CN116516315A - The method comprises the following steps of<010>beta-Ga with preferred orientation 2 O 3 Method for producing film - Google Patents
The method comprises the following steps of<010>beta-Ga with preferred orientation 2 O 3 Method for producing film Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 238000000151 deposition Methods 0.000 claims abstract description 73
- 239000010408 film Substances 0.000 claims abstract description 72
- 230000008021 deposition Effects 0.000 claims abstract description 70
- 239000000758 substrate Substances 0.000 claims abstract description 65
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims abstract description 32
- 239000011521 glass Substances 0.000 claims abstract description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 239000007789 gas Substances 0.000 claims abstract description 17
- 239000012159 carrier gas Substances 0.000 claims abstract description 15
- 238000001182 laser chemical vapour deposition Methods 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 239000012495 reaction gas Substances 0.000 claims abstract description 12
- 238000010790 dilution Methods 0.000 claims abstract description 11
- 239000012895 dilution Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000010409 thin film Substances 0.000 claims abstract description 11
- 238000000859 sublimation Methods 0.000 claims abstract description 4
- 230000008022 sublimation Effects 0.000 claims abstract description 4
- 239000013078 crystal Substances 0.000 claims description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- ZVYYAYJIGYODSD-LNTINUHCSA-K (z)-4-bis[[(z)-4-oxopent-2-en-2-yl]oxy]gallanyloxypent-3-en-2-one Chemical compound [Ga+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O ZVYYAYJIGYODSD-LNTINUHCSA-K 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000003085 diluting agent Substances 0.000 claims description 5
- 238000005137 deposition process Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 238000002441 X-ray diffraction Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000000843 powder Substances 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 6
- 238000000861 blow drying Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000003384 imaging method Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
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- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
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- 230000001105 regulatory effect Effects 0.000 description 1
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- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/48—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating by irradiation, e.g. photolysis, radiolysis, particle radiation
- C23C16/483—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating by irradiation, e.g. photolysis, radiolysis, particle radiation using coherent light, UV to IR, e.g. lasers
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Abstract
The present invention relates to a kind of<010>beta-Ga with preferred orientation 2 O 3 The preparation method of the film comprises the following specific steps: 1) Pretreating a glass substrate, putting the glass substrate into a deposition cavity, and vacuumizing the deposition cavity to below 10 Pa; 2) Introducing dilution gas into the deposition cavity to enable the deposition cavity to reach deposition pressure, closing the dilution gas, then heating the precursor in the raw material tank to sublimation temperature, opening laser to irradiate the surface of the glass substrate to enable the glass substrate to reach deposition temperature, simultaneously introducing carrier gas and reaction gas into the deposition cavity to perform deposition, and depositing beta-Ga on the glass substrate to obtain 2 O 3 A film. The invention adopts the laser chemical vapor deposition method, controls the orientation of the film by adjusting experimental parameters, and successfully prepares the film on the surface of the quartz glass substrate with low cost<010>beta-Ga with preferred orientation 2 O 3 Polycrystalline thin film for broadening beta-Ga 2 O 3 The application range of the polycrystalline film has very important significance.
Description
Technical Field
The invention belongs to the technical field of single crystal growth, and in particular relates to a method for preparing a single crystal<010>beta-Ga with preferred orientation 2 O 3 A method for preparing a film.
Background
β-Ga 2 O 3 Is a novel wide bandgap semiconductor material with a bandgap of about 4.9eV. Large forbidden band width enables beta-Ga 2 O 3 The device has the capability of manufacturing high-voltage-resistance, high-power and low-loss power devices and deep ultraviolet photoelectric devices; in addition to that, beta-Ga 2 O 3 And is also widely applied to the fields of high-temperature gas-sensitive sensing, photoelectric conversion, LED luminescence and the like. beta-Ga 2 O 3 Is monoclinic structure crystal, space group is C2/m, lattice constant is α=β=90°, γ= 103.82 °, and the structural asymmetry thereof causes anisotropy in performance. For example, beta-Ga 2 O 3 (Single Crystal)<010>Thermal conductivity in the direction (27.0 Wm -1 K -1 ) About 2 to 3 times in other directions, the conductivity (38Ω -1 cm -1 ) About<001>20 times in direction, the two-photon absorption coefficient TPA (1.2 cm/GW) is much higher than +.>β-Ga 2 O 3 Two-photon absorption coefficient (0.6 cm/GW). Currently, high quality beta-Ga 2 O 3 The cost of single crystal is still high, and the polycrystalline film with preferred orientation can also show anisotropic property, so that the theory of preferred orientation of the polycrystalline body is developedThe application range of the polycrystal can be widened, and meanwhile, the requirement for high-price single crystals can be reduced.
