CN108511322B - Method for preparing GaN film on two-dimensional graphite substrate - Google Patents
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 91
- 239000010439 graphite Substances 0.000 title claims abstract description 91
- 239000000758 substrate Substances 0.000 title claims abstract description 91
- 238000000034 method Methods 0.000 title claims abstract description 35
- 230000006911 nucleation Effects 0.000 claims abstract description 27
- 238000010899 nucleation Methods 0.000 claims abstract description 27
- 229910002704 AlGaN Inorganic materials 0.000 claims abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- 238000009832 plasma treatment Methods 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 18
- 238000000137 annealing Methods 0.000 claims abstract description 16
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 7
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 7
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 7
- 239000010408 film Substances 0.000 claims description 27
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 claims description 18
- 230000007547 defect Effects 0.000 claims description 14
- 230000004907 flux Effects 0.000 claims description 12
- 239000010409 thin film Substances 0.000 claims description 10
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 8
- 239000002390 adhesive tape Substances 0.000 claims description 7
- 238000005229 chemical vapour deposition Methods 0.000 claims description 7
- 238000005121 nitriding Methods 0.000 claims description 7
- 239000012159 carrier gas Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229920002120 photoresistant polymer Polymers 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- 239000013078 crystal Substances 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000012546 transfer Methods 0.000 abstract description 5
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- 238000002488 metal-organic chemical vapour deposition Methods 0.000 abstract 1
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- 238000004458 analytical method Methods 0.000 description 9
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
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- 238000009792 diffusion process Methods 0.000 description 3
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- 238000005411 Van der Waals force Methods 0.000 description 1
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- H—ELECTRICITY
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- 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
- H01L21/02175—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 characterised by the metal
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/54—Apparatus specially adapted for continuous coating
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- 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
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
Abstract
The invention belongs to the technical field of GaN film preparation, and provides a method for preparing a GaN film on a two-dimensional graphite substrate, aiming at solving the problems that the existing GaN film has larger lattice mismatch and thermal mismatch with a heterogeneous substrate, a large amount of threading dislocation is generated in the GaN film, the equipment performance is seriously influenced, and the like. Stripping HOPG by mechanical stripping method to obtain graphite substrate material, transferring the stripped graphite substrate material to SiO2Or forming a graphite substrate on the Si substrate, carrying out oxygen plasma treatment on the graphite substrate, placing the graphite substrate in an MOCVD reaction chamber to react to form an AlGaN nucleation layer, annealing, and growing a GaN epitaxial film. The obtained graphite has controllable thickness, realizes the integration of preparation and transfer, avoids the damage caused by the intermediate process, has better quality of the prepared crystal, and is easy to separate from the epitaxial layer. The prepared GaN film is less constrained by lattice matching, has high quality and excellent photoelectric property, and can be used in transferable GaN-based devices.
Description
Technical Field
The invention belongs to the technical field of GaN film preparation, and particularly relates to a method for preparing a GaN film on a two-dimensional graphite substrate, belonging to a preparation method for growing a high-quality GaN film on a pure two-dimensional substrate material.
Background
Currently, Metal Organic Chemical Vapor Deposition (MOCVD) heteroepitaxial growth has become the primary route to the production of GaN semiconductor thin films. Sapphire, SiC, Si, and the like are generally used as foreign substrates for growing GaN thin films, but large numbers of threading dislocations are generated in the GaN thin films due to large lattice mismatch and thermal mismatch between GaN and the foreign substrates, which seriously affect the performance of the device.
Due to its excellent properties, lamellar graphite becomes a new substrate material for epitaxial growth, and the specific interlayer van der Waals force of the graphite lamellar structure can reduce the requirement of the material system for lattice matching, so far, many researches for successfully growing GaN thin films on graphene have been made, but most of the graphene used by them is prepared by Chemical Vapor Deposition (CVD) (reference, Chung K, Park S I, Baek H, et al, High-quality GaN ms growth on chemical vapor-deposited graphene films [ J ]. n Asia Materials, 2012, 4: e 24.) or epitaxial SiC (reference, Kim J, bayer C, Park H, et al, principal of diamond of ceramic van der Waals of single-crystal graphene films [ 2014J ],2014, 5(5):4836.). CVD graphene is easy to damage a substrate material in a transfer process, graphene which is directly epitaxially grown on a SiC substrate does not face damage caused in the transfer process, but the prepared graphene crystal has a plurality of defects which can influence a GaN thin film which is subsequently grown on the substrate material, and the GaN crystal which is directly grown on the two-dimensional material by using a traditional two-step method finally presents a large crystal grain state and is difficult to form a film.
