CN112103178A - GaN film coated on copper surface and preparation method thereof - Google Patents
GaN film coated on copper surface and preparation method thereof Download PDFInfo
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 68
- 239000010949 copper Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 34
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052582 BN Inorganic materials 0.000 claims abstract description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 11
- 238000000151 deposition Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 238000005070 sampling Methods 0.000 claims abstract description 7
- 239000010408 film Substances 0.000 claims description 35
- 239000011889 copper foil Substances 0.000 claims description 7
- 239000010409 thin film Substances 0.000 claims description 3
- 230000017525 heat dissipation Effects 0.000 abstract description 7
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical group C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000010453 quartz Substances 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 239000007789 gas Substances 0.000 description 12
- 238000001451 molecular beam epitaxy Methods 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 230000035882 stress Effects 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 3
- 230000008646 thermal stress Effects 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
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- 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
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02367—Substrates
- H01L21/0237—Materials
- H01L21/02425—Conductive materials, e.g. metallic silicides
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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
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02436—Intermediate layers between substrates and deposited layers
- H01L21/02439—Materials
- H01L21/02455—Group 13/15 materials
- H01L21/02458—Nitrides
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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
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02436—Intermediate layers between substrates and deposited layers
- H01L21/02494—Structure
- H01L21/02496—Layer structure
- H01L21/02505—Layer structure consisting of more than two layers
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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
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02538—Group 13/15 materials
- H01L21/0254—Nitrides
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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
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
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- 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
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/02631—Physical deposition at reduced pressure, e.g. MBE, sputtering, evaporation
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- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/20—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only AIIIBV compounds
- H01L29/2003—Nitride compounds
Abstract
The invention discloses a preparation method of a GaN film coated on a copper surface, which comprises the following steps: step S1, sampling the copper substrate, carrying out ultrasonic treatment and then drying the copper substrate by using nitrogen; step S2, growing a boron nitride material layer on the upper surface of the copper substrate; step S3, depositing an AlN layer on the boron nitride material layer; step S4, depositing Al with continuously variable components on the AlN layerxGa1‑xN layers; step S5, in the AlxGa1‑xAnd depositing a GaN layer on the N layer to obtain the GaN film coated on the surface of the copper. According to the invention, the GaN film directly grows on the copper substrate, and the prepared GaN film coated on the copper surface has the advantages of small internal stress, less dislocation and good heat dissipation, is suitable for preparing high-power electronic devices and lighting devices, has good practicability and has wide industrial popularization value.
Description
Technical Field
The invention relates to the technical field of semiconductor films, in particular to a GaN film coated on a copper surface and a preparation method thereof.
Background
The GaN material is used as a representative material of a third-generation semiconductor, has the characteristics of wide forbidden band, high saturation drift velocity, high critical breakdown electric field, high temperature resistance, radiation resistance and the like, and therefore has wide application potential and good market prospect in the fields of LED illumination, power electronic devices, radio frequency power devices and the like.
Although GaN devices made of GaN materials can withstand higher operating temperatures than first generation semiconductor silicon devices, the operating temperature of GaN devices is increasing as the power of GaN devices is increasing. The inventor of the invention finds that the traditional GaN device has poor heat dissipation effect due to the adoption of the substrate with the thickness of silicon, SiC or sapphire and the like, and causes the temperature rise of the GaN device, thereby causing the technical problem of electrical property degradation and even failure of the GaN device.
In order to solve the technical problem of temperature rise, a person skilled in the art usually adopts a wet etching or mechanical polishing method to reduce the thickness of the substrate, but the method still cannot completely solve the technical problem of poor heat dissipation, and the research and development and popularization progress of the high-power GaN device is severely restricted. Therefore, how to design or develop a GaN thin film material with good heat dissipation and suitable for manufacturing high-power electronic devices becomes a technical problem to be solved by those skilled in the art.
Disclosure of Invention
Aiming at the defects or improvement requirements in the prior art, the invention provides the GaN film coated on the copper surface and the preparation method thereof.
The purpose of the invention is realized by the following technical scheme:
according to one aspect of the present invention, a method for preparing a GaN film coated on a copper surface is provided, which comprises the following steps:
step S1, sampling the copper substrate, carrying out ultrasonic treatment and then drying the copper substrate by using nitrogen;
step S2, growing a boron nitride material layer on the upper surface of the copper substrate;
step S3, depositing an AlN layer on the boron nitride material layer;
step S4, depositing Al with continuously variable components on the AlN layerxGa1-xN layers;
step S5, in the AlxGa1-xAnd depositing a GaN layer on the N layer to obtain the GaN film coated on the surface of the copper.
