A gallium oxide thin film and a preparation device and method of a heterojunction thereof

Abstract

The present application relates to the field of material preparation, more particularly to a gallium oxide thin film and a preparation device and method of a heterojunction thereof, and the present application comprises: a vacuum coating equipment with a cavity structure, a source material evaporation source, a heatable substrate, a laser source and an air inlet, the source material evaporation source is arranged at the bottom of the vacuum coating equipment, the heatable substrate is arranged at the top of the vacuum coating equipment, the laser source is arranged at one side of the vacuum coating equipment, and the air inlet is arranged at the other side of the vacuum coating equipment.The present application realizes in-situ preparation of a gallium oxide thin film and a heterojunction thereof in the same device, and realizes functions such as semiconductor doping, laser-induced recrystallization, interface state regulation and semiconductor annealing treatment, and in-situ regulation of the electrical properties and crystal structure of the gallium oxide thin film and the heterojunction thereof, so as to prepare a low-cost and high-quality gallium oxide thin film and a heterojunction thereof.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of material preparation, and more particularly, to a gallium oxide thin film and a heterojunction preparation device and method thereof. BACKGROUND

[0002] Solar blind ultraviolet detectors play a crucial role in various high-tech fields due to their unique spectral response characteristics. In space exploration, they can accurately detect solar blind ultraviolet radiation from distant galaxies, providing valuable cosmic information for scientists. In military equipment, they can be used for covert communication and precise navigation of guidance systems, greatly enhancing the stealth and accuracy of military operations. In radiation monitoring, they can monitor the radiation level around nuclear facilities in real time, ensuring public safety. In ultraviolet lithography technology, they can be used to precisely control the lithography process, improving the manufacturing precision of semiconductor devices. In addition, in scientific research, they are an important tool for exploring the microscopic structure and properties of matter.

[0003] Gallium oxide, as a semiconductor material with excellent photoelectric properties, has a band gap of about 4.9 eV, corresponding to an optical absorption wavelength in the solar blind ultraviolet region, making it an ideal material for the preparation of solar blind ultraviolet detectors. However, despite its excellent performance, the preparation of single-crystal gallium oxide thin films faces technical complexity and high cost. Traditional single-crystal gallium oxide thin film preparation processes often require high-precision equipment and complex operation procedures, which not only increase production costs but also limit the possibility of large-scale application.

[0004] To break through this technical bottleneck, researchers have begun to explore simpler and more economical preparation processes. Among them, vacuum deposition technology is favored due to its simple operation and low cost. Through vacuum deposition technology, researchers have successfully prepared amorphous gallium oxide thin films. Although amorphous thin films may be slightly inferior to single-crystal thin films in some performance, the significant reduction in preparation cost and simplification of the preparation process make amorphous gallium oxide thin films still have broad application prospects in the field of solar blind ultraviolet detectors.

[0005] However, amorphous gallium oxide thin film alone is not enough to meet the needs of high-performance solar blind ultraviolet detectors. In order to achieve low dark current, high charge collection efficiency, high sensitivity and fast response characteristics, researchers begin to focus on gallium oxide heterojunction detectors. By constructing the heterojunction of gallium oxide and other semiconductor materials, the performance of the detector can be further optimized. However, the interface state of gallium oxide heterojunction has become a key problem to be solved. The existence of interface state will seriously affect the photoelectric response characteristics of the detector, resulting in increased dark current, reduced response speed and other problems. Therefore, how to effectively regulate the interface state of gallium oxide heterojunction to improve the comprehensive performance of the detector has become a research hotspot and difficulty in the field. SUMMARY

[0006] The present application provides a gallium oxide thin film and a preparation device and method for gallium oxide heterojunction to overcome at least one of the above-mentioned defects of the prior art.

[0007] The present application aims to at least partially solve the above technical problems.

[0008] To solve the above technical problems, the technical solutions of the present application are as follows:

[0009] A gallium oxide thin film and a preparation device and method for gallium oxide heterojunction, comprising: a vacuum coating equipment with a hollow structure, a source material evaporation source, a heatable substrate, a laser source and an air inlet, the source material evaporation source is arranged at the bottom of the vacuum coating equipment, the top of the source material evaporation source is provided with a heatable substrate, the lower surface of the heatable substrate is provided with a substrate, and the laser source and the air inlet are both arranged on the vacuum coating equipment.

[0010] Further, the source material evaporation source comprises at least three crucibles, and semiconductor particles are arranged in the crucibles.

