CN113584587A - Sn-doped metastable gallium oxide crystalline phase film and preparation method and application thereof - Google Patents
Sn-doped metastable gallium oxide crystalline phase film and preparation method and application thereof Download PDFInfo
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- 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 157
- 229910001195 gallium oxide Inorganic materials 0.000 title claims abstract description 156
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 115
- 238000000137 annealing Methods 0.000 claims abstract description 45
- 229910052594 sapphire Inorganic materials 0.000 claims abstract description 30
- 239000010980 sapphire Substances 0.000 claims abstract description 30
- 238000004549 pulsed laser deposition Methods 0.000 claims abstract description 28
- 239000011224 oxide ceramic Substances 0.000 claims abstract description 27
- 239000013077 target material Substances 0.000 claims abstract description 22
- 238000005516 engineering process Methods 0.000 claims abstract description 10
- 239000010408 film Substances 0.000 claims description 110
- 230000008021 deposition Effects 0.000 claims description 67
- 238000000151 deposition Methods 0.000 claims description 66
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 claims description 48
- 239000013078 crystal Substances 0.000 claims description 37
- 238000001816 cooling Methods 0.000 claims description 35
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 28
- 239000001301 oxygen Substances 0.000 claims description 28
- 229910052760 oxygen Inorganic materials 0.000 claims description 28
- 239000010409 thin film Substances 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 27
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- 230000009466 transformation Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 238000002441 X-ray diffraction Methods 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
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- 239000000463 material Substances 0.000 description 6
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- 230000009286 beneficial effect Effects 0.000 description 2
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- 230000008025 crystallization Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001451 molecular beam epitaxy Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
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Abstract
The invention discloses a Sn-doped metastable gallium oxide crystalline phase film and a preparation method and application thereof. The preparation method comprises the following steps: adopting a pulsed laser deposition technology, taking a Sn-doped gallium oxide ceramic target as a target material, epitaxially growing a film on the surface of sapphire serving as a substrate, and annealing to obtain a Sn-doped metastable gallium oxide crystalline phase film; wherein the molar percentage of Sn in the target material is 0.1-5%. The invention adopts the Sn-doped gallium oxide ceramic target material, can stably regulate and control the transformation of the gallium oxide film between alpha and epsilon phases, and widens the preparation method of the metastable crystalline phase of gallium oxide; meanwhile, the prepared metastable gallium oxide film has consistent grain orientation, high crystallinity and higher growth rate.
Description
Technical Field
The invention belongs to the technical field of semiconductor materials, and particularly relates to a Sn-doped metastable gallium oxide crystalline phase film and a preparation method and application thereof.
Background
Binary compound Ga2O3The crystal is a novel wide-bandgap semiconductor material, has 6 crystal forms, and is respectively alpha, beta, gamma, delta, epsilon and kappa phases. Wherein beta-Ga2O3Is a thermally stable phase at high temperature, grows most easily and is targeted by researchers at beta-Ga2O3The preparation of thin films and the study of devices are the most extensive. Metastable phase alpha-Ga2O3And ε -Ga2O3All belonging to the Hexagonal system (Hexagonal), alpha-Ga2O3The band gap is close to 5.3eV, corresponding to a wavelength of 230nm, the breakdown field strength is expected to be greater than 10MV/cm, and the BarlGae value is higher. ε -Ga2O3The spontaneous polarization characteristic can promote the directional transport of current carriers, and further generate polarization charges and two-dimensional electron gas, thereby being beneficial to improving the detection sensitivity of the device and reducing the contact resistance. More importantly, the beta-Ga has a monoclinic structure2O3Compared with the alpha phase and the epsilon phase of a corundum structure, the material can be better compared with other substrate materials with hexagonal structures (such as Al)2O3ZnO and GaN) to obtain epitaxial film with high crystal quality, and can be used as solar blind ultraviolet photodetector and high-power electronic device2O3Has better application prospect.
How to prepare metastable Ga with high crystal quality2O3Epitaxial thin film of Ga of high Performance2O3A key step in optoelectronic devices. Ga2O3Epitaxial filmThe growth techniques of the film are various, and generally adopted are: pulsed Laser Deposition (PLD), Radio Frequency Magnetron Sputtering (RFMS), Molecular Beam Epitaxy (MBE), and Metal Organic Chemical Vapor Deposition (MOCVD).
The MBE and MOCVD methods have the problem of high equipment price, but the MOCVD and RFMS methods have poor gallium oxide crystallization quality in the film growth process, and annealing is needed in an annealing furnace outside the growth equipment to improve the crystallinity, which inevitably causes film pollution and resource waste. The metastable gallium oxide film obtained by the technical method has thin thickness, and is converted into a thermally stable beta phase after exceeding a certain thickness, so that a single-orientation crystal phase is difficult to obtain. Thus, a method for preparing metastable Ga with high crystal quality is provided2O3Epitaxial thin films are a problem that needs to be solved.