Current research often limits the orientation of the crystal film by selecting single crystal substrates with low mismatch rates, and has been successful in producing high quality on heterogeneous substrates<100>、<001>Andoriented beta-Ga 2 O 3 A film. However, the process is not limited to the above-described process,<010>lower symmetry of crystal face and<010>oriented beta-Ga 2 O 3 Heterogeneous substrates with films conforming to epitaxial relations are not found yet, but homogeneous substrates are expensive and poor in electrical and thermal conductivity; in addition to this, the process is carried out,<010>the surface energy of the face is relatively high (about 2.78J/m 2 ) At deposition temperatures (less than 1100 ℃) of conventional fabrication methods, the reactive atoms cannot acquire enough energy to align along the high energy plane to form<010>Preferred orientation. For the above reasons, no researchers have prepared on heterogeneous substrates<010>beta-Ga with preferred orientation 2 O 3 Polycrystalline thin films, which limit highly oriented beta-Ga 2 O 3 Development of polycrystalline thin films. Thus, a preparation is explored<010>beta-Ga with preferred orientation 2 O 3 The method of the polycrystalline film has great significance for widening the application range.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for solving the defects existing in the prior art
<010>beta-Ga with preferred orientation 2 O 3 A method for preparing a film.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
providing a kind of<010>beta-Ga with preferred orientation 2 O 3 The preparation method of the film comprises the following specific steps:
1) Placing the precursor in a raw material tank of cold-wall type laser chemical vapor deposition equipment, pretreating a glass substrate, placing the glass substrate into a deposition cavity, adjusting the position of the glass substrate to be positioned in a laser coverage range, and vacuumizing the deposition cavity to below 10 Pa;
2) Introducing dilution gas into the deposition cavity to enable the deposition cavity to reach deposition pressure, closing the dilution gas, heating the precursor in the raw material tank to sublimation temperature, opening laser to irradiate the surface of the glass substrate to enable the glass substrate to reach deposition temperature, simultaneously introducing carrier gas and reaction gas into the deposition cavity to perform deposition, closing the carrier gas, the reaction gas and the laser in sequence after the deposition is finished, naturally cooling to room temperature, and depositing on the glass substrate to obtain the glass substrate<010>beta-Ga with preferred orientation 2 O 3 A film.
According to the scheme, the precursor in the step 1) is powdered gallium acetylacetonate (Ga (acac) 3 ). The sublimation temperature of the precursor gallium acetylacetonate is 200 ℃.
According to the above scheme, the glass substrate in step 1) is a quartz glass substrate, and the pretreatment method of the glass substrate comprises the following steps: sequentially placing glass substrate into acetone and ethanol for ultrasonic cleaning, then washing with deionized water, and finally using N 2 And drying the surface of the glass substrate.
According to the scheme, the diluent gas in the step 2) is Ar, the purity of Ar is more than 99.999vol%, and the flow rate of Ar is 100-500 sccm.
According to the scheme, the deposition pressure in the step 2) is 100-10000 Pa.
According to the scheme, the laser wavelength in the step 2) is 800-1200 nm.
According to the scheme, the carrier gas in the step 2) is Ar, the flow is 100-200 sccm, the purity is more than 99.999vol%, and the reaction gas is O 2 The flow rate is 100-500 sccm, and the purity is more than 99.999 vol%.
According to the scheme, the deposition process conditions in the step 2) are as follows: the deposition temperature is 850-1100 ℃, and the deposition time is 5-20 min.
According to the scheme, step 2) beta-Ga 2 O 3 The deposition growth rate of the film is 10-45 mu m/h.