[0011] Further, the semiconductor particles include any one of pre-set element-doped gallium oxide particles, P-type semiconductor particles or N-type semiconductor particles.

[0012] Further, the pre-set element-doped gallium oxide particles include one or more combinations of SiO2, MgO, NiO, ZnO, TiO2, In2O3, SnO2 and MnO doped in Ga2O3.

[0013] Further, the material of the substrate is any one of silicon wafer, quartz, glass, ceramic and stainless steel.

[0014] Further, the laser source is a structure with adjustable rotation angle, laser wavelength and light power density.

[0015] Further, the direction of the laser source and the evaporation direction of the source material evaporation source are both the surface of the heatable substrate.

[0016] A gallium oxide film and a heterojunction preparation method thereof, applied to the gallium oxide film and the heterojunction preparation device thereof, comprising the following steps:

[0017] S1: fixing a substrate on the lower surface of a heatable substrate, and evacuating the interior of a vacuum film coating device to a vacuum state through a gas inlet;

[0018] S2: evaporating P-type semiconductor particles of a source material evaporation source to deposit a P-type semiconductor film on the surface of the substrate;

[0019] S3: feeding a preset gas to the surface of the P-type semiconductor film through the gas inlet, and performing laser irradiation treatment on the surface of the P-type semiconductor film using a laser source;

[0020] S4: evaporating gallium oxide particles doped with a preset element of the source material evaporation source to deposit a gallium oxide film on the surface of the P-type semiconductor film;

[0021] S5: feeding a preset gas to the surface of the gallium oxide film through the gas inlet, and performing laser irradiation treatment on the surface of the gallium oxide film using a laser source;

[0022] S6: evaporating N-type semiconductor particles of the source material evaporation source to deposit an N-type semiconductor film on the surface of the gallium oxide film;

[0023] S7: feeding a preset gas to the surface of the N-type semiconductor film through the gas inlet, and performing laser irradiation treatment on the surface of the N-type semiconductor film using a laser source (5) to obtain a gallium oxide film and a heterojunction thereof.

[0024] Further, after step S7, the gallium oxide film and the heterojunction thereof obtained are further subjected to high-temperature annealing treatment, comprising:

[0025] The gallium oxide film and the heterojunction thereof obtained are subjected to high-temperature annealing treatment by heating the heatable substrate to a preset temperature.

[0026] Further, the gas inlet has a gas flow range of 0.2-40 SCCM.

[0027] Compared with the prior art, the technical scheme of the present application has the beneficial effects that:

[0028] The source material evaporation source is arranged at the bottom of the vacuum coating equipment, the heatable substrate is arranged at the top of the source material evaporation source, the laser source is arranged at one side of the vacuum coating equipment, the gas inlet is arranged at the other side of the vacuum coating equipment, and the gallium oxide film and the heterojunction are arranged on the surface of the heatable substrate. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1 A gallium oxide film and a heterojunction preparation device structure schematic view is shown in the figure.

[0030] Figure 2 A gallium oxide film and a heterojunction preparation device structure schematic view is shown in the figure.

[0031] Figure 3 A gallium oxide film and a heterojunction preparation method flow chart is shown in the figure.

[0032] Figure 4 A gallium oxide film and a heterojunction preparation method flow chart is shown in the figure.

[0033] Figure 5 A gallium oxide film surface topography is shown in the figure.

[0034] In the figure, 1 is a vacuum coating equipment, 2 is a source material evaporation source, 3 is a source material vapor flow, 4 is a heatable substrate, 5 is a laser source, 6 is a laser, 7 is a gas inlet, 8 is a substrate, 9 is a gallium oxide film and a heterojunction, 10 is a P-type semiconductor thin film, 11 is a silicon-doped gallium oxide film, and 12 is an N-type semiconductor thin film. DETAILED DESCRIPTION

[0035] The attached drawings are only used for illustrative description and cannot be understood as a limitation of the patent;

[0036] In order to better illustrate the embodiment, some components in the attached drawings may be omitted, enlarged or reduced, and do not represent the actual product size;

[0037] For those skilled in the art, it is understandable that some known structures and their descriptions in the drawings may be omitted.

[0038] The technical solutions of the present application will be further described below in combination with the drawings and embodiments.