Disclosure of Invention
The invention mainly aims to provide a Sn-doped metastable gallium oxide crystalline phase film, and a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of a Sn-doped metastable gallium oxide crystalline phase film, which comprises the following steps:
providing sapphire as a substrate;
and adopting a pulsed laser deposition technology, taking the Sn-doped gallium oxide ceramic target as a target material, epitaxially growing a film on the surface of the substrate, and annealing to obtain a Sn-doped metastable gallium oxide crystalline phase film;
wherein the molar percentage content of Sn in the target material is 0.1-5%; the process conditions adopted by the pulse laser deposition technology comprise: the oxygen pressure is 0.1-200 mT, the deposition temperature is 600-900 ℃, and the pulse laser energy density is 0.5-3J/cm2。
The embodiment of the invention also provides the Sn doped metastable gallium oxide crystal phase thin prepared by the methodA film, wherein a metastable gallium oxide crystalline phase in the metastable gallium oxide crystalline phase film comprises a-Ga2O3Crystal phase and/or epsilon-Ga2O3And the molar percentage of Sn in the metastable gallium oxide crystalline phase film is 0.1-5%.
The embodiment of the invention also provides application of the Sn-doped metastable gallium oxide crystalline phase film in preparing solar blind ultraviolet photodetectors or high-power electronic devices.
The embodiment of the invention also provides an optoelectronic device which comprises the Sn-doped metastable state gallium oxide crystalline phase film.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention adopts Sn-doped gallium oxide ceramic target material (the mol percentage content is 0.1-5%), can stably regulate and control the transformation of the gallium oxide film between alpha and epsilon, and widens the preparation method of the metastable crystal phase of gallium oxide;
(2) the metastable gallium oxide film prepared by the invention has consistent crystal grain orientation, high crystallinity and higher growth rate;
(3) the method of the invention adopts the pulse laser deposition technology, and the growth and annealing processes of the film are continuous in the deposition chamber, so that the pollution of the film during the post-annealing treatment of the prior art can be avoided;
(4) the substrate selected by the invention is sapphire, compared with Ga2O3Substrates such as single crystals, GaN and diamond have great cost advantages.
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 description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an X-ray diffraction pattern of a Sn-doped metastable gallium oxide crystalline phase thin film prepared in example 1 of the present invention;
FIG. 2 is an X-ray diffraction pattern of a Sn-doped metastable gallium oxide crystalline phase thin film prepared in example 2 of the present invention;
FIG. 3 is an X-ray diffraction pattern of a Sn-doped metastable gallium oxide crystalline phase thin film prepared in example 3 of the present invention;
FIG. 4 is an X-ray diffraction pattern of a Sn-doped metastable gallium oxide crystalline phase thin film prepared in example 4 of the present invention;
FIG. 5 is an X-ray diffraction pattern of a Sn-doped metastable gallium oxide crystalline phase thin film prepared in example 5 of the present invention;
FIG. 6 is an X-ray diffraction pattern of a gallium oxide crystal phase thin film prepared in comparative example 1 of the present invention;
FIG. 7 is an X-ray diffraction pattern of a gallium oxide crystal phase thin film prepared by comparative example 2 of the present invention;
FIG. 8 is an SEM image of a Sn-doped metastable gallium oxide crystalline phase thin film prepared in example 1 of the present invention;
FIG. 9 is an SEM image of a Sn-doped metastable gallium oxide crystalline phase thin film prepared in example 2 of the present invention;
FIG. 10 is an X-ray diffraction pattern of a gallium oxide crystal phase thin film prepared in comparative example 3 of the present invention;
FIG. 11 is an X-ray diffraction pattern of a Sn-doped metastable gallium oxide crystalline phase thin film prepared in example 6 of the present invention.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has long studied and largely practiced to propose the technical solution of the present invention, which will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
One aspect of the embodiments of the present invention provides a method for preparing a Sn-doped metastable gallium oxide crystalline phase film, which includes:
providing sapphire as a substrate;
and adopting a pulsed laser deposition technology, taking the Sn-doped gallium oxide ceramic target as a target material, epitaxially growing a film on the surface of the substrate, and annealing to obtain a Sn-doped metastable gallium oxide crystalline phase film;
wherein the molar percentage content of Sn in the target material is 0.1-5%;
the process conditions adopted by the pulse laser deposition technology comprise: the oxygen pressure is 0.1-200 mT, the deposition temperature is 600-900 ℃, and the pulse laser energy density is 0.5-3J/cm2The frequency of the pulse laser is 2-10 Hz, and the number of pulse deposition times is 3000-20000.
In some more specific embodiments, the preparation method comprises:
placing sapphire as a substrate in a pulsed laser deposition system, and vacuumizing the reaction cavity to 10 DEG-5Heating the substrate to 600-900 ℃ at the heating rate of 5-30 ℃/min below Pa, and then carrying out heat preservation treatment for more than 1200 s;
and adopting a pulse laser deposition technology, taking the Sn-doped gallium oxide ceramic target as a target material, performing pre-deposition on the surface of the substrate, and then performing epitaxial growth film and annealing treatment to obtain the Sn-doped metastable gallium oxide crystalline phase film.
Further, the distance between the target and the substrate is 3-10 cm; preferably 5 cm.