The invention also comprises the preparation method<010>beta-Ga with preferred orientation 2 O 3 A film of<010>beta-Ga with preferred orientation 2 O 3 A compact structure composed of columnar crystals. The thickness of the film can be regulated and controlled according to the deposition time.
The invention selects a quartz glass substrate and adopts a Laser Chemical Vapor Deposition (LCVD) method to prepare the high-orientation beta-Ga 2 O 3 Polycrystalline film, beta-Ga is controlled by adjusting parameters such as pressure, temperature and the like 2 O 3 Orientation of the crystals. The laser chemical vapor deposition method is used because the excitation of the high-energy laser beam can accelerate the thermodynamic and kinetic processes of decomposition, adsorption, film formation and the like of the reaction gas, under different deposition conditions, the growth rates (namely the formation energy) of different crystal faces are different, the crystal faces in the high-speed growth crystallography can quickly cover the crystal faces in other orientations, and the crystal grows along a certain specific crystal direction as a result of the competition growth of various crystal faces. The experimental results show that: when the quartz glass substrate is selected and the deposition temperature is between 850 and 1100 ℃, the film is formed by a large amount of<010>beta-Ga with preferred orientation 2 O 3 The columnar crystals form a high-density structure.
The invention has the beneficial effects that: the invention adopts the laser chemical vapor deposition method, controls the orientation of the film by adjusting experimental parameters, and successfully prepares the film on the surface of the quartz glass substrate with low cost<010>beta-Ga with preferred orientation 2 O 3 Polycrystalline thin film for broadening beta-Ga 2 O 3 The application range of the polycrystalline film has very important significance.
Drawings
FIG. 1 is a block diagram of the present invention prepared in example 1<010>Oriented beta-Ga 2 O 3 XRD pattern of the film;
FIG. 2 is a schematic diagram of the process of example 1<010>Oriented beta-Ga 2 O 3 SEM image of the film;
FIG. 3 is a diagram of the preparation of example 2<010>Oriented beta-Ga 2 O 3 XRD pattern of the film;
FIG. 4 is a diagram of the preparation of example 2<010>Oriented beta-Ga 2 O 3 SEM image of the film;
FIG. 5 is a graph of the preparation of comparative example 1Oriented beta-Ga 2 O 3 XRD pattern of the film;
FIG. 6 is a graph of the preparation of comparative example 1Oriented beta-Ga 2 O 3 SEM image of the film;
FIG. 7 shows the preferred orientation-free beta-Ga prepared in comparative example 2 2 O 3 XRD pattern of the film;
FIG. 8 shows the beta-Ga without preferential orientation prepared in comparative example 2 2 O 3 SEM image of the film.
Detailed Description
The present invention will be described in further detail below with reference to the accompanying drawings, so that those skilled in the art can better understand the technical scheme of the present invention.
Example 1
The method comprises the following steps of<010>beta-Ga with preferred orientation 2 O 3 The preparation method of the film material comprises the following specific steps:
1) Sequentially ultrasonically cleaning quartz glass substrate (10 mm×10mm×1 mm) in acetone for 10min, ultrasonically cleaning in ethanol for 5min, washing with deionized water, and finally washing with N 2 Blow-drying;
2) Grinding 0.5g of precursor gallium acetylacetonate into powder with the particle size of 1-10 mu m, placing the powder into a raw material tank of cold wall type laser chemical vapor deposition equipment, placing a cleaned quartz glass substrate into a deposition cavity of the laser chemical vapor deposition equipment, adjusting the position of the quartz glass substrate to be positioned in a laser coverage area, vacuumizing the deposition cavity to 10Pa, and keeping the vacuum for 5min;
3) Introducing dilution gas Ar with the flow rate of 500sccm and the purity of 99.999vol%, closing the dilution gas after the deposition pressure is 7000Pa, simultaneously heating a raw material tank to 200 ℃, starting laser to irradiate the quartz glass substrate, enabling the laser output wavelength to be 808nm, heating the surface of the quartz glass substrate to 850 ℃, and simultaneously introducing carrier gas Ar and reaction gas O into the deposition cavity 2 Deposition was carried out with an Ar flow of 200sccm and a purity of 99.999vol%, O 2 The flow rate is 200sccm, the purity is 99.999vol%, the deposition time is 10min, and the carrier gases Ar and O are sequentially closed after the deposition is finished 2 Closing the laser, and naturally cooling the quartz glass substrate to room temperature to obtain the final product<010>beta-Ga with preferred orientation 2 O 3 A film.