[0039] Embodiment 1

[0040] A gallium oxide film and a heterojunction preparation device, as shown inFigure 1 As shown, it comprises: a vacuum coating equipment 1 with an internal cavity structure, a source material evaporation source 2, a heatable substrate 4, a laser source 5 and an air inlet 7, the source material evaporation source 2 is arranged at the bottom of the vacuum coating equipment 1, the top of the source material evaporation source 2 is provided with the heatable substrate 4, the lower surface of the heatable substrate 4 is provided with a substrate 8, and the laser source 5 and the air inlet 7 are both arranged on the vacuum coating equipment 1.

[0041] In the specific implementation process, the source material evaporation source is arranged at the bottom of the vacuum coating equipment, the heatable substrate is arranged at the top of the source material evaporation source, the laser source is arranged on one side of the vacuum coating equipment, the air inlet is arranged on the other side of the vacuum coating equipment, and the gallium oxide film is arranged on the surface of the heatable substrate. The gallium oxide film and its heterojunction, semiconductor doping, laser-induced recrystallization, interface state regulation and semiconductor annealing process are prepared in situ in the same device, the material preparation cost is reduced, and the electrical properties and crystal structure of the gallium oxide film and its heterojunction are regulated in situ, so that a high-quality gallium oxide film and its heterojunction are prepared.

[0042] Embodiment 2

[0043] This embodiment continues to disclose the following contents on the basis of embodiment 1:

[0044] The source material evaporation source 2 comprises at least three crucibles, the semiconductor particles are arranged in the crucibles, and the source material can be melted and evaporated within a specific time.

[0045] In the specific implementation process, the source material is P-type semiconductor particles, N-type semiconductor particles and silicon-doped gallium oxide particles, the source material evaporation source is composed of 5 crucibles, each crucible contains one kind of source material, and the source material can be melted and evaporated within a specific time. The preparation of the gallium oxide film and its heterojunction and the semiconductor doping process are realized in situ on the same device.

[0046] Embodiment 3

[0047] This embodiment continues to disclose the following contents on the basis of embodiments 1 and 2:

[0048] The semiconductor particles comprise any one of the following: pre-set element-doped gallium oxide particles, P-type semiconductor particles or N-type semiconductor particles.

[0049] The pre-set element-doped gallium oxide particles comprise one or more combinations of SiO2, MgO, NiO, ZnO, TiO2, In2O3, SnO2 and MnO doped in Ga2O3.

[0050] The substrate is one of the following: a silicon wafer, quartz, glass, ceramic and stainless steel.

[0051] Embodiment 4

[0052] This embodiment continues to disclose the following on the basis of Embodiments 1, 2 and 3:

[0053] The laser source 5 is adjustable in rotation angle, laser wavelength and optical power density.

[0054] The laser wavelength of the laser source ranges from 200 to 1500 nm, and the optical power density ranges from 0.1 to 150 mW / cm 2 The laser of the laser source can be precisely irradiated on any position on the heatable substrate.

[0055] The semiconductor thin film undergoes recrystallization effect under laser irradiation, realizing polycrystalline or single-crystal semiconductor thin film. On the other hand, the laser irradiation treatment can remove the interface state of the semiconductor thin film, preparing a gallium oxide thin film heterojunction with low interface state density. The preparation of gallium oxide thin film and its heterojunction, laser-induced recrystallization and interface state regulation treatment can be realized in situ on the same device.

[0056] The orientation of the laser source 5 and the evaporation direction of the source material evaporation source 2 are both the surface of the heatable substrate 4.

[0057] Embodiment 5

[0058] This embodiment continues to disclose the following on the basis of Embodiments 1, 2, 3 and 4:

[0059] A gallium oxide thin film and a heterojunction preparation method thereof, applied to a gallium oxide thin film and a heterojunction preparation device thereof, comprising the following steps:

[0060] S1: fixing the substrate 8 to the lower surface of the heatable substrate 4, and evacuating the interior of the vacuum coating equipment 1 to a vacuum state through the gas inlet 7;

[0061] S2: evaporating P-type semiconductor particles of the source material evaporation source 2 to deposit a P-type semiconductor thin film on the surface of the substrate 8;

[0062] S3: the gas inlet 7 transports a preset gas to the surface of the P-type semiconductor thin film, and the laser source 5 is used for laser irradiation treatment on the surface of the P-type semiconductor thin film;

[0063] S4: evaporating gallium oxide particles doped with a preset element of the source material evaporation source 2 to deposit a gallium oxide thin film on the surface of the P-type semiconductor thin film;

[0064] S5: the gas inlet 7 transports a preset gas to the surface of the gallium oxide thin film, and the laser source 5 is used for laser irradiation treatment on the surface of the gallium oxide thin film;

[0065] S6: Evaporate N-type semiconductor particles of the source material evaporation source 2 to deposit N-type semiconductor thin film on the surface of the gallium oxide thin film;

[0066] S7: The gas inlet 7 delivers preset gas to the surface of the N-type semiconductor thin film, and the laser source 5 is used to perform laser irradiation treatment on the surface of the N-type semiconductor thin film to obtain the gallium oxide thin film and its heterojunction.

