CN115376886A - Nitrogen-doped p-type gallium oxide film and preparation method and application thereof - Google Patents
Nitrogen-doped p-type gallium oxide film and preparation method and application thereof Download PDFInfo
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- CN115376886A CN115376886A CN202210878667.6A CN202210878667A CN115376886A CN 115376886 A CN115376886 A CN 115376886A CN 202210878667 A CN202210878667 A CN 202210878667A CN 115376886 A CN115376886 A CN 115376886A
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- 229910001195 gallium oxide Inorganic materials 0.000 title claims abstract description 166
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 title claims abstract description 165
- 238000002360 preparation method Methods 0.000 title claims abstract description 56
- 229910002601 GaN Inorganic materials 0.000 claims abstract description 147
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 108
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000001301 oxygen Substances 0.000 claims abstract description 63
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 57
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 56
- 239000013077 target material Substances 0.000 claims abstract description 40
- 230000001590 oxidative effect Effects 0.000 claims abstract description 16
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000005240 physical vapour deposition Methods 0.000 claims abstract description 12
- 239000010408 film Substances 0.000 claims description 148
- 239000000758 substrate Substances 0.000 claims description 133
- 239000000919 ceramic Substances 0.000 claims description 73
- 239000010409 thin film Substances 0.000 claims description 64
- 239000000843 powder Substances 0.000 claims description 49
- 229910052594 sapphire Inorganic materials 0.000 claims description 34
- 239000010980 sapphire Substances 0.000 claims description 34
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 33
- 238000000151 deposition Methods 0.000 claims description 32
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 28
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 26
- 239000000395 magnesium oxide Substances 0.000 claims description 23
- 238000000498 ball milling Methods 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 230000008021 deposition Effects 0.000 claims description 18
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 18
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 16
- 229910052733 gallium Inorganic materials 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 13
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 13
- 238000005245 sintering Methods 0.000 claims description 12
- 238000004544 sputter deposition Methods 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 9
- 238000004549 pulsed laser deposition Methods 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001451 molecular beam epitaxy Methods 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 abstract description 21
- 239000013078 crystal Substances 0.000 abstract description 15
- 239000004065 semiconductor Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000001035 drying Methods 0.000 description 18
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- 239000000203 mixture Substances 0.000 description 5
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 4
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- 238000004098 selected area electron diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 1
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- 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
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Abstract
The invention provides a nitrogen element doped p-type gallium oxide film and a preparation method and application thereof. The preparation method of the invention ablates, sputters or evaporates the GaN target material in the vacuum cavity by the physical vapor deposition method to obtain the GaN cluster, and then utilizes O 2 Oxidizing the GaN clusters to obtain N-doped Ga 2 O 3 A film; by adjusting the oxygen pressure, i.e. optimizing control of N in Ga 2 O 3 To obtain P-type conductive N-doped Ga 2 O 3 A film. The method obtains nitrogen-doped gallium oxide by oxidizing the gallium nitride small clusters, effectively improves the solubility of nitrogen in the gallium oxide film, and generates voids by substituting oxygen with nitrogenA hole, thereby realizing a p-type conductive gallium oxide film; the gallium oxide film prepared by the invention has high hole carrier concentration, low resistivity, high film crystal quality, simple required equipment and preparation process and low production cost, and can promote the application of gallium oxide in the field of ultra-wide bandgap semiconductor devices.
Description
Technical Field
The invention relates to the technical field of ultra-wide bandgap semiconductor materials and devices, in particular to a nitrogen-doped p-type gallium oxide film and a preparation method and application thereof.
Background
With the rapid development of new energy, rail transit, smart grid and other fields, people urgently need semiconductor power devices capable of working under high voltage and high power. Gallium oxide as a novel ultra-wide bandgap semiconductor material has a band gap of 4.8eV, a large breakdown-resistant field strength and good thermal stability, and is very suitable for being applied to the fields of solar blind ultraviolet detection, high-power electronic devices and the like, so that the gallium oxide is greatly concerned by researchers.
Gallium oxide has five different crystal structures, wherein beta-Ga 2 O 3 Most stable, beta-Ga 2 O 3 The crystal lattice constant of the monoclinic structure is a =12.23A, b =3.04A and c =5.80A. beta-Ga 2 O 3 The high-quality epitaxial growth of the film is the basis for preparing the gallium oxide device, and the beta-Ga can be realized on the c-plane sapphire substrate 2 O 3 Epitaxial growth of thin films, but c-plane sapphire and beta-Ga 2 O 3 The lattice mismatch is 7.4%, which allows for the epitaxial growth of β -Ga on c-plane sapphire substrates 2 O 3 The quality of the film is not high.
After many years of efforts, epitaxial growth, bandgap control and n-type doping of gallium oxide films have made great progress. However, the p-type doping of the gallium oxide thin film is limited by the low solubility of the doping elements, the hole self-trapping and the background electron self-compensation effect, so that the preparation of the p-type gallium oxide thin film still has great challenges. In order to realize the large-scale application of the gallium oxide thin film, the bipolar doping of the gallium oxide thin film must be solved. In recent years, N is considered to be the most potential element for p-type doping of gallium oxide, considering that the atomic size of N element is close to that of O element and the level of nitrogen element acceptor impurity is shallow in gallium oxide. However, nitrogen element faces the problem of low solubility in gallium oxide, so that the preparation of nitrogen-doped p-type gallium oxide thin films is difficult to realize.
Disclosure of Invention
In view of this, the invention provides a nitrogen-doped p-type gallium oxide thin film, and a preparation method and an application thereof, so as to improve the solubility of an N element, and the nitrogen element replaces an oxygen element to generate a cavity, thereby preparing the p-type gallium oxide thin film.
In a first aspect, the present invention provides a method for preparing a nitrogen-doped p-type gallium oxide thin film, comprising the following steps:
providing a GaN ceramic target material;
providing a substrate;
and placing the substrate in a vacuum cavity of a deposition device, using the GaN ceramic target material as a nitrogen source and a gallium source, ablating, sputtering or evaporating the GaN target material by adopting a physical vapor deposition method to obtain a GaN cluster, and oxidizing the GaN cluster by using oxygen so as to grow on the substrate to obtain the nitrogen-doped p-type gallium oxide film.