beta-Ga prepared in this example 2 O 3 The X-ray diffraction pattern and field emission scanning imaging pattern of the thin film material are shown in fig. 1 and 2. FIG. 1 is beta-Ga 2 O 3 Comparison of film X-ray diffraction pattern with standard PDF card, wherein (010) diffraction peak at 61 ° is higher than other peaks, whereas the strongest peak in standard PDF card (JCPDS 76-0573) is (111) diffraction peak at 35.2 °, which means β -Ga prepared in this example 2 O 3 The film is remarkable<010>Preferred orientation. FIG. 2 (a) is beta-Ga 2 O 3 The surface morphology of the film, FIG. 2 (b) is beta-Ga 2 O 3 The cross-sectional morphology of the film shows that the film material prepared in the embodiment is prepared from large-size beta-Ga 2 O 3 The columnar crystal structure is a compact structure, which is one of typical characteristics of a high-orientation polycrystalline film, and the thickness of the film is 6.2 mu m, and the growth rate of the film reaches 38.4 mu m/h.
Example 2
The method comprises the following steps of<010>beta-Ga with preferred orientation 2 O 3 The preparation method of the film material comprises the following specific steps:
1) Sequentially ultrasonically cleaning quartz glass substrate (10 mm×10mm×1 mm) in acetone for 10min, ultrasonically cleaning in ethanol for 5min, washing with deionized water, and finally washing with N 2 Blow-drying;
2) Grinding 0.5g of precursor gallium acetylacetonate into powder with the particle size of 1-10 mu m, placing the powder into a raw material tank of cold wall type laser chemical vapor deposition equipment, placing a cleaned quartz glass substrate into a deposition cavity of the laser chemical vapor deposition equipment, adjusting the position of the quartz glass substrate to be positioned in a laser coverage area, vacuumizing the deposition cavity to 10Pa, and keeping the vacuum for 5min;
3) Introducing dilution gas Ar into the deposition cavity, wherein the Ar flow is 500sccm, and the purity is 99.999vol%Closing the diluent gas after the deposition pressure is 7000Pa, simultaneously heating the raw material tank to 200 ℃, starting laser to irradiate the quartz glass substrate, enabling the laser output wavelength to be 808nm, heating the surface of the quartz glass substrate to 1100 ℃, and simultaneously introducing carrier gas Ar and reaction gas O into the deposition cavity 2 Deposition was carried out with an Ar flow of 200sccm and a purity of 99.999vol%, O 2 The flow rate is 200sccm, the purity is 99.999vol%, the deposition time is 10min, and the carrier gases Ar and O are sequentially closed after the deposition is finished 2 Closing the laser, and naturally cooling the quartz glass substrate to room temperature to obtain the final product<010>beta-Ga with preferred orientation 2 O 3 A film.
beta-Ga prepared in this example 2 O 3 The X-ray diffraction pattern and field emission scanning imaging pattern of the thin film material are shown in fig. 3 and 4. FIG. 3 is beta-Ga 2 O 3 Comparison of film X-ray diffraction Pattern and Standard PDF card, beta-Ga prepared in this example 2 O 3 The films were all remarkable as in example 1<010>Preferred orientation. FIG. 4 (a) is beta-Ga 2 O 3 The surface morphology of the film, the crystal grain is beta-Ga in figure 4 (b) 2 O 3 The cross-sectional morphology of the film, from which it is understood that the film material prepared in this example is also made of beta-Ga 2 O 3 The columnar crystals consisted of a dense structure, but the higher growth temperature increased the grain size compared to example 1. beta-Ga prepared in this example 2 O 3 The film thickness was 6.8 μm and the growth rate was 41.1 μm/h.