According to another aspect of the invention, the GaN film coated on the copper surface is prepared by the preparation method, the GaN film coated on the copper surface comprises a copper substrate positioned at the bottom and a boron nitride material layer grown on the upper surface of the copper substrate, and an AlN layer and an Al layer are sequentially deposited on the boron nitride material layer from bottom to topxGa1-xAn N layer and a GaN layer.
Further, the thickness of the boron nitride material layer is 20 nm-200 nm.
Further, the AlN layer has a thickness of 50 nm to 200 nm.
Further, the AlxGa1-xThe thickness of the N layer is 100 nm-1 mm, wherein the variation range of x value in the Al component is 1-0.
Further, the thickness of the GaN layer is 100 nm-500 nm.
Further, the copper substrate is a copper foil.
Further, the thickness of the copper foil is 25 mm-100 mm.
Compared with the prior art, the technical scheme of the invention has the following advantages:
according to the invention, the GaN film directly grows on the copper substrate, and the prepared GaN film coated on the copper surface has the advantages of small internal stress, less dislocation and good heat dissipation, is suitable for preparing high-power electronic devices and lighting devices, has good practicability and has wide industrial popularization value.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the specific embodiments. The drawings are only for purposes of illustrating the particular embodiments and are not to be construed as limiting the invention. In the drawings:
FIG. 1 is a flow chart of the production process of the present invention;
FIG. 2 is a schematic diagram of a two-dimensional cross-sectional structure of a GaN film coated on a copper surface according to the invention;
in the figure: 1. copper liningA bottom; 2. a layer of boron nitride material; 3. an AlN layer; 4. al (Al)xGa1-xN layers; 5. and a GaN layer.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments. Examples of the embodiments are illustrated in the accompanying drawings, and specific embodiments described in the following embodiments of the invention are provided as illustrative of the embodiments of the invention only and are not intended to be limiting of the invention.
The invention provides a preparation method of a GaN film coated on a copper surface, as shown in figure 1, comprising the following steps:
and step S1, sampling the copper substrate 1 with the thickness of 25 mm-100 mm, carrying out ultrasonic treatment for 5 min-10 min by hydrochloric acid, carrying out ultrasonic treatment for 5 min-10 min by deionized water, and drying by nitrogen.
Step S21, placing the copper substrate 1 in a quartz furnace tube, vacuumizing to below 1 Pa, introducing hydrogen, wherein the flow rate of hydrogen gas is 100 ml/min-300 ml/min, and the temperature of the quartz furnace tube is maintained at 900 DEGoC ~ 1100oC, heating for 3-6 h.
Step S22, vacuumizing the quartz furnace tube to below 1 Pa, introducing argon gas with the flow rate of 100-300 ml/min, and heating the quartz furnace tube to 1000oC ~ 1200oC, keeping for 30-60 min; followed by introduction of BH3And NH3The mixed gas (volume ratio is 1: 1) is adopted to grow a Boron Nitride (BN) material layer 2 with the thickness of 20 nm-200 nm on a copper substrate 1 by adopting a Chemical Vapor Deposition (CVD) technology, wherein the flow rate of the mixed gas is 50 ml/min-200 ml/min, and the growth time is 60 min-90 min. In this step, BH3And NH3As a precursor material, namely a reaction source material, the BN film can grow by the reaction of the precursor material and the reaction source material at high temperature. The crystal structure of BN is the same as that of AlN, and dislocation defects are few in the growth process of the BN, so that the BN material layer can reduce or overcome the technical defects of lattice mismatch.
Step S3, growing a layer 2 of Boron Nitride (BN) material to a thickness by Molecular Beam Epitaxy (MBE)An AlN layer 3 of 50 nm to 200 nm, wherein the reaction source is trimethyl aluminum (TMAI) and NH3Growth temperature 500oC ~ 800oC, the growth time is 30-90 min, the growth pressure is 50-100 Pa, TMAI and NH3The flow rate is 40 ml/min to 100 ml/min.