Further, the sapphire includes a-plane sapphire, and is not limited thereto.
Further, the a-plane sapphire includes a-plane (11-20) sapphire, and is not limited thereto.
Further, the process conditions adopted by the pre-deposition include: the pulse deposition frequency is 100-300 times, the interval time is 60-180 s, and the cycle frequency is 3-5 times.
Furthermore, the process conditions adopted by the pre-deposition include: the number of pulse depositions was 200, the interval time was 120s, and the number of cycles was 3.
Furthermore, the technological condition bag for epitaxial growth of the film by adopting the pulse laser deposition technologyComprises the following steps: oxygen pressure is 20mT, deposition temperature is 800 ℃, and pulse laser energy density is 1J/cm2The frequency of the pulse laser is 2-10 Hz, and the number of pulse deposition times is 3000-20000.
Further, the annealing treatment comprises: after the epitaxial growth of the film is finished, keeping the oxygen pressure of the reaction cavity to be 0.1-200 mT, and reducing the temperature to be below 100 ℃ at a cooling rate of 5-30 ℃/min, so as to finish the annealing treatment of the substrate of the epitaxial growth film.
In some more specific embodiments, when the molar percentage of Sn X in the Sn-doped gallium oxide ceramic target is between 0.1% and X < 0.75%, the metastable gallium oxide crystalline phase of the Sn-doped metastable gallium oxide crystalline phase film is epsilon-Ga2O3A crystalline phase;
furthermore, when the molar percentage content X of Sn in the Sn-doped gallium oxide ceramic target is more than or equal to 0.75 percent and less than or equal to 1 percent, the mesostable gallium oxide crystalline phase in the Sn-doped mesostable gallium oxide crystalline phase film is alpha-Ga2O3A crystalline phase;
furthermore, when the molar percentage content X of Sn in the Sn-doped gallium oxide ceramic target is more than 1% and less than or equal to 5%, the mesostable gallium oxide crystalline phase of the Sn-doped mesostable gallium oxide crystalline phase film is alpha-Ga2O3With ε -Ga2O3Mixed crystal phases of (2).
In some specific embodiments, when the molar percentage of Sn in the Sn-doped gallium oxide ceramic target is 0.1 to 0.5%, the metastable gallium oxide crystal phase of the Sn-doped metastable gallium oxide crystal phase thin film is epsilon-Ga2O3A crystalline phase.
Further, when the molar percentage of Sn in the Sn-doped gallium oxide ceramic target is 0.75-1%, the intermediate stable gallium oxide crystalline phase of the Sn-doped intermediate stable gallium oxide crystalline phase film is alpha-Ga2O3A crystalline phase.
Further, when the molar percentage of Sn in the Sn-doped gallium oxide ceramic target is 2-5%, the mesostable gallium oxide crystalline phase of the Sn-doped mesostable gallium oxide crystalline phase film is alpha-Ga2O3With ε -Ga2O3Mixed crystal phases of (2).
In some more specific embodiments, the preparation method further comprises: sapphire as a substrate is subjected to cleaning, drying and pre-annealing treatment.
Further, the pre-annealing treatment comprises the following steps: and carrying out pre-annealing treatment on the dried substrate for 1-4 h at 800-1300 ℃ in an air atmosphere.
Furthermore, the temperature of the dried substrate is increased to 800-1300 ℃ at the temperature increasing rate of 5-20 ℃/min, and then the substrate is cooled to room temperature at the temperature decreasing rate of 5-20 ℃/min, and the substrate is pre-annealed.
In some more specific embodiments, the method for preparing the Sn-doped metastable gallium oxide crystalline phase thin film comprises:
(1) selecting an a-surface sapphire substrate, cleaning, and drying by high-purity nitrogen;
(2) placing the substrate in a box furnace for pre-annealing, wherein the pre-annealing temperature is 800-1300 ℃, the time is 1-4 hours, the atmosphere is air, and the heating rate and the cooling rate are set to be 5-20 ℃/min, so that the substrate forms flat and uniform steps;
(3) adopting a gallium oxide ceramic target material with Sn doping concentration of 0.1-5% in mole fraction;
(4) fixing the pre-annealed substrate on a substrate holder, placing the substrate holder into a deposition chamber, adjusting the distance between the target and the substrate, and vacuumizing to a vacuum degree of 10-5Pa below;
(5) heating the substrate to 600-900 ℃ at the speed of 5-30 ℃/min, and preserving the heat for more than 1200 s;
(6) controlling the temperature of the deposition chamber to be constant, and setting oxygen pressure, pulse laser energy density, frequency and pre-deposition program by using a Pulse Laser Deposition (PLD) system and then starting epitaxial film;
(7) after the deposition is finished, setting the cooling rate to be 5-30 ℃/min, and annealing in the deposition chamber under the same oxygen pressure as that during the deposition;
(8) and cooling to below 100 ℃ and taking out a film sample (namely the Sn doped metastable gallium oxide crystalline phase film).
Preferably, in the step (1), the substrate is a-plane (11-20) sapphire.