[0067] In the specific implementation process, the raw material includes: specific element doped gallium oxide particles, the specific elements include Si, Mg, Ni, Zn, Ti, In, Sn and Mn, etc., the specific element doped gallium oxide is composed of Ga2O3 and one or more doped element oxides, the doped element oxides include SiO2, MgO, NiO, ZnO, TiO2, In2O3, SnO2 and MnO, etc., the mass content of the doped element oxides ranges from 1% to 60%;

[0068] P-type semiconductor particles, the P-type semiconductor includes any one of P-type NiO, Cu2O, CoO, Cu2S, SnO, SnS and MnO semiconductor;

[0069] N-type semiconductor particles, the N-type semiconductor includes any one of N-type WO3, TiO2, Fe2O3, ZnO, V2O5, CrO3 and BaO semiconductor.

[0070] The gas flow range of the gas inlet 7 is 0.2-40 SCCM, and the gas delivered by the gas inlet includes oxygen, ozone, nitrogen, argon and hydrogen, etc.

[0071] Example 6

[0072] This embodiment is based on examples 1, 2, 3, 4 and 5, and further discloses the following content:

[0073] After step S7, the obtained gallium oxide thin film and its heterojunction are further subjected to high-temperature annealing treatment, including:

[0074] The obtained gallium oxide thin film and its heterojunction are subjected to high-temperature annealing treatment by heating the heatable substrate 4 to a preset temperature.

[0075] The heating temperature range of the heatable substrate is 50-1200℃, the heatable substrate is a circular substrate with a diameter of 5-30 inches, and the semiconductor annealing treatment can be realized in situ on the same device.

[0076] Example 7

[0077] This embodiment is based on examples 1, 2, 3, 4, 5 and 6, and further discloses the following content:

[0078] As shown in Figure 2 Step one: quartz glass was used as the substrate, with an area of 2 cm x 2 cm and a thickness of 1 mm. The quartz glass substrate was sequentially cleaned by ultrasonic cleaning with acetone, anhydrous ethanol, and water for 15 min. The quartz glass substrate was fixed on a heatable substrate, and the vacuum degree of the chamber of the electron beam evaporation device was pumped to 3 x 10 -3 Pa.

[0079] Step two: P-type semiconductor particles of the source material evaporation source were evaporated to deposit a P-type semiconductor film on the surface of the substrate. The P-type semiconductor was NiO, the deposition rate was 0.05 nm / s, and the deposition thickness was 200 nm.

[0080] Step three: ozone was supplied to the surface of the NiO film through the gas inlet, and the surface of the NiO film was treated by laser irradiation using a laser source. The ozone flow rate was 6 SCCM, the laser wavelength was 550 nm, the light power density was 20 mW / cm 2 , and the irradiation time was 10 min.

[0081] Step four: silicon-doped gallium oxide particles of the source material evaporation source were evaporated to deposit a silicon-doped gallium oxide film on the surface of the NiO film. The silicon-doped gallium oxide particles were composed of gallium oxide and silicon dioxide, with a mass content of silicon dioxide of 30%. The deposition rate of the silicon-doped gallium oxide film was 0.1 nm / s, and the deposition thickness was 800 nm.

[0082] Step five: ozone was supplied to the surface of the gallium oxide film through the gas inlet, and the surface of the gallium oxide film was treated by laser irradiation using a laser source. The ozone flow rate was 10 SCCM, the laser wavelength was 550 nm, the light power density was 30 mW / cm 2 , and the irradiation time was 30 min.

[0083] Step six: N-type semiconductor particles of the source material evaporation source were evaporated to deposit an N-type semiconductor film on the surface of the gallium oxide film. The N-type semiconductor was ZnO, the deposition rate was 0.05 nm / s, and the deposition thickness was 200 nm.

[0084] Step seven: ozone was supplied to the surface of the ZnO film through the gas inlet, and the surface of the ZnO film was treated by laser irradiation using a laser source. The ozone flow rate was 6 SCCM, the laser wavelength was 550 nm, the light power density was 20 mW / cm 2 , and the irradiation time was 10 min.

