substrate by adopting a metal organic chemical vapor deposition method so as to prevent graphene from being decomposed due to high temperature and obtain a low-temperature gallium nitride substrate. The thickness of the low-temperature gallium nitride is 20-500 nm.
And step six, growing high-temperature gallium nitride.
Keeping the pressure of the reaction chamber unchanged, raising the temperature to 950 ℃, introducing hydrogen, ammonia gas and a gallium source, wherein the flow rate of the hydrogen is 800-1000sccm, the flow rate of the ammonia is 2000-3000sccm, and the flow rate of the gallium source is 60-120 mu mol/L, and growing high-temperature gallium nitride on a low-temperature gallium nitride substrate by adopting a metal organic chemical vapor deposition method so that the gallium nitride grows at a proper growth temperature. The thickness of the gallium nitride is 600-2000 nm. And cooling the temperature of the reaction chamber to room temperature, and taking out the sample to obtain the gallium nitride based on the graphene insertion layer structure and the pulse aluminum nitride transition layer structure.
Example 2: and growing gallium nitride on the graphene insertion layer and the direct method aluminum nitride transition layer structure.
Step a, magnetron sputtering aluminum nitride.
The method comprises the steps of placing a sapphire substrate with α surfaces in a magnetron sputtering system, introducing nitrogen and argon for 5min, and treating the sapphire substrate with α surfaces to obtain a treated sapphire substrate with α surfaces, wherein the nitrogen flow is 20-100sccm, the argon flow is 40-200sccm, a radio frequency magnetron sputtering method is adopted, aluminum with 99.999% purity is used as a target material, aluminum nitride is sputtered on the treated sapphire substrate with α surfaces, the sputtered aluminum nitride with good crystalline quality can relieve stress between the substrate and gallium nitride due to lattice mismatch, and the sputtered aluminum nitride substrate is obtained, and the thickness of the sputtered aluminum nitride is 10-100 nm.
And b, transferring the graphene.
And growing graphene on the metal substrate by adopting a chemical vapor deposition method. The thickness of the graphene is 0.34-3.4 nm. And (3) placing the metal substrate for growing the graphene in a mixed solution of 1mol/L ferric chloride and 2mol/L hydrochloric acid for 12 hours to remove the metal substrate, so as to obtain the graphene with the metal substrate removed. And transferring the graphene with the metal substrate removed onto a substrate sputtered with aluminum nitride, wherein the subsequent growth temperature depends on the temperature of the sapphire substrate due to the good heat conduction characteristic of the graphene, so that the substrate covered with the graphene is obtained.
And c, carrying out heat treatment on the substrate.
And placing the substrate covered with the graphene in a metal organic chemical vapor deposition reaction chamber, introducing hydrogen and ammonia gas into the reaction chamber for 4min, treating the substrate covered with the graphene, and using the hydrogen as a carrier gas to enable the substrate covered with the graphene to be in an ammonia gas environment to obtain the substrate covered with the graphene after gas treatment. The hydrogen flow is 800sccm, and the ammonia flow is 3000 sccm. And (3) heating the reaction chamber to 620 ℃, then carrying out heat treatment on the treated substrate covered with the graphene, removing impurities and chemical bonds on the surface of the substrate covered with the graphene, and optimizing the surface of the substrate covered with the graphene to obtain the substrate after heat treatment. The time of the heat treatment is 15-30 min.
And d, growing the aluminum nitride by a direct method.
And adjusting the pressure of the reaction chamber to 40Torr, raising the temperature to 1060 ℃, introducing hydrogen, ammonia gas and an aluminum source, and growing aluminum nitride on the heat-treated substrate by adopting a metal organic chemical vapor deposition method. The aluminum nitride is used as a transition layer to improve the crystallization quality of the material, and the aluminum nitride substrate is obtained. The thickness of the aluminum nitride is 10-40 nm.
And e, growing low-temperature gallium nitride.
Keeping the pressure of the reaction chamber unchanged, reducing the temperature to 900 ℃, introducing hydrogen, ammonia gas and a gallium source, wherein the flow rate of the hydrogen is 800-1000sccm, the flow rate of the ammonia is 2000-3000sccm, and the flow rate of the gallium source is 60-120 mu mol/L, and growing low-temperature gallium nitride on a pulse aluminum nitride substrate by adopting a metal organic chemical vapor deposition method so as to prevent graphene from being decomposed due to high temperature and obtain a low-temperature gallium nitride substrate. The thickness of the low-temperature gallium nitride is 20-500 nm.
And f, growing high-temperature gallium nitride.