Preferably, in the step (2), the pre-annealing temperature is 1000 ℃, the time is 2h, and the heating rate and the cooling rate are 10 ℃/min.
Preferably, in the step (3), the required Sn doping concentrations of different metastable crystal phases are different; obtaining epsilon-Ga2O3The preferred Sn doping concentration of the crystalline phase is 0.5%; obtaining alpha-Ga2O3The preferred Sn doping concentration of the crystalline phase is 1%; obtaining alpha-Ga2O3With ε -Ga2O3The preferred doping concentration of Sn for the mixed crystal phase is 2%.
Preferably, in the step (4), the distance between the target and the substrate can be 3-10 cm, and the preferred distance is 5 cm.
Preferably, in step (5), the substrate heating temperature is 800 ℃, the holding time is 1800s, and the heating rate is 20 ℃/min.
Preferably, in the step (6), the oxygen pressure can be selected from the range of 0.1-200 mT, preferably 20 mT; the energy density of the pulse laser can be selected within the range of 0.5-3J/cm2Preferably 1J/cm2(ii) a The frequency range of the pulse laser is 2-10 Hz, and preferably 5 Hz; the range of the pulse deposition times is 3000-20000 times, and 10000 times is preferred; the pre-deposition is preferably pulsed 200 times, separated by 120s and cycled 3 times.
Preferably, in step (6), the energy density of the pulsed laser refers to the actual energy density of the laser on the surface of the target.
Preferably, in step (7), the cooling rate is 20 ℃/min.
The invention optimizes the metastable state of the gallium oxide alpha-Ga2O3And ε -Ga2O3The growth parameters (laser energy, oxygen pressure, growth temperature, substrate crystal plane orientation, doping concentration and the like) are combined with PLD (typical non-equilibrium growth method) to grow metastable crystal phase, so that beta-Ga can be effectively avoided2O3Thereby achieving growth of a metastable crystalline phase.
Compared with a monoclinic structureOf beta phase, alpha-Ga2O3And ε -Ga2O3And has a hexagonal crystal structure with the sapphire substrate. After Sn element is doped, the volatilization of Ga element in the growth process can be inhibited, the proportion of octahedron and tetrahedron in the gallium oxide unit cell is influenced, and the crystallization path of gallium oxide is changed. Ga when the ratio of octahedra to tetrahedra is significantly elevated2O3Will form in the epsilon crystal phase. In another aspect, alpha-Ga2O3The formation of the structure also needs to be combined with the strain regulation and control of the growth substrate provided by the invention, and the lattice distortion of the epitaxial film is systematically reduced, so that the alpha-Ga which is highly matched with the crystal structure of the sapphire substrate is grown2O3。
In another aspect, the embodiments of the present invention further provide a Sn-doped metastable gallium oxide crystalline phase thin film prepared by the foregoing method, wherein the metastable gallium oxide crystalline phase in the metastable gallium oxide crystalline phase thin film comprises alpha-Ga2O3Crystal phase and/or epsilon-Ga2O3And the molar percentage of Sn in the metastable gallium oxide crystalline phase film is 0.1-5%.
In some more specific embodiments, when the molar percentage of Sn in the Sn-doped metastable gallium oxide crystalline phase film Y is between 0.1% and Y < 0.75%, the metastable gallium oxide crystalline phase is epsilon-Ga2O3A crystalline phase;
furthermore, when the molar percentage content Y of Sn in the Sn-doped metastable gallium oxide crystalline phase film is more than or equal to 0.75 percent and less than or equal to 1 percent, the metastable gallium oxide crystalline phase is alpha-Ga2O3A crystalline phase;
furthermore, when the molar percentage content Y of Sn in the Sn-doped metastable gallium oxide crystalline phase film is more than 1% and less than or equal to 5%, the metastable gallium oxide crystalline phase is alpha-Ga2O3With ε -Ga2O3Mixed crystal phases of (2).
In some specific embodiments, when the molar percentage of Sn in the Sn-doped metastable gallium oxide crystalline phase thin film is 0.1-0.5%, the metastable gallium oxide crystalline phase is epsilon-Ga2O3A crystalline phase.
Further, in the above-mentioned case,when the molar percentage of Sn in the Sn-doped metastable gallium oxide crystalline phase film is 0.75-1%, the metastable gallium oxide crystalline phase is alpha-Ga2O3A crystalline phase.
Further, when the molar percentage of Sn in the Sn-doped metastable gallium oxide crystalline phase film is 2-5%, the metastable gallium oxide crystalline phase is alpha-Ga2O3With ε -Ga2O3Mixed crystal phases of (2).
Furthermore, the thickness of the metastable gallium oxide crystalline phase film is 200-400 nm.
In another aspect of the embodiments of the present invention, there is also provided a use of the Sn-doped metastable gallium oxide crystalline phase thin film in the preparation of solar blind ultraviolet photodetectors or high-power electronic devices.
In another aspect, the embodiments of the present invention also provide an optoelectronic device, which includes the aforementioned Sn-doped metastable gallium oxide crystalline phase thin film.
The technical solutions of the present invention are further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and a detailed implementation manner and a specific operation process are provided, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified.