[0085] Step eight: the heatable substrate was heated to 500°C, and the prepared gallium oxide heterojunction was annealed for 1 hour.

[0086] In the implementation process, the preparation process can be used to realize in-situ preparation of gallium oxide thin film and heterojunction, semiconductor doping, laser-induced recrystallization, interface state regulation and semiconductor annealing treatment on the same device, and the electrical properties and crystal structure of the gallium oxide thin film and heterojunction are in-situ regulated, so that the high-quality gallium oxide thin film and heterojunction are prepared. Figure 5 is a surface morphology diagram of the gallium oxide thin film prepared by the above scheme.

[0087] Embodiment 8

[0088] This embodiment is based on embodiments 1, 2, 3, 4, 5, 6 and 7, and the following contents are further disclosed:

[0089] In the process of this embodiment, in steps three to seven, oxygen is supplied to the film deposition position of the sample during the deposition of the NiO thin film, the gallium oxide thin film and the ZnO thin film, and laser irradiation treatment is performed, the oxygen flow is 8 SCCM, the laser wavelength is 550 nm, and the light power density is 15 mW / cm 2 Through this embodiment, the crystallinity of the gallium oxide thin film and the heterojunction is further improved.

[0090] The same or similar reference signs correspond to the same or similar components;

[0091] The terms used to describe the positional relationship in the drawings are only used for exemplary illustration, and cannot be understood as a limitation on the patent;

[0092] Obviously, the above embodiments of the application are only examples for clearly illustrating the application, and are not intended to limit the implementation modes of the application. Based on the above description, other different forms of changes or variations can be made by those skilled in the art. Here, all the implementation modes do not need to be exhausted. Any modification, equivalent replacement and improvement made within the spirit and principle of the application should be included in the protection scope of the claims of the application.

Claims

1. A method for preparing a gallium oxide thin film and its heterojunction, characterized in that, The method comprises the following steps: S1: fixing a substrate (8) to the lower surface of a heatable substrate (4), and evacuating the interior of a vacuum coating device (1) to a vacuum state through an air inlet (7); S2: evaporating P-type semiconductor particles of a source material evaporation source (2) to deposit a P-type semiconductor thin film on the surface of the substrate (8); S3: The gas inlet (7) delivers a preset gas to the surface of the P-type semiconductor film, and a laser source (5) is used to perform laser irradiation treatment on the surface of the P-type semiconductor film; wherein the laser wavelength of the laser source (5) is 550 nm, the optical power density is 20 mW / cm 2 , and the irradiation time is 10 min; S4: evaporating pre-set element-doped gallium oxide particles of the source material evaporation source (2) to deposit a gallium oxide thin film on the surface of the P-type semiconductor thin film; S5: The gas inlet (7) delivers a preset gas to the surface of the gallium oxide film, and a laser source (5) is used to perform laser irradiation treatment on the surface of the gallium oxide film; wherein the laser wavelength of the laser source (5) is 550 nm, the light power density is 30 mW / cm 2 , and the irradiation time is 30 min. S6: The gallium oxide film is taken out from the laser source (5) and is placed in a vacuum drying oven (6) for vacuum drying treatment for 30 min. S7: The gallium oxide film is taken out from the vacuum drying oven (6) and is placed in a vacuum coating machine (8) for vacuum coating treatment for 30 min. S8: The gallium oxide film is taken out from the vacuum coating machine S6: evaporating N-type semiconductor particles of the source material evaporation source (2) to deposit an N-type semiconductor thin film on the surface of the gallium oxide thin film; S7: The gas inlet (7) delivers a preset gas to the surface of the N-type semiconductor film, and a laser source (5) is used to perform laser irradiation treatment on the surface of the N-type semiconductor film to obtain a gallium oxide film and a heterojunction thereof; wherein the laser wavelength of the laser source (5) is 550 nm, the optical power density is 20 mW / cm 2 , and the irradiation time is 10 min.

2. The gallium oxide thin film and the heterojunction preparation method thereof according to claim 1, characterized in that, After step S7, the method further comprises high-temperature annealing treatment of the obtained gallium oxide thin film and heterojunction, comprising: high-temperature annealing treatment of the obtained gallium oxide thin film and heterojunction by heating the heatable substrate (4) to a pre-set temperature.

3. The gallium oxide thin film and the heterojunction preparation method thereof according to claim 1, characterized in that, The air inlet flow range of the air inlet (7) is 0.2 ~ 40 SCCM.

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