Keeping the pressure of the reaction chamber unchanged, raising the temperature to 950 ℃, introducing hydrogen, ammonia gas and a gallium source, wherein the flow rate of the hydrogen is 800-1000sccm, the flow rate of the ammonia is 2000-3000sccm, and the flow rate of the gallium source is 60-120 mu mol/L, and growing high-temperature gallium nitride on a low-temperature gallium nitride substrate by adopting a metal organic chemical vapor deposition method so that the gallium nitride grows at a proper growth temperature. The thickness of the gallium nitride is 600-2000 nm. And cooling the temperature of the reaction chamber to room temperature, and taking out the sample to obtain the gallium nitride based on the graphene insertion layer structure and the direct method aluminum nitride transition layer structure.
Example 3: and growing gallium nitride on the graphene insertion layer structure.
Step I, magnetron sputtering aluminum nitride.
The method comprises the steps of placing a sapphire substrate with α surfaces in a magnetron sputtering system, introducing nitrogen and argon for 5min, and treating the sapphire substrate with α surfaces to obtain a treated sapphire substrate with α surfaces, wherein the nitrogen flow is 20-100sccm, the argon flow is 40-200sccm, a radio frequency magnetron sputtering method is adopted, aluminum with 99.999% purity is used as a target material, aluminum nitride is sputtered on the treated sapphire substrate with α surfaces, the sputtered aluminum nitride with good crystalline quality can relieve stress between the substrate and gallium nitride due to lattice mismatch, and the sputtered aluminum nitride substrate is obtained, and the thickness of the sputtered aluminum nitride is 10-100 nm.
And II, transferring the graphene.
And growing graphene on the metal substrate by adopting a chemical vapor deposition method. The thickness of the graphene is 0.34-3.4 nm. And (3) placing the metal substrate for growing the graphene in a mixed solution of 1mol/L ferric chloride and 2mol/L hydrochloric acid for 12 hours to remove the metal substrate, so as to obtain the graphene with the metal substrate removed. And transferring the graphene with the metal substrate removed onto a substrate sputtered with aluminum nitride, wherein the subsequent growth temperature depends on the temperature of the sapphire substrate due to the good heat conduction characteristic of the graphene, so that the substrate covered with the graphene is obtained.
And step III, carrying out heat treatment on the substrate.
And placing the substrate covered with the graphene in a metal organic chemical vapor deposition reaction chamber, introducing hydrogen and ammonia gas into the reaction chamber for 4min, treating the substrate covered with the graphene, and using the hydrogen as a carrier gas to enable the substrate covered with the graphene to be in an ammonia gas environment to obtain the substrate covered with the graphene after gas treatment. The hydrogen flow is 800sccm, and the ammonia flow is 3000 sccm. And (3) heating the reaction chamber to 620 ℃, then carrying out heat treatment on the treated substrate covered with the graphene, removing impurities and chemical bonds on the surface of the substrate covered with the graphene, and optimizing the surface of the substrate covered with the graphene to obtain the substrate after heat treatment. The time of the heat treatment is 15-30 min.
And IV, growing low-temperature gallium nitride.
Keeping the pressure of the reaction chamber unchanged, reducing the temperature to 900 ℃, introducing hydrogen, ammonia gas and a gallium source, wherein the flow rate of the hydrogen is 800-1000sccm, the flow rate of the ammonia is 2000-3000sccm, and the flow rate of the gallium source is 60-120 mu mol/L, and growing low-temperature gallium nitride on a pulse aluminum nitride substrate by adopting a metal organic chemical vapor deposition method so as to prevent graphene from being decomposed due to high temperature and obtain a low-temperature gallium nitride substrate. The thickness of the low-temperature gallium nitride is 20-500 nm.
And V, growing high-temperature gallium nitride.
Keeping the pressure of the reaction chamber unchanged, raising the temperature to 950 ℃, introducing hydrogen, ammonia gas and a gallium source, wherein the flow rate of the hydrogen is 800-1000sccm, the flow rate of the ammonia is 2000-3000sccm, and the flow rate of the gallium source is 60-120 mu mol/L, and growing high-temperature gallium nitride on a low-temperature gallium nitride substrate by adopting a metal organic chemical vapor deposition method so that the gallium nitride grows at a proper growth temperature. The thickness of the gallium nitride is 600-2000 nm. And cooling the temperature of the reaction chamber to room temperature, and taking out the sample to obtain the gallium nitride based on the graphene insertion layer structure and the aluminum nitride-free transition layer structure.