Graphene is an ideal two-dimensional material, and the researchers and the collaborators in the national center for nanometer science in Sunjian find that the morphology of a gold film is closely related to the number of graphene layers after gold is evaporated on graphene with different layers. Through a series of experiments, they proposed that the diffusion coefficient and diffusion barrier of Gold at the surface of graphene of different layers are closely related to the number of layers due to quantum size effects, and thus the relationship between the diffusion barrier and the number of graphene layers was calculated (reference, Zhou H, Qiu C, Liu Z, et al. Thickness-Dependent Morphologies of Gold on N-Layer graphies [ J ]. Journal of the American Chemical Society, 2010, 132(3): 944.). This related research effort has been published in the well-known journal of the American society for chemistry, journal (JACS 132,944 (2010)). And was reported by Chemical & Engineering News under the heading "Gilded Graphene" on 11.1.2010. The work has important guiding significance for developing graphene and device researches thereof.
Disclosure of Invention
The invention provides a method for preparing a GaN film on a two-dimensional graphite substrate, which aims to solve the problems that a large amount of threading dislocation is generated in the GaN film due to larger lattice mismatch and thermal mismatch between GaN and a heterogeneous substrate at present, the performance of equipment is seriously influenced and the like.
The invention is realized by the following technical scheme: a method for preparing GaN film on two-dimensional graphite substrate includes stripping highly oriented pyrolytic graphite HOPG by mechanical stripping method to obtain graphite substrate material, transferring the stripped graphite substrate material to SiO2Forming a graphite substrate on the substrate or the Si substrate, carrying out oxygen plasma treatment on the prepared graphite substrate, then placing the graphite substrate in Metal Organic Chemical Vapor Deposition (MOCVD) reaction chamber to react and form an AlGaN nucleation layer, annealing and growing a GaN epitaxial film.
The method comprises the following specific steps:
(1) preparing a graphite substrate: sticking high oriented pyrolytic graphite HOPG onto photoresist, heating at 80-120 deg.C for 3-8 min, repeatedly stripping with transparent adhesive tape for 5-8 times to obtain graphite with thickness of 30-100nm, and transferring the graphite to SiO2A substrate or a Si substrate;
(2) oxygen plasma treatment: carrying out oxygen plasma treatment on the graphite substrate prepared in the step 1), wherein the pressure of the oxygen plasma treatment is 20-200mbar, the power is 80-600mW, and the time is 10-30 s;
(3) growing an AlGaN nucleation layer: placing the graphite substrate obtained by the treatment in the step 2) into an MOCVD reaction chamber, and carrying out reaction at the temperature of more than or equal to 1100 ℃ and under the pressure of 120-200 mbar2Cleaning for 8-15 min in atmosphere, and keeping the temperature and pressure unchanged under NH condition3High under atmosphereNitriding for 8-12 min; then with high purity H2Or N2Or H2And N2The mixed gas is used as carrier gas, an AlGaN nucleation layer grows on the surface of the graphite substrate at 900-1040 ℃ and 100-150mbar, the ratio of introduced V/III is 600-800, wherein the group III element Ga accounts for 80-90%, the Al accounts for 10-20%, and NH is introduced3The flux of trimethyl gallium (TMGa) and trimethyl aluminum (TMAl) is 0.02-0.0266 mol/min, 26.64-29.97 mu mol/min and 3.33-6.66 mu mol/min respectively, and the growth time is 150-;
(4) annealing treatment: annealing the AlGaN nuclear layer prepared in the step 3) at the temperature of 1100-1280 ℃ and the pressure of 100-150mbar for 2-6 min, wherein NH is introduced during annealing3The flow rate is 0.036-0.063 mol/min;
(5) growing a GaN epitaxial film: and 4) treating the obtained AlGaN nucleation layer in the step 4), keeping the flux of the Ga source unchanged, further merging and growing the GaN epitaxial layer at 1060-1200 ℃ and 100-150mbar, wherein the ratio of the introduced V/III is 300-800, the fluxes of introduced NH3 and TMGa are respectively 0.01-0.02 mol/min and 26-30 mu mol/min, and the growth time is 800-1000 s.
SiO in step (1)2The substrate or Si substrate thickness was 300 nm. And (3) in the step (2), the proportion of the surface defects of the graphite substrate after the oxygen plasma treatment to the total area of the substrate is 20-30%. NH introduced during nitridation in step (3)3The flow rate is controlled to be 0.025-0.036 mol/min; the size of the nuclear island forming the AlGaN nucleation layer is 30-50 nm. The thickness of the GaN epitaxial film grown in the step (5) is 0.6-1 μm.