Preferably, the preparation method of the nitrogen-doped p-type gallium oxide film comprises the steps of placing the substrate in a vacuum cavity of a deposition device, heating the substrate to 400-750 ℃, ablating, sputtering or evaporating the GaN target material by using a physical vapor deposition method by using the GaN ceramic target material as a nitrogen source and a gallium source to obtain a GaN cluster, introducing oxygen into the vacuum cavity, and oxidizing the GaN cluster by using the oxygen to grow the nitrogen-doped p-type gallium oxide film on the substrate.
Preferably, the preparation method of the nitrogen-doped p-type gallium oxide film comprises any one of a magnetron sputtering method, a pulsed laser deposition method and a molecular beam epitaxy method;
and/or the substrate comprises at least one of a c-plane sapphire substrate, a magnesium oxide substrate, a gallium nitride substrate, a silicon substrate, an NSTO substrate, a quartz glass substrate, an r-plane sapphire and an a-plane sapphire.
Preferably, the preparation method of the nitrogen element doped p-type gallium oxide film comprises the steps of ablating a GaN target material by adopting a pulse laser deposition method to obtain a GaN cluster, introducing oxygen into a vacuum cavity, and adjusting the oxygen pressure of a growth chamber to be 0-4 Pa; wherein the pulse laser energy is 150-400 mJ, the number of pulses is 9000-54000, and the pulse frequency is 1-10 Hz.
Preferably, the preparation method of the nitrogen-doped p-type gallium oxide film comprises the steps of sputtering a GaN target by adopting a magnetron sputtering method, simultaneously introducing argon and oxygen into a vacuum cavity, adjusting the flow of the argon to be 10-60 sccm, the flow of the oxygen to be 0-30 sccm, starting pressure in a growth chamber to be 1-6 Pa, depositing film pressure to be 0.2-4 Pa, sputtering power of the target to be 40-160W, and depositing for 30-120 min.
Preferably, the preparation method of the nitrogen-doped p-type gallium oxide thin film comprises the following steps:
carrying out ball milling on the GaN powder to obtain fine powder;
pressing the fine powder subjected to ball milling into a ceramic green sheet;
sintering the ceramic green sheet at 800-1200 ℃ to obtain the GaN ceramic target.
Preferably, in the preparation method of the nitrogen element doped p-type gallium oxide film, the fine powder after ball milling is pressed into a ceramic blank sheet with the thickness of 2-5 mm under the pressure of 2-10 Mpa; sintering the ceramic green sheet at 800-1200 ℃ for 2-5 h to obtain the GaN ceramic target.
Preferably, the preparation method of the nitrogen-doped p-type gallium oxide film further comprises the step of sequentially cleaning the substrate with acetone, absolute ethyl alcohol and deionized water before placing the substrate in a vacuum cavity of a pulse laser deposition system.
In a second aspect, the invention also provides a nitrogen-doped p-type gallium oxide film prepared by the preparation method.
In a third aspect, the invention also provides an application of the nitrogen element doped p-type gallium oxide film prepared by the preparation method or the nitrogen element doped p-type gallium oxide film in preparing solar blind ultraviolet detectors and high-power electronic devices.
Compared with the prior art, the nitrogen-doped p-type gallium oxide film and the preparation method and the application thereof have the following technical effects:
the preparation method of the nitrogen element doped p-type gallium oxide film comprises the steps of ablating, sputtering or evaporating a GaN target material in a vacuum cavity by a physical vapor deposition method to obtain a GaN cluster, and then utilizing O 2 Oxidizing the GaN clusters to obtain N-doped Ga 2 O 3 A film; oxygen pressure of GaN cluster is oxidized by adjusting, namely N in Ga is optimally controlled 2 O 3 To obtain P-type conductive N-doped Ga 2 O 3 A film. According to the method, nitrogen-doped gallium oxide is obtained by oxidizing the gallium nitride small clusters, so that the solubility of nitrogen in the gallium oxide film is effectively improved; nitrogen replaces oxygen to generate holes, so that the p-type conductive gallium oxide film is realized; the nitrogen element doped p-type gallium oxide film prepared by the method is a high-quality epitaxial film, the hole carrier concentration is high, the resistivity is low, the required equipment and preparation process are simple, the production cost is low, and the application of gallium oxide in the field of ultra-wide bandgap semiconductor devices is promoted.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is a schematic flow chart of a method for preparing a nitrogen-doped p-type gallium oxide film according to the present invention;
FIG. 2 is an x-ray diffraction pattern of a nitrogen-doped p-type gallium oxide thin film prepared in examples 2 to 3 of the present invention;
FIG. 3 is an x-ray diffraction rocking curve spectrum of a nitrogen-doped p-type gallium oxide thin film prepared in examples 2 to 3 of the present invention;
FIG. 4 is a transmission spectrum of a nitrogen-doped p-type gallium oxide thin film prepared in example 2 of the present invention, and the inset shows (α hv) of the nitrogen-doped p-type gallium oxide thin film 2 Graph of relationship to hv;
FIG. 5 is a transmission spectrum of a nitrogen-doped p-type gallium oxide thin film prepared in example 3 of the present invention, and the inset shows (α hv) of the nitrogen-doped p-type gallium oxide thin film 2 Graph of relationship to hv;
FIG. 6 is an x-ray diffraction (XRD) pattern of a nitrogen-doped p-type gallium oxide thin film prepared in example 5 of the present invention;
FIG. 7 is an XRD rocking curve pattern of a nitrogen-doped p-type gallium oxide thin film prepared in example 5 of the present invention;
FIG. 8 shows a nitrogen-doped p-type gallium oxide thin film prepared in example 5 of the present invention
A map;
FIG. 9 shows a transmission spectrum of a nitrogen-doped p-type gallium oxide thin film prepared in example 5 of the present invention, wherein the inset shows (α hv) of the nitrogen-doped p-type gallium oxide thin film 2 Graph of relationship to hv;
FIG. 10 is a cross-sectional view of a field emission scanning electron microscope (FE-SEM) of a nitrogen-doped p-type gallium oxide thin film prepared in example 5 of the present invention;
FIG. 11 is a surface view of a field emission scanning electron microscope (FE-SEM) of a nitrogen-doped p-type gallium oxide thin film prepared in example 5 of the present invention;
FIG. 12 is an element distribution diagram (EDS-mapping) of a nitrogen-doped p-type gallium oxide thin film prepared in example 5 of the present invention;
FIG. 13 is a High Resolution Transmission Electron Micrograph (HRTEM) of a nitrogen doped p-type gallium oxide thin film prepared in example 5 of the present invention;
fig. 14 is a selected area electron diffraction pattern (SAED) of nitrogen-doped p-type gallium oxide thin film prepared in example 5 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments.