Claims (7)
1. A gallium nitride growth method based on a graphene insertion layer structure is characterized in that an aluminum nitride film is subjected to magnetron sputtering on a sapphire substrate with an α plane, graphene is transferred on the magnetron sputtering aluminum nitride film, and pulsed aluminum nitride, low-temperature gallium nitride and high-temperature gallium nitride are sequentially epitaxially grown on the graphene by adopting a metal organic chemical vapor deposition method, wherein the method comprises the following specific steps:
(1) magnetron sputtering of aluminum nitride:
(1a) placing the sapphire substrate with the α surface in a magnetron sputtering system, introducing nitrogen and argon for 5min under the pressure of 1Pa in a reaction chamber to obtain a processed sapphire substrate with the α surface;
(1b) performing magnetron sputtering on the treated α -plane sapphire substrate by using 99.999% purity aluminum as a target material by adopting a magnetron sputtering method, wherein the thickness of the magnetron sputtering aluminum nitride is 10-100nm, so as to obtain a magnetron sputtering aluminum nitride substrate;
(2) transferring graphene:
(2a) growing graphene with the thickness of 0.34-3.4nm on a metal substrate by adopting a chemical vapor deposition method;
(2b) placing the metal substrate for growing the graphene in a mixed solution of 1mol/L ferric chloride and 2mol/L hydrochloric acid for 12 hours to remove the metal substrate, and obtaining the graphene with the metal substrate removed;
(2c) transferring the graphene with the metal substrate removed onto a magnetron sputtering aluminum nitride substrate to obtain a substrate covering the graphene;
(3) carrying out heat treatment on the substrate:
(3a) placing the substrate covered with the graphene in a metal organic chemical vapor deposition reaction chamber, introducing hydrogen and ammonia gas into the reaction chamber for 4min, and treating the substrate covered with the graphene to obtain a substrate covered with the graphene after gas treatment;
(3b) after the temperature of the reaction chamber is raised to 620 ℃, carrying out heat treatment on the substrate which is subjected to gas treatment and covered with the graphene to obtain a heat-treated substrate;
(4) growing pulse aluminum nitride:
adjusting the pressure of the reaction chamber to 40Torr, raising the temperature to 1060 ℃, introducing hydrogen, ammonia gas and an aluminum source, wherein the flow rate of the hydrogen is 800-1000sccm, the flow rate of the ammonia gas is 2000-3000sccm, the flow rate of the aluminum source is 6-20 mu mol/L, and growing pulse aluminum nitride on the substrate after heat treatment by adopting a pulse metal organic chemical vapor deposition method to obtain a pulse aluminum nitride substrate;
(5) growing low-temperature gallium nitride:
keeping the pressure of the reaction chamber unchanged, reducing the temperature to 900 ℃, introducing hydrogen, ammonia gas and a gallium source, wherein the flow rate of the hydrogen is 800-1000sccm, the flow rate of the ammonia is 2000-3000sccm, the flow rate of the gallium source is 60-120 mu mol/L, growing low-temperature gallium nitride on a pulse aluminum nitride substrate by adopting a metal organic chemical vapor deposition method, and obtaining a low-temperature gallium nitride substrate, wherein the thickness of the low-temperature gallium nitride is 20-500 nm;
(6) growing high-temperature gallium nitride:
(6a) keeping the pressure of the reaction chamber unchanged, raising the temperature to 950 ℃, introducing hydrogen, ammonia gas and a gallium source, wherein the flow rate of the hydrogen is 800-1000sccm, the flow rate of the ammonia gas is 2000-3000sccm, the flow rate of the gallium source is 60-120 mu mol/L, and growing high-temperature gallium nitride on a low-temperature gallium nitride substrate by adopting a metal organic chemical vapor deposition method;
(6b) and cooling the temperature of the reaction chamber to room temperature, and taking out the sample to obtain the gallium nitride based on the graphene insertion layer structure.
2. The method for growing gallium nitride based on graphene insertion layer structure according to claim 1, wherein the flow rate of nitrogen in step (1a) is 20-100sccm and the flow rate of argon is 40-200 sccm.
3. The method according to claim 1, wherein the hydrogen flow rate in step (3a) is 800sccm and the ammonia gas flow rate is 3000 sccm.
4. The method for growing gallium nitride based on graphene insertion layer structure according to claim 1, wherein the time of the heat treatment in step (3b) is 15-30 min.
5. The method for growing gallium nitride based on graphene insertion layer structure according to claim 1, wherein the pulsed metal organic chemical vapor deposition in step (4) is performed in a pulse period T1+T2Within, at T1Introducing ammonia gas at T2Ammonia gas is not introduced during the time; the T is1Time is set to 12s, T2The time is set to 6s, and the number of pulse period repetitions is 80-200.
6. The method for growing gallium nitride based on graphene insertion layer structure according to claim 1, wherein the thickness of the pulsed aluminum nitride in step (4) is 10-40 nm.
7. The method as claimed in claim 1, wherein the thickness of the high temperature GaN layer in step (6a) is 600-2000 nm.
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