The invention utilizes a controllable process to obtain graphite with a certain thickness from HOPG mechanical stripping and transfer the graphite to SiO2Or Si substrate, after which defects are fabricated in the substrate surface to provide nucleation sites. On the basis of the traditional two-step method, Al element is added into the nucleation layer and corresponding process parameters are set, so that the nucleation rate is improved, and the two-dimensional growth of the GaN film is finally realized.
The graphite obtained by the mechanical stripping method is a pure two-dimensional material, the thickness of the graphite obtained by the process can be controlled to be 30-100nm, the preparation and transfer integration is realized, the damage caused by the intermediate process is avoided, the quality of the prepared crystal is better, and the crystal is easy to separate from an epitaxial layer. The GaN film prepared on the substrate with the thickness is less constrained by lattice matching, has high quality and excellent photoelectric performance, and can be used in transferable GaN-based devices.
Drawings
FIG. 1 is a flow chart of a process for fabricating a GaN thin film according to the invention; FIG. 2 is a graph showing the results of Raman analysis of graphite before and after treatment in example 1; FIG. 3 is a graph showing the results of Raman analysis of graphite before and after treatment in example 2; FIG. 4 is a graph showing the results of Raman analysis of graphite before and after treatment in example 3; FIG. 5 is a scanning electron microscope image of a GaN epitaxial layer; fig. 6 is a graph showing the analysis result of GaN epitaxial layer PL photoluminescence test.
Detailed Description
The present invention now will be described more fully hereinafter with reference to the accompanying drawings, which illustrate process flows of various embodiments, and which are not intended to be limiting of the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the invention to those skilled in the art. The present invention will be described more specifically with reference to the following embodiments with reference to the accompanying drawings.
Example 1: a method for preparing GaN film on two-dimensional graphite substrate includes stripping highly oriented pyrolytic graphite HOPG by mechanical stripping method to obtain graphite substrate material, transferring the stripped graphite substrate material to SiO2Forming a graphite substrate on the Si substrate, carrying out oxygen plasma treatment on the prepared graphite substrate, then placing the graphite substrate in Metal Organic Chemical Vapor Deposition (MOCVD) reaction chamber to react and form an AlGaN nucleation layer, annealing and growing a GaN epitaxial film.
The method comprises the following specific steps:
1) preparing a graphite substrate; pasting a thin graphite layer of HOPG onto the photoresist at 80oAnd C, heating for 3 min, and repeatedly stripping the thin graphite for 5 times by using a transparent adhesive tape through a micro-mechanical stripping technology to obtain graphite with the thickness of 80 nm. The graphite on the tape was pasted onto a 300nm Si substrate.
2) Oxygen plasma treatment; and (3) carrying out oxygen plasma treatment on the graphite substrate material at the pressure of 20 mbar and the power of 80 mW for 20 s, wherein the surface defects of the obtained graphite substrate approximately account for 25% of the total area of the substrate. Raman analysis was performed on the graphite before and after the treatment, as shown in fig. 2, it can be seen that a D peak reflecting defects appeared after the treatment, indicating that the oxygen plasma treatment increased the defects of the graphite.
3) Growing an AlGaN nucleation layer; before growth, the substrate is placed in the MOCVD reaction chamber at 1100oC, 120 mbar, in H2And (5) carrying out high-temperature cleaning for 10 min in the atmosphere. After the cleaning step, NH under constant temperature and pressure3Nitriding at high temperature for 8min under atmosphere with NH introduced during nitriding3The flow rate was 0.027 mol/min. Followed by high purity H2As carrier gas, the pressure during the entire nucleation was set at 100mbar at 1040 oGrowing AlGaN nucleation layer 150 s under C, wherein the introduced V/III ratio is about 600, the Ga of the III group element accounts for 80%, the Al accounts for about 20%, the fluxes of introduced NH3, trimethyl gallium (TMGa) and trimethyl aluminum (TMAl) are respectively 0.027 mol/min, 26.64 mu mol/min and 6.66 mu mol/min, and the size of the nuclear island is about 35 nm.
4) Annealing; AlGaN nucleation layer at 1100 oC, annealing at 100mbar for 2min with NH introduced3The flow rate was 0.036 mol/min.
5) Growing a GaN epitaxial layer; at 1200 oC. Growing GaN epitaxial layer at 100mbar for 800 s, introducing V/III ratio of about 300, and introducing NH3And the flux of trimethyl gallium (TMGa) was 0.0104 mol/min and 26. mu. mol/min, respectively, and the film thickness was 0.7. mu.m.