Example 1
(1) Selecting an a-surface (11-20) sapphire substrate, cleaning, and drying by high-purity nitrogen;
(2) placing the substrate in a box furnace for pre-annealing at 1000 ℃ for 2h in air at a heating rate and a cooling rate of 10 ℃/min to form a flat and uniform step on the substrate;
(3) adopting a gallium oxide ceramic target material with Sn doping concentration of 0.5% mole fraction;
(4) fixing the pre-annealed substrate on a substrate holder, placing the substrate holder into a deposition chamber, adjusting the distance between the target and the substrate to 5cm, and vacuumizing to reach vacuum degree10-5Pa below;
(5) heating the substrate to 800 ℃ at the speed of 20 ℃/min, and keeping the temperature for 1800 s;
(6) introducing high-purity oxygen by adopting a Pulsed Laser Deposition (PLD) system, and controlling the gas pressure to be 20 mT; setting the energy density of the pulse laser to 1J/cm2The frequency is 5Hz, and the pulse is 10000 times; pre-pulsing for 200 times, performing cycle for 3 times at intervals of 120s, and then starting epitaxial growth of the film;
(7) after the deposition is finished, setting the cooling rate to be 20 ℃/min, and annealing in the deposition chamber under the same oxygen pressure as that during the deposition;
(8) and cooling to below 100 ℃ and taking out a film sample (namely the Sn doped metastable gallium oxide crystalline phase film).
The X-ray diffraction pattern of the Sn-doped metastable gallium oxide crystal phase film prepared in this example is shown in fig. 1, which shows that the metastable gallium oxide crystal phase film prepared in this example is an epsilon-phase gallium oxide film, and the SEM image of the Sn-doped metastable gallium oxide crystal phase film prepared in this example is shown in fig. 8.
Example 2
(1) Selecting an a-surface (11-20) sapphire substrate, cleaning, and drying by high-purity nitrogen;
(2) placing the substrate in a box type furnace for pre-annealing, wherein the pre-annealing temperature is 1000 ℃, the time is 2 hours, the atmosphere is air, and the heating rate and the cooling rate are set to be 10 ℃ per minute, so that the substrate forms a flat and uniform step;
(3) adopting a gallium oxide ceramic target material with Sn doping concentration of 1% mole fraction;
(4) fixing the pre-annealed substrate on a substrate holder, placing the substrate holder into a deposition chamber, adjusting the distance between the target and the substrate to 5cm, and vacuumizing to 10 DEG-5Pa below;
(5) heating the substrate to 800 ℃ at the speed of 20 ℃/min, and keeping the temperature for 1800 s;
(6) introducing high-purity oxygen by adopting a Pulsed Laser Deposition (PLD) system, and controlling the gas pressure to be 20 mT; setting the energy density of the pulse laser to 1J/cm2The frequency is 5Hz, and the pulse is 10000 times; prepulse 200 times in advance, interval 120s and cycle 3 times and then startEpitaxially growing a film;
(7) after the deposition is finished, setting the cooling rate to be 20 ℃/min, and annealing in the deposition chamber under the same oxygen pressure as that during the deposition;
(8) and cooling to below 100 ℃ and taking out a film sample (namely the Sn doped metastable gallium oxide crystalline phase film).
The X-ray diffraction pattern of the Sn-doped metastable gallium oxide crystal phase film prepared in this example is shown in fig. 2, which shows that the metastable gallium oxide crystal phase film prepared in this example is an α -phase gallium oxide film, and the SEM image of the Sn-doped metastable gallium oxide crystal phase film prepared in this example is shown in fig. 9.
Example 3
(1) Selecting an a-surface (11-20) sapphire substrate, cleaning, and drying by high-purity nitrogen;
(2) placing the substrate in a box furnace for pre-annealing at 1000 ℃ for 2h in air at a heating rate and a cooling rate of 10 ℃/min to form a flat and uniform step on the substrate;
(3) adopting a gallium oxide ceramic target material with Sn doping concentration of 2% mole fraction;
(4) fixing the pre-annealed substrate on a substrate holder, placing the substrate holder into a deposition chamber, adjusting the distance between the target and the substrate to 5cm, and vacuumizing to 10 DEG-5Pa below;
(5) heating the substrate to 800 ℃ at the speed of 20 ℃/min, and keeping the temperature for 1800 s;
(6) introducing high-purity oxygen by adopting a Pulsed Laser Deposition (PLD) system, and controlling the gas pressure to be 20 mT; setting the energy density of the pulse laser to 1J/cm2The frequency is 5Hz, and the pulse is 10000 times; pre-pulsing for 200 times, performing cycle for 3 times at intervals of 120s, and then starting epitaxial growth of the film;
(7) after the deposition is finished, setting the cooling rate to be 20 ℃/min, and annealing in the deposition chamber under the same oxygen pressure as that during the deposition;
(8) and cooling to below 100 ℃ and taking out a film sample (namely the Sn doped metastable gallium oxide crystalline phase film).