Comparative example 1
Preparation of beta-Ga by MgO substrate 2 O 3 The film material comprises the following specific steps:
1) Will be<111>MgO substrate (10 mm. Times.10 mm. Times.0.5 mm) was sequentially ultrasonically cleaned in acetone for 10min, in ethanol for 5min, then rinsed with deionized water, finally N 2 Blow-drying;
2) Grinding 0.5g of precursor gallium acetylacetonate into powder with the particle size of 1-10 mu m, placing the powder into a raw material tank of cold wall type laser chemical vapor deposition equipment, placing a cleaned MgO substrate into a deposition cavity of the laser chemical vapor deposition equipment, adjusting the position of the MgO substrate to be positioned in a laser coverage area, vacuumizing the deposition cavity to 10Pa, and maintaining for 5min;
3) Introducing a diluent gas Ar into the deposition cavity, wherein the Ar flow is 500sccm, the purity is 99.999vol%, the deposition pressure is 7000Pa, then closing the diluent gas, simultaneously heating a raw material tank to 200 ℃, starting laser to irradiate the MgO substrate, the output wavelength of the laser is 808nm, heating the surface of the MgO substrate to 1100 ℃, and simultaneously introducing a carrier gas Ar and a reaction gas O into the deposition cavity 2 Deposition was carried out with an Ar flow of 200sccm and a purity of 99.999vol%, O 2 The flow rate is 200sccm, the purity is 99.999vol%, the deposition time is 10min, and the carrier gases Ar and O are sequentially closed after the deposition is finished 2 Turning off the laser, naturally cooling the MgO substrate to room temperature, and obtaining the product on the surface of the MgO substratebeta-Ga with preferred orientation 2 O 3 A film.
beta-Ga prepared in this comparative example 2 O 3 The X-ray diffraction pattern and field emission scanning imaging pattern of the thin film material are shown in fig. 5 and 6. FIG. 5 is beta-Ga 2 O 3 Comparison of film X-ray diffraction pattern with standard PDF card, wherein at 18.9 °The diffraction peak is the strongest peak, located at 38.2 +.>The diffraction peak is the second strongest peak, which means that the beta-Ga prepared in this comparative example 2 O 3 The film is obvious->Preferred orientation. FIG. 6 is beta-Ga 2 O 3 The surface and section morphology of the film, beta-Ga can be observed 2 O 3 The film is formed by large-sized prismatic beta-Ga 2 O 3 The crystal grain is formed, and the surface and the section have obvious lamellar structure. beta-Ga prepared in this comparative example 2 O 3 The film growth rate was 30.48 μm/h.
Comparative example 2
Preparation of beta-Ga at a deposition temperature of 800 DEG C 2 O 3 The film comprises the following specific steps:
1) Sequentially ultrasonically cleaning quartz glass substrate (10 mm×10mm×1 mm) in acetone for 10min, ultrasonically cleaning in ethanol for 5min, washing with deionized water, and finally washing with N 2 Blow-drying;
2) Grinding 0.5g of precursor gallium acetylacetonate into powder with the particle size of 1-10 mu m, placing the powder into a raw material tank of cold wall type laser chemical vapor deposition equipment, placing a cleaned quartz glass substrate into a deposition cavity of the laser chemical vapor deposition equipment, adjusting the position of the quartz glass substrate to be positioned in a laser coverage area, vacuumizing the deposition cavity to 10Pa, and keeping the vacuum for 5min;
3) Introducing dilution gas Ar with the flow rate of 500sccm and the purity of 99.999vol%, closing the dilution gas after the deposition pressure is 7000Pa, simultaneously heating a raw material tank to 200 ℃, starting laser to irradiate the quartz glass substrate, enabling the laser output wavelength to be 808nm, heating the surface of the quartz glass substrate to 800 ℃, and simultaneously introducing carrier gas Ar and reaction gas O into the deposition cavity 2 Deposition was carried out with an Ar flow of 200sccm and a purity of 99.999vol%, O 2 The flow rate is 200sccm, the purity is 99.999vol%, the deposition time is 10min, and the carrier gases Ar and O are sequentially closed after the deposition is finished 2 Closing the laser, and obtaining beta-Ga without preferred orientation on the surface of the quartz glass substrate after the quartz glass substrate is naturally cooled to room temperature 2 O 3 A film.
beta-Ga prepared in this comparative example 2 O 3 The X-ray diffraction pattern and field emission scanning imaging pattern of the thin film material are shown in fig. 7 and 8. As shown in FIG. 5, beta-Ga 2 O 3 The X-ray diffraction pattern of the film shows typical polycrystalline characteristics and has no obvious preferred orientation. FIGS. 8 (a) and 8 (b) are beta-Ga, respectively 2 O 3 The surface and cross-sectional morphology of the thin film shows that the comparative example is beta-Ga prepared at low deposition temperature 2 O 3 The film material is made of a large amount of flat beta-Ga without preferred orientation 2 O 3 Composition of plate-like small particlesIs a dense structure of (a).