Example 2: a method for preparing a GaN film on a two-dimensional graphite substrate comprises the following specific steps:
1) preparing a multilayer graphite substrate; pasting a thin graphite layer of HOPG onto the photoresist at 90oAnd C, heating for 5min, and repeatedly stripping the thin graphite layer for 8 times by using a transparent adhesive tape through a micro-mechanical stripping technology to obtain graphite with the thickness of 30 nm. Sticking the graphite layer on the adhesive tape to SiO with the thickness of 300nm2On a substrate.
2) Oxygen plasma treatment; and (3) carrying out oxygen plasma treatment on the surface of the graphite substrate under the pressure of 100mbar and the power of 300 mW for 30s, wherein the defects on the surface of the obtained graphite substrate account for about 20% of the total area of the substrate. Raman analysis was performed on the graphite before and after the treatment, as shown in fig. 3, it can be seen that a D peak reflecting defects appeared after the treatment, indicating that the oxygen plasma treatment increased the defects of the graphite.
3) Growing an AlGaN nucleation layer; before growth, the substrate is placed in the MOCVD reaction chamber at 1200oC, 150mbar, in H2And (5) carrying out high-temperature cleaning for 8min in the atmosphere. After the cleaning step, NH under constant temperature and pressure3Nitriding at high temperature for 10 min in the atmosphere with NH introduced during nitriding3The flow rate was 0.036 mol/min. Then with H2And N2The gas mixture as carrier gas, the pressure of the whole nucleation process is set to 120 mbar at 1020 DEG C oGrowing AlGaN nucleation layer 150 s under C, introducing V/III at a ratio of 700, wherein Ga in group III is 85%, Al is 15%, introducing NH3The flux of trimethyl gallium (TMGa) and trimethyl aluminum (TMAl) is 0.02 mol/min, 30 mu mol/min and 3.33 mu mol/min respectively, and the size of the nuclear island is about 30 nm.
4) Annealing; AlGaN nucleation layer at 1160oC. Annealing at 120 mbar for 3 min with NH introduced3The flow rate is 0.052 mol/min.
5) Growing a GaN epitaxial layer; at 1120 oC. Growing GaN epitaxial layer at 120 mbar for 1000s, introducing V/III ratio of 700, and introducing NH3And flux of trimethyl gallium (TMGa) is 0.021 mol/min and 30 μmol/min, respectively, and the film thickness is about 1 μm.
Example 3: a method for preparing a GaN film on a two-dimensional graphite substrate comprises the following specific steps:
1) preparing a multilayer graphite substrate; pasting a thin graphite layer of HOPG onto the photoresist at 120oAnd C, heating for 8min, and repeatedly stripping the thin graphite layer for 6 times by using a transparent adhesive tape through a micro-mechanical stripping technology to obtain graphite with the thickness of 100 nm. Sticking the graphite layer on the adhesive tape to SiO with the thickness of 300nm2On a substrate.
2) Oxygen plasma treatment; and (3) carrying out oxygen plasma treatment on the surface of the graphite substrate under the pressure of 200mbar and the power of 600mW for 10s, wherein the defects on the surface of the graphite substrate account for about 30% of the total area of the substrate. Raman analysis was performed on the graphite before and after the treatment, as shown in fig. 4, it can be seen that a D peak reflecting defects appeared after the treatment, indicating that the oxygen plasma treatment increased the defects of the graphite.
3) Growing an AlGaN nucleation layer; prior to growth, the substrate is placed in the MOCVD reaction chamber at 1300oC, 200mbar, in H2And (5) carrying out high-temperature cleaning for 15 min in the atmosphere. After the cleaning step, NH under constant temperature and pressure3High-temperature nitriding at atmosphere for 12min with NH introduced during nitriding3The flow rate was 0.025 mol/min. Followed by high purity N2As carrier gas, the pressure of the whole nucleation process is set to 150mbar at 900 oGrowing AlGaN nucleation layer 180s under C, introducing V/III ratio of 800, wherein group III element Ga accounts for 90%, Al accounts for 10%, introducing NH3The flux of trimethyl gallium (TMGa) and trimethyl aluminum (TMAl) is 0.027 mol/min, 28 μmol/min and 5.55 μmol/min respectively, and the size of the nuclear island is about 50 nm.
4) Annealing; AlGaN nucleation layer at 1280oC. Annealing at 150mbar for 6 min with NH introduced3The flow rate was 0.063 mol/min.