The X-ray diffraction pattern of the Sn-doped metastable gallium oxide crystalline phase film prepared in this example is shown in fig. 3, which shows that the metastable gallium oxide crystalline phase film prepared in this example is a mixed crystalline phase gallium oxide film of α and ∈.
Example 4
(1) Selecting an a-surface (11-20) sapphire substrate, cleaning, and drying by high-purity nitrogen;
(2) placing the substrate in a box furnace for pre-annealing at 800 ℃ for 4h in air at a temperature rise rate and a temperature reduction rate of 5 ℃/min to form a flat and uniform step on the substrate;
(3) adopting a gallium oxide ceramic target material with Sn doping concentration of 0.1% mole fraction;
(4) fixing the pre-annealed substrate on a substrate holder, placing the substrate holder into a deposition chamber, adjusting the distance between the target and the substrate to 3cm, and vacuumizing to 10 DEG-5Pa below;
(5) heating the substrate to 600 ℃ at the speed of 5 ℃/min, and preserving the temperature for 1800 s;
(6) introducing high-purity oxygen by adopting a Pulsed Laser Deposition (PLD) system, and controlling the gas pressure to be 0.1 mT; the pulse laser energy density was set to 0.5J/cm2The frequency is 2Hz, and the pulse is 3000 times; pre-pulsing for 200 times, performing cycle for 3 times at intervals of 120s, and then starting epitaxial growth of the film;
(7) after the deposition is finished, setting the cooling rate to be 5 ℃/min, and annealing in the deposition chamber under the same oxygen pressure as that during the deposition;
(8) and cooling to below 100 ℃ and taking out a film sample (namely the Sn doped metastable gallium oxide crystalline phase film).
The X-ray diffraction pattern of the Sn-doped metastable gallium oxide crystalline phase thin film prepared in this example is shown in fig. 4, which shows that the metastable gallium oxide crystalline phase thin film prepared in this example is an epsilon-phase gallium oxide thin film.
Example 5
(1) Selecting an a-surface (11-20) sapphire substrate, cleaning, and drying by high-purity nitrogen;
(2) placing the substrate in a box furnace for pre-annealing, wherein the pre-annealing temperature is 1300 ℃, the time is 1h, the atmosphere is air, and the heating rate and the cooling rate are set to be 20 ℃/min, so that the substrate forms a flat and uniform step;
(3) adopting a gallium oxide ceramic target material with Sn doping concentration of 5% mole fraction;
(4) fixing the pre-annealed substrate on a substrate holder, placing the substrate holder into a deposition chamber, adjusting the distance between the target and the substrate to 10cm, and vacuumizing to 10-5Pa below;
(5) heating the substrate to 900 ℃ at the speed of 30 ℃/min, and preserving the heat for 1200 s;
(6) introducing high-purity oxygen by adopting a Pulsed Laser Deposition (PLD) system, and controlling the gas pressure to be 200 mT; setting the energy density of the pulse laser to 3J/cm2The frequency is 10Hz, and the pulse frequency is 20000 times; pre-pulsing for 200 times, performing cycle for 3 times at intervals of 120s, and then starting epitaxial growth of the film;
(7) after the deposition is finished, setting the cooling rate to be 30 ℃/min, and annealing in the deposition chamber under the same oxygen pressure as that during the deposition;
(8) and cooling to below 100 ℃ and taking out a film sample (namely the Sn doped metastable gallium oxide crystalline phase film).
The X-ray diffraction pattern of the Sn-doped metastable gallium oxide crystalline phase film prepared in this example is shown in fig. 5, which shows that the metastable gallium oxide crystalline phase film prepared in this example is a mixed crystalline phase gallium oxide film of α and ∈.
Comparative example 1
(1) Selecting an a-surface (11-20) sapphire substrate, cleaning, and drying by high-purity nitrogen;
(2) placing the substrate in a box furnace for pre-annealing at 1000 ℃ for 2h in air at a heating rate and a cooling rate of 10 ℃/min to form a flat and uniform step on the substrate;
(3) adopting a gallium oxide ceramic target material with Sn doping concentration of 0% mole fraction;
(4) fixing the pre-annealed substrate on a substrate holder, placing the substrate holder into a deposition chamber, adjusting the distance between the target and the substrate to 5cm, and vacuumizing to 10 DEG-5Pa below;
(5) heating the substrate to 800 ℃ at the speed of 20 ℃/min, and keeping the temperature for 1800 s;
(6) introducing high-purity oxygen by adopting a Pulsed Laser Deposition (PLD) system, and controlling the gas pressure to be 20 mT; setting the energy density of the pulse laser to 1J/cm2The frequency is 5Hz, and the pulse is 10000 times; pre-pulsing for 200 times, performing cycle for 3 times at intervals of 120s, and then starting epitaxial growth of the film;
(7) after the deposition is finished, setting the cooling rate to be 20 ℃/min, and annealing in the deposition chamber under the same oxygen pressure as that during the deposition;
(8) and cooling to below 100 ℃ to take out a film sample (namely the gallium oxide film).
The X-ray diffraction pattern of the gallium oxide film prepared in this comparative example is shown in fig. 6, and it can be seen that the beta-phase gallium oxide film prepared in this example is thermally stable.