Step S4, growing Al with the thickness of 100 nm-1 mm and continuously variable components on the AlN layer 3 by adopting a Molecular Beam Epitaxy (MBE) technologyxGa1-xN layer 4, wherein solid metal Ga, Trimethylaluminum (TMAI) and NH are used3As a reaction source, the growth temperature is 500oC ~ 750oC, the growth pressure is 10 Pa to 40 Pa, the starting flow rate of TMAI is 50 ml/min to 300 ml/min, NH3The initial flow is 0, and then the TMAI flow is reduced by 10 ml/min and NH at intervals of 5 min-10 min in sequence3The flow rate is increased by 10 ml/min until the TMAI flow rate is reduced to 0, and Al grows in the processxGa1-xThe composition of the N layer 4 changes continuously as shown by the decrease of the value of x from 1 to 0 in the Al composition.
Due to the large difference between the lattice constant and the thermal expansion coefficient of AlN and GaN, if a GaN layer is directly grown on the AlN layer, dislocation and even cracking are easily generated under the dual action of lattice stress and thermal stress. Therefore, in this step, the grown Al is caused to grow by controlling the flow rate of the reaction sourcexGa1-xThe Al composition of the N layer is slowly changed from 1 to 0, which is beneficial to reducing the stress generated when the active GaN layer is grown subsequently. AlN layer 3 grown in step S3 and Al grown in this step and having continuously variable compositionxGa1-xThe N layers 4 are all used as growth buffer layers, and the technical problem of thermal stress generated in the growth process of the GaN film can be reduced or overcome.
Step S5, Molecular Beam Epitaxy (MBE) is performed on AlxGa1-xA GaN layer 5 with the thickness of 100 nm-500 nm is grown on the N layer 4, wherein the reaction source is solid metal Ga and NH3Growth temperature 500oC ~ 800oC, the growth time is 30-60 min, the growth air pressure is 10-40 Pa, and NH is added3The flow rate is 40 ml/min-100 ml/min, so that the GaN film coated on the copper surface is prepared.
The invention is prepared by the preparation methodThe GaN film coated on the copper surface comprises a copper substrate 1 positioned at the bottom and a boron nitride material layer 2 growing on the upper surface of the copper substrate, wherein an AlN layer 3 and Al with continuously changed components are sequentially deposited and grown on the boron nitride material layer 2 from bottom to topxGa1-xN layer 4 and GaN layer 5.
The invention adopts a chemical synthesis method to directly grow a GaN film on a copper substrate, wherein the GaN film comprises a boron nitride material layer, an AlN layer and Al which are sequentially grown on the copper substrate from bottom to topxGa1-xAn N layer and a GaN layer. Based on the characteristic of strong heat conductivity of copper, before a GaN layer grows, a BN material layer grows on a copper substrate to reduce dislocation and lattice mismatch defects, and then an AlN layer and Al with continuously variable components grow in sequencexGa1-xThe N layer is used as a growth buffer layer to eliminate thermal stress; on the basis, the GaN layer is finally grown, and the GaN film coated on the copper surface prepared by the preparation method has the advantages of small internal stress, less dislocation and good heat dissipation, is suitable for preparing high-power electronic devices and lighting devices, has good practicability and has wide industrial popularization value.