The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments of the present invention, belong to the protection scope of the present invention.
The embodiment of the application provides a preparation method of a nitrogen-doped p-type gallium oxide film, as shown in fig. 1, comprising the following steps:
s1, providing a GaN ceramic target material;
s2, providing a substrate;
and S3, placing the substrate in a vacuum cavity of a deposition device, using the GaN ceramic target material as a nitrogen source and a gallium source, ablating, sputtering or evaporating the GaN target material by adopting a physical vapor deposition method to obtain a GaN cluster, and oxidizing the GaN cluster by using oxygen so as to grow on the substrate to obtain the nitrogen-doped p-type gallium oxide film.
The preparation method of the nitrogen-doped p-type gallium oxide thin film comprises the steps of ablating, sputtering or evaporating a GaN target material in a vacuum cavity by a physical vapor deposition method to obtain a GaN cluster, and then utilizing O 2 Oxidizing the GaN clusters to obtain N-doped Ga 2 O 3 A film; the oxygen pressure of the GaN cluster is oxidized by adjusting, namely, N is optimally controlled at Ga 2 O 3 To obtain P-type conductive N-doped Ga 2 O 3 A film. According to the technical scheme, nitrogen-doped gallium oxide is obtained by oxidizing the small clusters of gallium nitride, so that the solubility of nitrogen in the gallium oxide film is effectively improved; the nitrogen element replaces the oxygen element to generate a hole, so that the p-type conductive gallium oxide film is realized.
In some embodiments, a substrate is placed in a vacuum cavity of a deposition device, the substrate is heated to 400-750 ℃, the GaN ceramic target is used as a nitrogen source and a gallium source, the GaN target is ablated, sputtered or evaporated by adopting a physical vapor deposition method to obtain a GaN cluster, oxygen is introduced into the vacuum cavity, and the GaN cluster is oxidized by using the oxygen, so that the nitrogen-doped p-type gallium oxide film is grown on the substrate.
In some embodiments, the physical vapor deposition method includes any one of a magnetron sputtering method, a pulsed laser deposition method, and a molecular beam epitaxy method;
and/or the substrate comprises at least one of a c-plane sapphire substrate, a magnesium oxide substrate, a gallium nitride substrate, a silicon substrate, a NSTO substrate, a quartz glass substrate, r-plane sapphire and a-plane sapphire. Preferably, the substrate is a magnesium oxide substrate, the magnesium oxide substrate and beta-Ga 2 O 3 The lattice mismatch rate of the magnesium oxide substrate is lower than 3 percent, so that the magnesium oxide substrate is more suitable for growing high-quality epitaxial beta-Ga 2 O 3 The preparation of single crystal thin films and high-quality epitaxial gallium oxide thin films is the premise and the basis of the application of gallium oxide thin film devices.
In some embodiments, a pulsed laser deposition method is adopted to ablate a GaN target material to obtain a GaN cluster, oxygen is introduced into a vacuum cavity, and the oxygen pressure of a growth chamber is adjusted to be 0-4 Pa; wherein the pulse laser energy is 150-400 mJ, the number of pulses is 9000-54000, and the pulse frequency is 1-10 Hz.
In some embodiments, a magnetron sputtering method is adopted to sputter the GaN target, argon and oxygen are introduced into the vacuum cavity at the same time, the flow of the argon is adjusted to be 10-60 sccm, the flow of the oxygen is 0-30 sccm, the starting pressure in the growth chamber is 1-6 Pa, the pressure of the deposited film is 0.2-4 Pa, the sputtering power of the target is 40-160W, and the deposition time is 30-120 min.
In some embodiments, the method of preparing a GaN ceramic target comprises:
carrying out ball milling on the GaN powder to obtain fine powder;
pressing the fine powder subjected to ball milling into a ceramic green sheet;
sintering the ceramic green sheet at 800-1200 ℃ to obtain the GaN ceramic target.
In some embodiments, the fine powder after ball milling is pressed into ceramic green sheets with the diameter of 2-5 mm under the pressure of 2-10 Mpa; sintering the ceramic green sheet at 800-1200 ℃ for 2-5 h to obtain the GaN ceramic target.
Specifically, gaN powder is placed in a ball milling tank, deionized water accounting for 55-65% of the total mass of the powder is added for ball milling for 6-10 hours, and the powder is placed in a vacuum drying oven for drying treatment to obtain dry powder, namely fine powder, wherein the specific drying temperature is 110-130 ℃, and the drying time is 6-10 hours; then adding absolute ethyl alcohol with the total mass of 1-5% of the powder into the dried fine powder, grinding and stirring uniformly, and pressing into ceramic green sheets with the thickness of 2-5 mm under the pressure of 2-10 Mpa; sintering the ceramic green sheet at 800-1200 ℃ for 2-5 h to obtain the GaN ceramic target.
In some embodiments, before placing the substrate in the vacuum chamber of the pulsed laser deposition system, the method further comprises sequentially cleaning the substrate with acetone, absolute ethyl alcohol, and deionized water.