Comparative example 2
(1) Selecting a c-plane (0001) sapphire substrate, cleaning, and drying by high-purity nitrogen;
(2) placing the substrate in a box furnace for pre-annealing at 1000 ℃ for 2h in air at a heating rate and a cooling rate of 10 ℃/min to form a flat and uniform step on the substrate;
(3) adopting a gallium oxide ceramic target material with Sn doping concentration of 1% mole fraction;
(4) fixing the pre-annealed substrate on a substrate holder, placing the substrate holder into a deposition chamber, adjusting the distance between the target and the substrate to 5cm, and vacuumizing to 10 DEG-5Pa below;
(5) heating the substrate to 800 ℃ at the speed of 20 ℃/min, and keeping the temperature for 1800 s;
(6) introducing high-purity oxygen by adopting a Pulsed Laser Deposition (PLD) system, and controlling the gas pressure to be 200 mT; setting the energy density of the pulse laser to 1J/cm2The frequency is 5Hz, and the pulse is 10000 times; pre-pulsing for 200 times, performing cycle for 3 times at intervals of 120s, and then starting epitaxial growth of the film;
(7) after the deposition is finished, setting the cooling rate to be 20 ℃/min, and annealing in the deposition chamber under the same oxygen pressure as that during the deposition;
(8) and cooling to below 100 ℃ to take out a film sample (namely the gallium oxide film).
The X-ray diffraction pattern of the gallium oxide film prepared in this comparative example is shown in fig. 7, and it can be seen that the beta-phase gallium oxide film prepared in this example is thermally stable.
Comparative example 3
(1) Selecting an a-surface (11-20) sapphire substrate, cleaning, and drying by high-purity nitrogen;
(2) placing the substrate in a box furnace for pre-annealing at 1000 ℃ for 2h in air at a heating rate and a cooling rate of 10 ℃/min to form a flat and uniform step on the substrate;
(3) adopting a gallium oxide ceramic target material with Sn doping concentration of 5.5% by mole fraction;
(4) fixing the pre-annealed substrate on a substrate holder, placing the substrate holder into a deposition chamber, adjusting the distance between the target and the substrate to 5cm, and vacuumizing to 10 DEG-5Pa below;
(5) heating the substrate to 800 ℃ at the speed of 20 ℃/min, and keeping the temperature for 1800 s;
(6) introducing high-purity oxygen by adopting a Pulsed Laser Deposition (PLD) system, and controlling the gas pressure to be 20 mT; setting the energy density of the pulse laser to 1J/cm2The frequency is 5Hz, and the pulse is 10000 times; pre-pulsing for 200 times, performing cycle for 3 times at intervals of 120s, and then starting epitaxial growth of the film;
(7) after the deposition is finished, setting the cooling rate to be 20 ℃/min, and annealing in the deposition chamber under the same oxygen pressure as that during the deposition;
(8) and cooling to below 100 ℃ to take out a film sample (namely the gallium oxide film).
The X-ray diffraction pattern of the Sn-doped metastable gallium oxide crystalline phase film prepared in this comparative example is shown in fig. 10, and it can be seen that the gallium oxide crystalline phase film prepared in this example is a mixed crystalline phase gallium oxide film of α, β and ∈.
Example 6
(1) Selecting an a-surface (11-20) sapphire substrate, cleaning, and drying by high-purity nitrogen;
(2) placing the substrate in a box furnace for pre-annealing at 1000 ℃ for 2h in air at a heating rate and a cooling rate of 10 ℃/min to form a flat and uniform step on the substrate;
(3) adopting a gallium oxide ceramic target material with Sn doping concentration of 0.75% mole fraction;
(4) fixing the pre-annealed substrate on a substrate holder, placing the substrate holder into a deposition chamber, adjusting the distance between the target and the substrate to 5cm, and vacuumizing to 10 DEG-5Pa below;
(5) heating the substrate to 800 ℃ at the speed of 20 ℃/min, and keeping the temperature for 1800 s;
(6) introducing high-purity oxygen by adopting a Pulsed Laser Deposition (PLD) system, and controlling the gas pressure to be 20 mT; setting the energy density of the pulse laser to 1J/cm2The frequency is 5Hz, and the pulse is 10000 times; pre-pulsing for 200 times, performing cycle for 3 times at intervals of 120s, and then starting epitaxial growth of the film;
(7) after the deposition is finished, setting the cooling rate to be 20 ℃/min, and annealing in the deposition chamber under the same oxygen pressure as that during the deposition;
(8) and cooling to below 100 ℃ and taking out a film sample (namely the Sn doped metastable gallium oxide crystalline phase film).
The X-ray diffraction pattern of the Sn-doped metastable gallium oxide crystalline phase film prepared in this example is shown in fig. 11, which shows that the metastable gallium oxide crystalline phase film prepared in this example is an α -phase gallium oxide film.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
It should be understood that the technical solution of the present invention is not limited to the above-mentioned specific embodiments, and all technical modifications made according to the technical solution of the present invention fall within the protection scope of the present invention without departing from the spirit of the present invention and the protection scope of the claims.