Example 1
The embodiment provides a method for preparing a GaN film coated on a copper surface, which comprises the following steps:
step S1, sampling a copper foil substrate 1 with the thickness of 50 mm, carrying out ultrasonic treatment for 8 min by hydrochloric acid, then carrying out ultrasonic treatment for 7 min by deionized water, and drying by nitrogen;
step S21, placing the copper foil substrate 1 in a quartz furnace tube, vacuumizing to below 1 Pa, introducing hydrogen, wherein the flow rate of hydrogen gas is 200 ml/min, and the temperature of the quartz furnace tube is kept at 1000 DEGoC, heating for 4.5 hours;
step S22, vacuumizing the quartz furnace tube to below 1 Pa, introducing argon gas with the flow rate of 200 ml/min, and heating the quartz furnace tube to 1100 DEG CoC, keeping for 45 min; followed by introduction of BH in a volume ratio of 1:13And NH3The mixed gas of (2) is used for growing a boron nitride material layer 2 with the thickness of 50 nm on a copper foil substrate 1 by adopting a CVD technology, wherein the flow rate of the mixed gas is 100 ml/min,the growth time is 75 min;
step S3, growing an AlN layer 3 with a thickness of 100 nm on the boron nitride material layer 2 by adopting an MBE technology, wherein the reaction sources are trimethyl aluminum and NH3Growth temperature 600oC, growth time of 60min, growth pressure of 80Pa, trimethylaluminum and NH3The flow rate is 70 ml/min;
step S4, growing Al with the thickness of 500 nm and continuously variable components on the AlN layer 3 by adopting MBE technologyxGa1-xN layer 4, using solid metal Ga, trimethylaluminum and NH3As a reaction source, growth temperature 600oC, the growth pressure is 30Pa, the initial flow rate of the trimethylaluminum is 200 ml/min, and NH is3The initial flow rate is 0, then the flow rate of the trimethylaluminum is reduced by 10 ml/min and NH are carried out at intervals of 8 min in sequence3The flow rate is increased by 10 ml/min until the TMAI flow rate is reduced to 0, and Al grows in the processxGa1-xThe composition of the N layer 4 is changed continuously, and the value of x in the Al composition is reduced from 1 to 0;
step S5, adopting MBE technology to AlxGa1-xA GaN layer 5 with the thickness of 200 nm is grown on the N layer 4, and the reaction sources are solid metal Ga and NH3Growth temperature 700oAnd C, growing for 45min, wherein the growth pressure is 20Pa, and the NH3 flow is 70 ml/min, so that the GaN film coated on the copper surface is prepared.
Example 2
The embodiment provides a method for preparing a GaN film coated on a copper surface, which comprises the following steps:
step S1, sampling a copper substrate 1 with the thickness of 25 mm, carrying out ultrasonic treatment for 5min by hydrochloric acid, carrying out ultrasonic treatment for 5min by deionized water, and drying by nitrogen;
step S21, placing the copper substrate 1 in a quartz furnace tube, vacuumizing to below 1 Pa, introducing hydrogen, wherein the flow rate of hydrogen gas is 100 ml/min, and the temperature of the quartz furnace tube is kept at 900 DEGoC, heating for 3 hours;
step S22, vacuumizing the quartz furnace tube to below 1 Pa, introducing argon gas with the flow rate of 100 ml/min, and heating the quartz furnace tube to 1000oC, keeping for 30 min; followed by introduction of BH3And NH3Mixed gas (body) of (2)Volume ratio of 1: 1), growing a BN material layer 2 with the thickness of 20 nm on a copper substrate 1 by adopting a CVD technology, wherein the flow rate of mixed gas is 50 ml/min, and the growth time is 60 min;
step S3, growing an AlN layer 3 with a thickness of 50 nm on the BN material layer 2 by adopting the MBE technology, wherein the reaction sources are TMAI and NH3Growth temperature 500oC, growth time of 30 min, growth pressure of 50 Pa, TMAI and NH3The flow rate is 40 ml/min;
step S4, growing Al with the thickness of 100 nm and continuously variable components on the AlN layer 3 by adopting MBE technologyxGa1-xN layer 4, using solid metal Ga, TMAI and NH3As a reaction source, the growth temperature is 500oC, growth pressure 10 Pa, TMAI starting flow 50 ml/min, NH3The flow rate is 0, then the TMAI flow rate is reduced by 10 ml/min and NH are carried out every 5min in sequence3The flow rate is increased by 10 ml/min until the TMAI flow rate is reduced to 0, and Al grows in the processxGa1-xThe composition of the N layer 4 is changed continuously, and the value of x in the Al composition is reduced from 1 to 0;
step S5, adopting MBE technology to AlxGa1-xA GaN layer 5 with the thickness of 500 nm is grown on the N layer 4, and the reaction sources are solid metal Ga and NH3Growth temperature 800oC, growth time is 60min, growth pressure is 40 Pa, NH3The flow rate was 00 ml/min, and a GaN film coated on the copper surface was obtained.