Meanwhile, the prior art discloses a p-type nitrogen-doped gallium oxide film and a preparation method thereof, wherein the preparation method of the film comprises the following steps: and placing the gallium nitride film containing the substrate in a cavity of thermal growth equipment, introducing purge gas, annealing at a first temperature, injecting oxygen from the upper surface of the gallium nitride film to the inside, performing thermal oxidation to form a gallium nitride-gallium oxide heterojunction, wherein the injection depth of the oxygen is less than the thickness of the gallium nitride film, continuing annealing at a second temperature, continuously injecting the oxygen until the depth is consistent with the thickness of the gallium nitride film, and annealing at a third temperature to finish the preparation of the p-type nitrogen-doped gallium oxide film. Obviously, the method is to prepare a gallium oxide film on a substrate containing a gallium nitride film; the method directly prepares the p-type nitrogen-doped gallium oxide film on the substrate, and the p-type nitrogen-doped gallium oxide film does not contain gallium nitride, so that the film structure finally prepared by the method is completely different from the film structure prepared in the prior art. Meanwhile, in the prior art, a p-type nitrogen-doped gallium oxide film is prepared by diffusing and oxidizing a gallium nitride film, while in the application, a GaN cluster is sputtered first, and then the GaN cluster is oxidized to prepare the p-type nitrogen-doped gallium oxide film, which is shown in the applicationThe principle of the preparation method is completely different from that of the prior art, and compared with the prior art, the preparation method is easier to react; moreover, the substrate in the prior art includes a substrate containing a gallium nitride film, but the substrate in the method of the present application can be freely selected without containing a gallium nitride film, so that the substrate used by the substrate and the substrate used by the substrate are different. Furthermore, the thickness of the p-type nitrogen-doped gallium oxide film prepared in the prior art is 1-4 μm, but the thickness of the gallium oxide film prepared in the present application is not limited, and can be, for example, 0-1 μm. In a word, the substrate used for preparing the p-type nitrogen-doped gallium oxide film, the preparation principle and the structure and the thickness of the finally prepared gallium oxide film are different from those of the prior art. The p-type gallium oxide thin film prepared by the method has good crystal quality, the ultraviolet visible transmittance exceeds 90%, and the conductivity is good. The preparation method of the p-type gallium oxide film provided by the invention utilizes a physical vapor deposition method and O 2 The GaN oxide cluster effectively improves the content of N element in Ga 2 O 3 Solubility in thin films, N-substituted Ga 2 O 3 The middle O element generates a cavity, thereby realizing p-type conductive Ga 2 O 3 A film. The p-type gallium oxide film prepared by the method has high hole carrier concentration, low resistivity, high film crystal quality, simple required equipment and preparation process and low production cost, and can promote the application of gallium oxide in the field of ultra-wide bandgap semiconductor devices.
Based on the same inventive concept, the embodiment of the application also provides a nitrogen-doped p-type gallium oxide film which is prepared by adopting the preparation method.
Based on the same inventive concept, the embodiment of the application also provides the application of the nitrogen element doped p-type gallium oxide film in the preparation of solar blind ultraviolet detectors and high-power electronic devices.
The following further describes the preparation method and application of the nitrogen-doped p-type gallium oxide thin film of the present application with specific examples. This section further illustrates the present invention with reference to specific examples, which should not be construed as limiting the invention. The technical means employed in the examples are conventional means well known to those skilled in the art, unless otherwise specified. Reagents, methods and apparatus employed in the present invention are conventional in the art unless otherwise indicated.
Example 1
The embodiment of the application provides a preparation method of a nitrogen-doped p-type gallium oxide film, which comprises the following steps:
s1, providing a GaN ceramic target material;
s2, providing a c-plane sapphire substrate;
s3, cleaning the c-surface sapphire substrate for 15 minutes by using acetone, absolute ethyl alcohol and deionized water in sequence, blow-drying by using high-purity nitrogen to obtain a clean substrate, putting the clean substrate into a vacuum cavity of a pulse laser deposition system, and vacuumizing to 1 x 10 -4 Pa, heating the substrate to 700 ℃, introducing oxygen into the vacuum cavity, wherein the oxygen is a growth atmosphere, adjusting the oxygen pressure of the growth chamber to be 0.5Pa, and growing a nitrogen-doped gallium oxide film on the substrate by using a pulse laser ablation deposition method by using a GaN ceramic target material as a nitrogen source and a gallium source, wherein the thickness of the film is about 120nm;
the preparation method of the GaN ceramic target comprises the following steps:
placing GaN powder into a ball milling tank, adding deionized water accounting for 60% of the total mass of the powder, performing ball milling for 8 hours, and then placing the GaN powder into a vacuum drying oven for drying treatment to obtain fine powder; the specific drying temperature is 120 ℃, and the drying time is 8 hours;
then, adding absolute ethyl alcohol accounting for 3 percent of the total mass of the powder into the dried fine powder, grinding and stirring uniformly, and pressing the mixture in a tablet press under the pressure of 4MPa to prepare ceramic green sheets with the thickness of 3mm;
sintering the GaN ceramic blank sheet for 4 hours in a vacuum tube furnace at the temperature of 950 ℃ to obtain a GaN ceramic target material;
in the embodiment of the application, the GaN target is ablated by a pulse laser deposition method to obtain the GaN cluster, and then the nitrogen-doped p-type gallium oxide film is prepared by oxidizing the GaN cluster by oxygen.
Example 2
The embodiment of the application provides a preparation method of a nitrogen-doped p-type gallium oxide film, which comprises the following steps:
s1, providing a GaN ceramic target material;
s2, providing a c-plane sapphire substrate;
s3, cleaning the c-surface sapphire substrate for 15 minutes by using acetone, absolute ethyl alcohol and deionized water in sequence, blow-drying by using high-purity nitrogen to obtain a clean substrate, putting the clean substrate into a vacuum cavity of a pulse laser deposition system, and vacuumizing to 1 x 10 -4 Pa, heating the substrate to 700 ℃, introducing oxygen into the vacuum cavity, wherein the oxygen is a growth atmosphere, adjusting the oxygen pressure of the growth chamber to 1Pa, and growing a nitrogen-doped gallium oxide film on the substrate by using a pulse laser ablation deposition method by using a GaN ceramic target material as a nitrogen source and a gallium source, wherein the thickness of the film is about 120nm;
the preparation method of the GaN ceramic target comprises the following steps:
placing GaN powder into a ball milling tank, adding deionized water accounting for 60% of the total mass of the powder, performing ball milling for 8 hours, and then placing the GaN powder into a vacuum drying oven for drying treatment to obtain fine powder; the specific drying temperature is 120 ℃, and the drying time is 8 hours;
then, adding absolute ethyl alcohol accounting for 3% of the total mass of the powder into the dried fine powder, grinding and uniformly stirring, and pressing the mixture in a tablet press under the pressure of 4MPa to prepare ceramic green sheets, wherein the thickness of the ceramic green sheets is 3mm;
sintering the GaN ceramic blank sheet for 4 hours in a vacuum tube furnace at the temperature of 950 ℃ to obtain a GaN ceramic target material;
in the embodiment of the application, the GaN target is ablated by a pulse laser deposition method to obtain the GaN cluster, and then the nitrogen-doped p-type gallium oxide film is prepared by oxidizing the GaN cluster by oxygen.