5) Growing a GaN epitaxial layer; at 1060 oC. Growing GaN epitaxial layer at 150mbar for 900 s with V/III ratio of about 800 and NH3And trimethylgallium (TMGa) at fluxes of 0.01 mol/min and 28. mu. mol/min, respectively, and a film thickness of about 0.6. mu.m. We performed surface topography analysis and photoelectric property analysis on the GaN epitaxial layer, as shown in fig. 5 and 6, respectively, to obtain a flat surface of the epitaxial layer, and the epitaxial layer has a light-emitting wavelength of 365nm and good photoelectric properties.
Claims (5)
1. A method for preparing a GaN film on a two-dimensional graphite substrate is characterized by comprising the following steps: stripping highly oriented pyrolytic graphite HOPG by mechanical stripping method to obtain graphite substrate material, transferring the stripped graphite substrate material to SiO2Forming a graphite substrate on a substrate or a Si substrate, and preparationPerforming oxygen plasma treatment on the graphite substrate, then placing the graphite substrate in a Metal Organic Chemical Vapor Deposition (MOCVD) reaction chamber to react to form an AlGaN nucleation layer, and performing annealing treatment to grow a GaN epitaxial film;
the method comprises the following specific steps:
(1) preparing a graphite substrate: sticking high oriented pyrolytic graphite HOPG onto photoresist, heating at 80-120 deg.C for 3-8 min, repeatedly stripping with transparent adhesive tape for 5-8 times to obtain graphite with thickness of 30-100nm, and transferring the graphite to SiO2A substrate or a Si substrate;
(2) oxygen plasma treatment: carrying out oxygen plasma treatment on the graphite substrate prepared in the step 1), wherein the pressure of the oxygen plasma treatment is 20-200mbar, the power is 80-600mW, and the time is 10-30s, so that defects are formed on the transferred graphite substrate;
(3) growing an AlGaN nucleation layer: placing the graphite substrate obtained by the treatment in the step 2) into an MOCVD reaction chamber, and carrying out reaction at the temperature of more than or equal to 1100 ℃ and under the pressure of 120-200 mbar2Cleaning for 8-15 min in atmosphere, and keeping the temperature and pressure unchanged under NH condition3Nitriding at high temperature for 8-12 min; then with high purity H2Or N2Or H2And N2The mixed gas is used as carrier gas, an AlGaN nucleation layer grows on the surface of the graphite substrate at 900-1040 ℃ and 100-150mbar, the ratio of introduced V/III is 600-800, wherein the group III element Ga accounts for 80-90%, the Al accounts for 10-20%, and NH is introduced3The flux of trimethyl gallium (TMGa) and trimethyl aluminum (TMAl) is 0.02-0.027 mol/min, 26.64-30 mu mol/min and 3.33-6.66 mu mol/min respectively, and the growth time is 100-;
(4) annealing treatment: annealing the AlGaN nuclear layer prepared in the step 3) at the temperature of 1100-1280 ℃ and the pressure of 100-150mbar for 2-6 min, wherein NH is introduced during annealing3The flow rate is 0.036-0.063 mol/min;
(5) growing a GaN epitaxial film: step 4) processing the obtained AlGaN nucleation layer, keeping the flux of the Ga source unchanged, further growing a GaN epitaxial layer at 1060-1200 ℃ and 100-150mbar, introducing NH, wherein the ratio of V to III is 300-8003The flux of TMGa is 0.01-0.021 mol/min and 26-30 mu mol/min, and the growth timeIs 800-.
2. The method for preparing GaN thin film on two-dimensional graphite substrate as claimed in claim 1, wherein: SiO in step (1)2The substrate or Si substrate thickness was 300 nm.
3. The method for preparing GaN thin film on two-dimensional graphite substrate as claimed in claim 2, wherein: and (3) in the step (2), the proportion of the surface defects of the graphite substrate after the oxygen plasma treatment to the total area of the substrate is 20-30%.
4. The method for preparing GaN thin film on two-dimensional graphite substrate as claimed in claim 1, wherein: NH introduced during nitridation in step (3)3The flow rate is controlled to be 0.025-0.036 mol/min; the size of the nuclear island forming the AlGaN nucleation layer is 30-50 nm.
5. The method for preparing GaN thin film on two-dimensional graphite substrate as claimed in claim 1, wherein: the thickness of the GaN epitaxial film grown in the step (5) is 0.6-1 μm.
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| CN201810273092.9A CN108511322B (en) | 2018-03-29 | 2018-03-29 | Method for preparing GaN film on two-dimensional graphite substrate |
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| CN201810273092.9A CN108511322B (en) | 2018-03-29 | 2018-03-29 | Method for preparing GaN film on two-dimensional graphite substrate |
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| Publication Number | Publication Date |
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