Example 3
The embodiment provides a method for preparing a GaN film coated on a copper surface, which comprises the following steps:
step S1, sampling a copper substrate 1 with the thickness of 100 mm, carrying out ultrasonic treatment for 10min by hydrochloric acid, then carrying out ultrasonic treatment for 10min by deionized water, and drying by nitrogen;
step S21, placing the copper substrate 1 in a quartz furnace tube, vacuumizing to below 1 Pa, introducing hydrogen, wherein the flow rate of the hydrogen is 300 ml/min, and the temperature of the quartz furnace tube is kept at 1100 DEGoC, heating for 6 hours;
step S22, vacuumizing the quartz furnace tube to below 1 Pa, introducing argon gas with the flow rate of 300 ml/min, and heating the quartz furnace tube to 1200 DEG CoC, keeping for 60 min; followed by introduction of BH3And NH3The mixed gas (volume ratio is 1: 1) is adopted to grow a BN material layer 2 with the thickness of 200 nm on a copper substrate 1 by adopting a CVD technology, wherein the flow rate of the mixed gas is 200 ml/min, and the growth time is 90 min;
step S3, growing an AlN layer 3 with a thickness of 200 nm on the BN material layer 2 by adopting the MBE technology, wherein the reaction sources are TMAI and NH3Growth temperature 800oC, growth time is 90 min, growth pressure is 100 Pa, TMAI and NH3The flow rate is 100 ml/min;
step S4, growing Al with the thickness of 1 mm and continuously variable components on the AlN layer 3 by adopting MBE technologyxGa1-xN layer 4, using solid metal Ga, TMAI and NH3As a reaction source, growth temperature 750oC, growth pressure 40 Pa, TMAI starting flow 300 ml/min, NH3The flow rate is 0, then the TMAI flow rate is reduced by 10 ml/min and NH are carried out every 10min in sequence3The flow rate is increased by 10 ml/min until the TMAI flow rate is reduced to 0, and Al grows in the processxGa1-xThe composition of the N layer 4 is changed continuously, and the value of x in the Al composition is reduced from 1 to 0;
step S5, adopting MBE technology to AlxGa1-xA GaN layer 5 with the thickness of 500 nm is grown on the N layer 4, and the reaction sources are solid metal Ga and NH3Growth temperature 800oC, growth time is 60min, growth pressure is 40 Pa, NH3The flow rate was 100 ml/min, thereby obtaining a GaN thin film coated on the copper surface.
In the embodiments of the invention, the GaN film directly grows on the copper substrate, and the GaN film coated on the copper surface prepared by the process has the advantages of small internal stress, less dislocation and good heat dissipation, is suitable for preparing high-power electronic devices and lighting devices, has good practicability and has wide industrial popularization value.
It should be noted that the above-mentioned embodiments illustrate rather than limit the invention, and that those skilled in the art will be able to design alternative embodiments without departing from the scope of the appended claims. The present embodiments are therefore to be considered as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein, and any reference signs in the claims are not intended to be construed as limiting the claim concerned. In the claims, the word "comprising" does not exclude the presence of data or steps not listed in a claim.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (8)
1. A preparation method of a GaN film coated on a copper surface is characterized by comprising the following steps:
step S1, sampling the copper substrate, carrying out ultrasonic treatment and then drying the copper substrate by using nitrogen;
step S2, growing a boron nitride material layer on the upper surface of the copper substrate;
step S3, depositing an AlN layer on the boron nitride material layer;
step S4, depositing Al with continuously variable components on the AlN layerxGa1-xN layers;
step S5, in the AlxGa1-xAnd depositing a GaN layer on the N layer to obtain the GaN film coated on the surface of the copper.
2. A GaN thin film coated on a copper surface, which is prepared by the preparation method of claim 1, characterized in that: the GaN film coated on the copper surface comprises a copper substrate positioned at the bottom and a boron nitride material layer growing on the upper surface of the copper substrate, wherein an AlN layer and Al are sequentially deposited on the boron nitride material layer from bottom to topxGa1-xAn N layer and a GaN layer.
3. The GaN film coated on the copper surface as recited in claim 2, wherein: the thickness of the boron nitride material layer is 20 nm-200 nm.
4. The GaN film coated on the copper surface as recited in claim 2, wherein: the AlN layer is 50 nm-200 nm thick.
5. The GaN film coated on the copper surface as recited in claim 2, wherein: the Al isxGa1-xThe thickness of the N layer is 100 nm-1 mm, wherein the variation range of x value in the Al component is 1-0.
6. The GaN film coated on the copper surface as recited in claim 2, wherein: the thickness of the GaN layer is 100 nm-500 nm.
7. The GaN film coated on the copper surface as recited in claim 2, wherein: the copper substrate is a copper foil.
8. The GaN film coated on the copper surface as recited in claim 7, wherein: the thickness of the copper foil is 25 mm-100 mm.
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