The nitrogen-doped gallium oxide thin film prepared by the embodiment of the application is subjected to structural, optical andand (3) testing the electrical property, wherein the test result is as follows: the film grows in a preferred orientation (-201), the visible light transmittance is 90%, the film is p-type conductive, and the hole concentration is 2.55 × 10 17 cm -3 Hole mobility of 2.43cm 2 V.s, resistivity of 10.1. Omega. Cm.
Example 3
The embodiment of the application provides a preparation method of a nitrogen-doped p-type gallium oxide film, which comprises the following steps:
s1, providing a GaN ceramic target material;
s2, providing a c-plane sapphire substrate;
s3, cleaning the c-surface sapphire substrate for 15 minutes by using acetone, absolute ethyl alcohol and deionized water in sequence, blow-drying by using high-purity nitrogen to obtain a clean substrate, placing the clean substrate into a vacuum cavity of a pulse laser deposition system, and vacuumizing to 1 multiplied by 10 -4 Pa, heating the substrate to 700 ℃, introducing oxygen into the vacuum cavity, wherein the oxygen is a growth atmosphere, adjusting the oxygen pressure of the growth chamber to 1.5Pa, and growing a nitrogen-doped gallium oxide film on the substrate by using a pulse laser ablation deposition method by using a GaN ceramic target material as a nitrogen source and a gallium source, wherein the thickness of the film is about 120nm;
the preparation method of the GaN ceramic target comprises the following steps:
placing GaN powder into a ball milling tank, adding deionized water accounting for 60% of the total mass of the powder, performing ball milling for 8 hours, and then placing the GaN powder into a vacuum drying oven for drying treatment to obtain fine powder; the specific drying temperature is 120 ℃, and the drying time is 8 hours;
then, adding absolute ethyl alcohol accounting for 3 percent of the total mass of the powder into the dried fine powder, grinding and stirring uniformly, and pressing the mixture in a tablet press under the pressure of 4MPa to prepare ceramic green sheets with the thickness of 3mm;
sintering the GaN ceramic blank sheet for 4 hours in a vacuum tube furnace at the temperature of 950 ℃ to obtain a GaN ceramic target material;
in the embodiment of the application, the GaN target is ablated by a pulse laser deposition method to obtain the GaN cluster, and then the nitrogen-doped p-type gallium oxide film is prepared by oxidizing the GaN cluster by oxygen.
The nitrogen-doped gallium oxide thin film prepared in the embodiment of the application is subjected to structural, optical and electrical performance tests, and the test results are as follows: the film grows in a preferred orientation of (-201), the visible light transmittance is 90 percent, the film is p-type conductive, and the hole concentration is 4.9 multiplied by 10 17 cm -3 Hole mobility of 0.213cm 2 V.s, resistivity of 60.6 omega cm.
Example 4
The embodiment of the application provides a preparation method of a nitrogen-doped p-type gallium oxide film, which comprises the following steps:
s1, providing a GaN ceramic target material;
s2, providing a c-plane sapphire substrate;
s3, cleaning the c-surface sapphire substrate for 15 minutes by using acetone, absolute ethyl alcohol and deionized water in sequence, blow-drying by using high-purity nitrogen to obtain a clean substrate, placing the clean substrate into a vacuum cavity of a pulse laser deposition system, and vacuumizing to 1 multiplied by 10 -4 Pa, heating the substrate to 700 ℃, introducing oxygen into the vacuum cavity, regulating the oxygen pressure of the growth chamber to 2Pa under the condition that the oxygen is a growth atmosphere, and growing a nitrogen-doped gallium oxide film on the substrate by using a pulse laser ablation deposition method by using a GaN ceramic target material as a nitrogen source and a gallium source, wherein the thickness of the film is about 120nm;
the preparation method of the GaN ceramic target comprises the following steps:
placing GaN powder into a ball milling tank, adding deionized water accounting for 60% of the total mass of the powder, performing ball milling for 8 hours, and then placing the GaN powder into a vacuum drying oven for drying treatment to obtain fine powder; the specific drying temperature is 120 ℃, and the drying time is 8 hours;
then, adding absolute ethyl alcohol accounting for 3% of the total mass of the powder into the dried fine powder, grinding and uniformly stirring, and pressing the mixture in a tablet press under the pressure of 4MPa to prepare ceramic green sheets, wherein the thickness of the ceramic green sheets is 3mm;
sintering the GaN ceramic blank sheet for 4 hours in a vacuum tube furnace at the temperature of 950 ℃ to obtain a GaN ceramic target material;
in the embodiment of the application, the GaN target is ablated by a pulse laser deposition method to obtain the GaN cluster, and then the nitrogen-doped p-type gallium oxide film is prepared by oxidizing the GaN cluster by oxygen.