The above specific embodiments further explain the purposes and technical solutions of the present invention in detail. Various modifications and alterations of this invention will occur to those skilled in the art, and it is intended that all such modifications, equivalents, and improvements fall within the true spirit and scope of the invention.
Claims (10)
1. The method comprises the following steps of<010>beta-Ga with preferred orientation 2 O 3 The preparation method of the film is characterized by comprising the following specific steps:
1) Placing the precursor in a raw material tank of cold-wall type laser chemical vapor deposition equipment, pretreating a glass substrate, placing the glass substrate into a deposition cavity, adjusting the position of the glass substrate to be positioned in a laser coverage range, and vacuumizing the deposition cavity to below 10 Pa;
2) Introducing dilution gas into the deposition cavity to enable the deposition cavity to reach deposition pressure, closing the dilution gas, heating the precursor in the raw material tank to sublimation temperature, opening laser to irradiate the surface of the glass substrate to enable the glass substrate to reach deposition temperature, simultaneously introducing carrier gas and reaction gas into the deposition cavity to perform deposition, closing the carrier gas, the reaction gas and the laser in sequence after the deposition is finished, naturally cooling to room temperature, and depositing on the glass substrate to obtain the glass substrate<010>beta-Ga with preferred orientation 2 O 3 A film.
2. The method according to claim 1<010>beta-Ga with preferred orientation 2 O 3 The preparation method of the film is characterized in that the precursor in the step 1) is powdery gallium acetylacetonate.
3. The method according to claim 1<010>beta-Ga with preferred orientation 2 O 3 The preparation method of the film is characterized in that the glass substrate in the step 1) is a quartz glass substrate, and the pretreatment method of the glass substrate comprises the following steps: sequentially placing glass substrate into acetone and ethanol for ultrasonic cleaning, then washing with deionized water, and finally using N 2 And drying the surface of the glass substrate.
4. The method according to claim 1<010>beta-Ga with preferred orientation 2 O 3 The method for producing a thin film is characterized in that the diluent gas in step 2) is Ar, the purity of Ar is 99.999vol% or more, and the flow rate of Ar is 100-500 sccm.
5. The method according to claim 1<010>beta-Ga with preferred orientation 2 O 3 The preparation method of the film is characterized in that the deposition pressure in the step 2) is 100-10000 Pa.
6. The method according to claim 1<010>beta-Ga with preferred orientation 2 O 3 The preparation method of the film is characterized in that the laser wavelength in the step 2) is 800-1200 nm.
7. The method according to claim 1<010>beta-Ga with preferred orientation 2 O 3 A method for producing a thin film, characterized in that in step 2), the carrier gas is Ar, the flow rate is 100-200 sccm, the purity is 99.999vol% or more, and the reaction gas is O 2 The flow rate is 100-500 sccm, and the purity is more than 99.999 vol%.
8. The method according to claim 1<010>beta-Ga with preferred orientation 2 O 3 The preparation method of the film is characterized in that the deposition process conditions in the step 2) are as follows: the deposition temperature is 850-1100 ℃, and the deposition time is 5-20 min.
9. The method according to claim 1<010>beta-Ga with preferred orientation 2 O 3 A process for producing a film, characterized by comprising the step of 2) beta-Ga 2 O 3 The deposition growth rate of the film is 10-45 mu m/h.
10. Obtained by a process according to any one of claims 1 to 9<010>beta-Ga with preferred orientation 2 O 3 A film, characterized in that the film is<010>beta-Ga with preferred orientation 2 O 3 A compact structure composed of columnar crystals.
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