Claims (10)
1. A method for preparing Sn doped metastable gallium oxide crystalline phase film is characterized by comprising the following steps:
providing sapphire as a substrate;
and adopting a pulsed laser deposition technology, taking the Sn-doped gallium oxide ceramic target as a target material, epitaxially growing a film on the surface of the substrate, and annealing to obtain a Sn-doped metastable gallium oxide crystalline phase film;
wherein the molar percentage content of Sn in the target material is 0.1-5%; the process conditions adopted by the pulse laser deposition technology comprise: the oxygen pressure is 0.1-200 mT, the deposition temperature is 600-900 ℃, and the pulse laser energy density is 0.5-3J/cm2。
2. The production method according to claim 1, characterized by comprising:
placing sapphire as a substrate in a pulsed laser deposition system, and vacuumizing the reaction cavity to 10 DEG-5Heating the substrate to 600-900 ℃ at the heating rate of 5-30 ℃/min below Pa, and then carrying out heat preservation treatment for more than 1200 s;
and adopting a pulse laser deposition technology, taking the Sn-doped gallium oxide ceramic target as a target material, performing pre-deposition on the surface of the substrate, and then performing epitaxial growth film and annealing treatment to obtain the Sn-doped metastable gallium oxide crystalline phase film.
3. The method of claim 2, wherein: the distance between the target and the substrate is 3 cm-10 cm;
and/or the sapphire comprises a-plane sapphire; preferably, the a-plane sapphire comprises a-plane (11-20) sapphire.
4. The method according to claim 2, wherein the pre-deposition is performed under process conditions including: the pulse deposition frequency is 100-300 times, the interval time is 60-180 s, and the cycle frequency is 3-5 times;
and/or, the annealing treatment comprises: after the epitaxial growth of the film is finished, keeping the oxygen pressure of the reaction cavity to be 0.1-200 mT, and reducing the temperature to be below 100 ℃ at the cooling rate of 5-30 ℃/min, thereby finishing the annealing treatment of the substrate of the epitaxial growth film.
5. The method of claim 2, wherein: when the molar percentage content X of Sn in the Sn-doped gallium oxide ceramic target is more than or equal to 0.1% and less than 0.75%, the mesostable gallium oxide crystalline phase of the Sn-doped mesostable gallium oxide crystalline phase film is epsilon-Ga2O3A crystalline phase;
and/or when the molar percentage content X of Sn in the Sn-doped gallium oxide ceramic target is more than or equal to 0.75 percent and less than or equal to 1 percent, the mesostable gallium oxide crystalline phase in the Sn-doped mesostable gallium oxide crystalline phase film is alpha-Ga2O3A crystalline phase;
and/or when the molar percentage content X of Sn in the Sn-doped gallium oxide ceramic target is more than 1% and less than or equal to 5%, the mesostable gallium oxide crystalline phase of the Sn-doped mesostable gallium oxide crystalline phase film is alpha-Ga2O3With ε -Ga2O3Mixed crystal phases of (2).
6. The method of claim 1, further comprising: sapphire as a substrate is subjected to cleaning, drying and pre-annealing treatment.
7. The method of manufacturing according to claim 6, wherein the pre-annealing treatment includes: in the air atmosphere, pre-annealing the dried substrate at 800-1300 ℃ for 1-4 h;
preferably, the dried substrate is heated to 800-1300 ℃ at the heating rate of 5-20 ℃/min, pre-annealing treatment is carried out, and then cooling is carried out to room temperature at the cooling rate of 5-20 ℃/min.
8. The Sn-doped metastable gallium oxide crystalline phase thin film prepared by the method of any one of claims 1-7, wherein the metastable gallium oxide crystalline phase in the metastable gallium oxide crystalline phase thin film comprises alpha-Ga2O3Crystal phase and/or epsilon-Ga2O3The molar percentage content of Sn in the metastable gallium oxide crystalline phase film is 0.115 percent;
preferably, the Sn is dopedWhen the molar percentage content Y of Sn in the metastable gallium oxide crystalline phase film is more than or equal to 0.1 percent and less than 0.75 percent, the metastable gallium oxide crystalline phase is epsilon-Ga2O3A crystalline phase;
preferably, when the molar percentage content Y of Sn in the Sn-doped metastable gallium oxide crystalline phase film is more than or equal to 0.75 percent and less than or equal to 1 percent, the metastable gallium oxide crystalline phase is alpha-Ga2O3A crystalline phase;
preferably, when the molar percentage content Y of Sn in the Sn-doped metastable gallium oxide crystalline phase film is more than 1% and less than or equal to 5%, the metastable gallium oxide crystalline phase is alpha-Ga2O3With ε -Ga2O3Mixed crystal phases of (4);
preferably, the thickness of the metastable gallium oxide crystalline phase film is 200-400 nm.
9. Use of the Sn-doped metastable gallium oxide crystalline phase thin film of claim 8 in the preparation of solar blind ultraviolet photodetectors or high power electronic devices.
10. An optoelectronic device comprising the Sn-doped metastable gallium oxide crystalline phase thin film of claim 8.
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