Example 5
The embodiment of the application provides a preparation method of a nitrogen-doped p-type gallium oxide film, which comprises the following steps:
s1, providing a GaN ceramic target material;
s2, providing a magnesium oxide substrate;
s3, cleaning the magnesium oxide substrate with acetone, absolute ethyl alcohol and deionized water for 15 minutes in sequence, blow-drying with high-purity nitrogen to obtain a clean substrate, placing the clean substrate into a vacuum cavity of a pulse laser deposition system, and vacuumizing to 1 multiplied by 10 -4 Pa, heating the substrate to 600 ℃, introducing oxygen into the vacuum cavity, wherein the oxygen is a growth atmosphere, adjusting the oxygen pressure of the growth chamber to be 1Pa, and growing a nitrogen-doped gallium oxide film on the substrate by using a pulse laser ablation deposition method by using a GaN ceramic target material as a nitrogen source and a gallium source, wherein the thickness of the film is about 160nm;
the preparation method of the GaN ceramic target comprises the following steps:
placing GaN powder into a ball milling tank, adding deionized water accounting for 60% of the total mass of the powder, performing ball milling for 8 hours, and then placing the GaN powder into a vacuum drying oven for drying treatment to obtain fine powder; the specific drying temperature is 120 ℃, and the drying time is 8 hours;
then, adding absolute ethyl alcohol accounting for 3% of the total mass of the powder into the dried fine powder, grinding and uniformly stirring, and pressing the mixture in a tablet press under the pressure of 4MPa to prepare ceramic green sheets, wherein the thickness of the ceramic green sheets is 3mm;
sintering the GaN ceramic blank sheet for 4 hours in a vacuum tube furnace at the temperature of 950 ℃ to obtain a GaN ceramic target material;
in the embodiment of the application, the GaN target is ablated by a pulse laser deposition method to obtain the GaN cluster, and then the nitrogen-doped p-type gallium oxide film is prepared by oxidizing the GaN cluster by oxygen.
The nitrogen-doped gallium oxide thin film prepared by the embodiment of the application is subjected to structural, optical and electrical performance tests, and the test result is as follows: the film is an epitaxial single crystal film grown in a preferred orientation (100), the visible light transmittance is 90 percent, the film is p-type conductive, and the hole concentration is 7.03 multiplied by 10 16 cm -3 Hole mobility of 4.25cm 2 V.s, resistivity of 20.9 Ω. Cm.
Example 6
The embodiment of the application provides a preparation method of a nitrogen-doped p-type gallium oxide film, which comprises the following steps:
s1, providing a GaN ceramic target material;
s2, providing a c-plane sapphire substrate;
s3, cleaning the c-surface sapphire substrate for 15 minutes by using acetone, absolute ethyl alcohol and deionized water in sequence, blow-drying by using high-purity nitrogen to obtain a clean substrate, putting the clean substrate into a vacuum cavity of a magnetron sputtering deposition system, and vacuumizing to 1 multiplied by 10 -4 And Pa, heating the substrate to 500 ℃, introducing oxygen and argon into the vacuum cavity, adjusting the flow of the oxygen to be 0.2sccm and the flow of the argon to be 40sccm, adjusting the starting pressure in the growth chamber to be 4Pa, adjusting the pressure of the deposited film to be 0.6Pa, using a GaN ceramic target material as a nitrogen source and a gallium source, and performing growth of a nitrogen element doped gallium oxide film on the substrate by adopting a magnetron sputtering method, wherein the target material power is 80W, and the film thickness is about 200nm.
In the embodiment of the application, the GaN target is sputtered by a magnetron sputtering method to obtain a GaN cluster, and then the GaN cluster is oxidized by oxygen to prepare the nitrogen-doped gallium oxide film.
Example 7
The embodiment of the application provides a preparation method of a nitrogen-doped p-type gallium oxide film, which comprises the following steps:
s1, providing a GaN ceramic target material;
s2, providing a c-plane sapphire substrate;
s3, cleaning the c-surface sapphire substrate for 15 minutes by using acetone, absolute ethyl alcohol and deionized water in sequence, blow-drying by using high-purity nitrogen to obtain a clean substrate, putting the clean substrate into a vacuum cavity of a magnetron sputtering deposition system, and vacuumizing to 1 multiplied by 10 -4 And Pa, heating the substrate to 500 ℃, introducing oxygen and argon into the vacuum cavity, adjusting the flow of the oxygen to be 0.5sccm and the flow of the argon to be 40sccm, adjusting the starting pressure in the growth chamber to be 4Pa, adjusting the pressure of the deposited film to be 0.6Pa, using a GaN ceramic target material as a nitrogen source and a gallium source, and performing growth of a nitrogen element doped gallium oxide film on the substrate by adopting a magnetron sputtering method, wherein the target material power is 80W, and the film thickness is about 200nm.
In the embodiment of the application, the GaN target is sputtered by a magnetron sputtering method to obtain a GaN cluster, and then the GaN cluster is oxidized by oxygen to prepare the nitrogen-doped gallium oxide film.
Example 8
The embodiment of the application provides a preparation method of a nitrogen-doped p-type gallium oxide film, which comprises the following steps:
s1, providing a GaN ceramic target material;
s2, providing a c-plane sapphire substrate;
s3, cleaning the c-surface sapphire substrate for 15 minutes by using acetone, absolute ethyl alcohol and deionized water in sequence, blow-drying by using high-purity nitrogen to obtain a clean substrate, putting the clean substrate into a vacuum cavity of a magnetron sputtering deposition system, and vacuumizing to 1 x 10 -4 And Pa, heating the substrate to 500 ℃, introducing oxygen and argon into the vacuum cavity, adjusting the flow of the oxygen to be 1sccm and the flow of the argon to be 40sccm, adjusting the starting pressure in the growth chamber to be 4Pa, the pressure of the deposited film to be 0.6Pa, using a GaN ceramic target as a nitrogen source and a gallium source, and performing growth of a nitrogen element doped gallium oxide film on the substrate by adopting a magnetron sputtering method, wherein the target power is 80W, and the film thickness is about 180nm.
In the embodiment of the application, the GaN target is sputtered by a magnetron sputtering method to obtain a GaN cluster, and then the GaN cluster is oxidized by oxygen to prepare the nitrogen-doped gallium oxide film.
Example 9
The embodiment of the application provides a preparation method of a nitrogen-doped p-type gallium oxide film, which comprises the following steps:
s1, providing a GaN ceramic target material;
s2, providing a c-plane sapphire substrate;
s3, cleaning the c-surface sapphire substrate for 15 minutes by using acetone, absolute ethyl alcohol and deionized water in sequence, blow-drying by using high-purity nitrogen to obtain a clean substrate, putting the clean substrate into a vacuum cavity of a magnetron sputtering deposition system, and vacuumizing to 1 x 10 -4 And Pa, heating the substrate to 500 ℃, introducing oxygen and argon into the vacuum cavity, adjusting the flow of the oxygen to be 2sccm and the flow of the argon to be 40sccm, starting the pressure in the growth chamber to be 4Pa, depositing the film to be 0.6Pa, using the GaN ceramic target as a nitrogen source and a gallium source, wherein the power of the target is 80W, and growing the nitrogen-doped gallium oxide film on the substrate by adopting a magnetron sputtering method, wherein the thickness of the film is about 150nm.
In the embodiment of the application, the GaN target is sputtered by a magnetron sputtering method to obtain a GaN cluster, and then the GaN cluster is oxidized by oxygen to prepare the nitrogen-doped gallium oxide film.
Performance testing
The nitrogen-doped p-type gallium oxide thin films prepared in examples 2, 3, and 5 were tested for their properties, and the results are shown in table 1 below.
TABLE 1-Properties of the Nitrogen-doped p-type gallium oxide films prepared in examples 2, 3 and 5
Fig. 2 is an x-ray diffraction (XRD) pattern of the nitrogen-doped p-type gallium oxide thin film prepared in examples 2 to 3 of the present invention.
FIG. 3 is a graph of the rocking curve of x-ray diffraction of nitrogen-doped p-type gallium oxide thin films prepared in examples 2 to 3 of the present invention.
FIG. 4 is a transmission spectrum of a nitrogen-doped p-type gallium oxide thin film prepared in example 2 of the present invention, and the inset shows (α hv) of the nitrogen-doped p-type gallium oxide thin film 2 Graph with hv.
FIG. 5 is a transmission spectrum of a nitrogen-doped p-type gallium oxide thin film prepared in example 3 of the present invention, and the inset shows (α hv) of the nitrogen-doped p-type gallium oxide thin film 2 Graph with hv.
Fig. 6 is an x-ray diffraction (XRD) pattern of the nitrogen-doped p-type gallium oxide thin film prepared in example 5 of the present invention.
FIG. 7 is a graph of the rocking curve of x-ray diffraction of a nitrogen-doped p-type gallium oxide thin film prepared in example 5 of the present invention.
FIG. 8 shows a nitrogen-doped p-type gallium oxide thin film prepared in example 5 of the present invention
And (4) mapping.
FIG. 9 shows a transmission spectrum of a nitrogen-doped p-type gallium oxide thin film prepared in example 5 of the present invention, wherein the inset shows (α hv) of the nitrogen-doped p-type gallium oxide thin film 2 Graph with hv.
FIG. 10 is a sectional view of a field emission scanning electron microscope (FE-SEM) of a nitrogen-doped p-type gallium oxide thin film prepared in example 5 of the present invention.
FIG. 11 is a surface view of a field emission scanning electron microscope (FE-SEM) of a nitrogen-doped p-type gallium oxide thin film prepared in example 5 of the present invention.
Fig. 12 is an element distribution diagram (EDS-mapping) of the nitrogen-doped p-type gallium oxide thin film prepared in example 5 of the present invention.
Fig. 13 is a High Resolution Transmission Electron Micrograph (HRTEM) of the nitrogen-doped p-type gallium oxide thin film prepared in example 5 of the present invention.
Fig. 14 is a selected area electron diffraction pattern (SAED) of nitrogen-doped p-type gallium oxide thin film prepared in example 5 of the present invention.
From the results of Hall tests on the films of examples 2, 3 and 5 of Table 1, it can be seen that the method provided in this patent is used to test different substrates (c-plane sapphire)Stone, magnesia) realizes the preparation of stable nitrogen element doped p-type gallium oxide film with good conductivity and high repeatability, and the nitrogen element doped p-type gallium oxide film grown on the c-plane sapphire has higher carrier concentration with the maximum of 4.9 multiplied by 10 17 (1/cm 3 ) The maximum hole mobility is 2.43 (cm) 2 V.s), film resistivity is 10.1 (Ω. Cm) at minimum; the lattice mismatch ratio of the c-plane sapphire substrate and gallium oxide is 7.4%, the lattice mismatch ratio of the magnesium oxide substrate and gallium oxide is lower than 3%, and the preparation of a high-quality epitaxial nitrogen element doped p-type gallium oxide single crystal film is realized on the magnesium oxide substrate by the method provided by the patent, so that a support is provided for the preparation of a gallium oxide film device; compared with the mobility of a nitrogen-doped p-type gallium oxide single crystal film grown on a magnesium oxide substrate on c-plane sapphire, the mobility of holes is as high as 4.25 (cm) 2 /V.s)。
As can be seen from FIGS. 2 to 5, the nitrogen-doped p-type gallium oxide thin films with the preferred orientation of (-201) were grown on the c-plane sapphire, and the full width at half maximum (FWHM) of XRD rocking curves of the thin films of examples 2 and 3 were 0.143 and 0.151, respectively, indicating that the crystalline quality of the thin films was good; the transmittance of the films of the examples 2 and 3 in the wavelength range of 200-3000nm is as high as more than 90%, which shows that the prepared nitrogen element doped p-type gallium oxide film has good transmittance and the band gap of the film is 5.08eV.
As can be seen from fig. 6 to 14, the (100) oriented nitrogen-doped p-type gallium oxide single crystal thin film is epitaxially grown on the MgO substrate, the full width at half maximum (FWHM) of the XRD rocking curve of the thin film is 0.105, and the nitrogen-doped p-type gallium oxide thin film grown on the MgO substrate has higher crystal quality, so that the thin film has higher hole mobility; of films
The result shows that the high-quality nitrogen-doped p-type gallium oxide film epitaxial growth is realized on the MgO substrate, and the out-of-plane epitaxial relationship between the film and the substrate is beta-Ga 2 O 3 (100) v/MgO (100), in-plane epitaxial relationship is β -Ga 2 O 3 [001]//MgO<011>. The nitrogen element doped p-type gallium oxide film grown on the MgO substrate has good penetrationThe transmittance of the film in the wavelength range of 200-3000nm is more than 90%, and the band gap of the film is 4.95eV. The section field emission test result of the film shows that the thickness of the film is about 160nm, the crystal grains on the surface of the film are consistent, and the Ga, O and N elements in the film are uniformly distributed. The test result of the high-resolution transmission electron microscope shows that the interface of the film and the substrate is clear and the atomic arrangement is regular. The result of selective area electron diffraction test shows that the method provided by the application realizes the preparation of the nitrogen-doped high-quality p-type gallium oxide single crystal film on the magnesium oxide substrate, and the out-of-plane epitaxial relationship between the film and the substrate is beta-Ga 2 O 3 (100) V/MgO (100), in-plane epitaxial relationship is beta-Ga 2 O 3 [001]//MgO<011>And XRD
The test results are consistent.
In conclusion, by using the method provided by the application, the nitrogen-doped p-type gallium oxide epitaxial film is prepared on the c-plane sapphire substrate, and the higher-quality nitrogen-doped p-type gallium oxide epitaxial single crystal film is realized on the MgO substrate; the p-type conductivity of the film is stable, the repeatability is high and the conductivity is good; the prepared nitrogen element doped p-type gallium oxide film has good optical permeability, the thickness of the film can be regulated, the crystal grain size on the surface of the film is consistent, and the elements (Ga, O and N) are uniformly distributed. The characteristics provide remarkable advantages for the application of the nitrogen element doped p-type gallium oxide epitaxial film prepared by the method in photoelectric detection devices and power electronic devices.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of a nitrogen element doped p-type gallium oxide film is characterized by comprising the following steps:
providing a GaN ceramic target material;
providing a substrate;
and placing the substrate in a vacuum cavity of deposition equipment, using the GaN ceramic target material as a nitrogen source and a gallium source, ablating, sputtering or evaporating the GaN target material by adopting a physical vapor deposition method to obtain a GaN cluster, and oxidizing the GaN cluster by using oxygen so as to grow on the substrate to obtain the nitrogen-doped p-type gallium oxide film.
2. The method according to claim 1, wherein the substrate is placed in a vacuum chamber of a deposition apparatus, the substrate is heated to 400-750 ℃, the GaN ceramic target is used as a nitrogen source and a gallium source, the GaN target is ablated, sputtered or evaporated by a physical vapor deposition method to obtain GaN clusters, oxygen is introduced into the vacuum chamber, and the GaN clusters are oxidized by the oxygen, so that the nitrogen-doped p-type gallium oxide film is grown on the substrate.
3. The method for preparing a nitrogen-doped p-type gallium oxide thin film according to claim 1, wherein said physical vapor deposition method comprises any one of magnetron sputtering, pulsed laser deposition and molecular beam epitaxy;
and/or the substrate comprises at least one of a c-plane sapphire substrate, a magnesium oxide substrate, a gallium nitride substrate, a silicon substrate, a NSTO substrate, a quartz glass substrate, r-plane sapphire and a-plane sapphire.
4. The method for preparing the nitrogen-doped p-type gallium oxide film according to claim 3, wherein a pulsed laser deposition method is used to ablate the GaN target material to obtain GaN clusters, oxygen is introduced into the vacuum chamber, and the oxygen pressure in the growth chamber is adjusted to 0-4 Pa; wherein the pulse laser energy is 150-400 mJ, the number of pulses is 9000-54000, and the pulse frequency is 1-10 Hz.
5. The method for preparing a nitrogen-doped p-type gallium oxide film as claimed in claim 3, wherein magnetron sputtering is used to sputter a GaN target, argon and oxygen are introduced into the vacuum chamber, the flow of argon is adjusted to 10-60 sccm, the flow of oxygen is adjusted to 0-30 sccm, the starting pressure in the growth chamber is 1-6 Pa, the pressure of the deposited film is 0.2-4 Pa, the sputtering power of the target is 40-160W, and the deposition time is 30-120 min.
6. The method for preparing the nitrogen-doped p-type gallium oxide thin film according to claim 1, wherein the method for preparing the GaN ceramic target comprises:
carrying out ball milling on the GaN powder to obtain fine powder;
pressing the fine powder subjected to ball milling into a ceramic green sheet;
sintering the ceramic green sheet at 800-1200 ℃ to obtain the GaN ceramic target.
7. The method for preparing a nitrogen-doped p-type gallium oxide thin film according to claim 6, wherein the fine powder after ball milling is pressed into a ceramic green sheet with a thickness of 2-5 mm under a pressure of 2-10 Mpa; sintering the ceramic green sheet at 800-1200 ℃ for 2-5 h to obtain the GaN ceramic target.
8. The method according to claim 1, wherein the step of cleaning the substrate with acetone, absolute ethyl alcohol, and deionized water sequentially comprises the step of cleaning the substrate with acetone, absolute ethyl alcohol, and deionized water before placing the substrate in the vacuum chamber of the pulsed laser deposition system.
9. A nitrogen-doped p-type gallium oxide thin film, characterized by being prepared by the preparation method of any one of claims 1 to 8.
10. An application of the nitrogen element doped p-type gallium oxide film prepared by the preparation method of any one of claims 1 to 8 or the nitrogen element doped p-type gallium oxide film of claim 9 in preparing solar blind ultraviolet detectors and high-power electronic devices.
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| JPH05201769A (en) * | 1992-01-28 | 1993-08-10 | Nippon Steel Corp | Combined ceramic material and its production |
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| CN107119258A (en) * | 2017-05-23 | 2017-09-01 | 鲁东大学 | P-type doping gallium oxide film and preparation method thereof |
| CN111341839A (en) * | 2020-01-19 | 2020-06-26 | 深圳第三代半导体研究院 | P-type nitrogen-doped gallium oxide film and preparation method thereof |
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2022
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| JPH05201769A (en) * | 1992-01-28 | 1993-08-10 | Nippon Steel Corp | Combined ceramic material and its production |
| CN102974379A (en) * | 2012-11-05 | 2013-03-20 | 南京大学 | Method for preparing nitrogen-doped photo-catalytic material containing gallium oxide at low temperature |
| CN107119258A (en) * | 2017-05-23 | 2017-09-01 | 鲁东大学 | P-type doping gallium oxide film and preparation method thereof |
| CN111341839A (en) * | 2020-01-19 | 2020-06-26 | 深圳第三代半导体研究院 | P-type nitrogen-doped gallium oxide film and preparation method thereof |
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