A gallium oxide thin film and a preparation method and application thereof

Abstract

The application provides a gallium oxide thin film and a preparation method and application thereof. The preparation method of the gallium oxide thin film comprises the following steps: in the presence of ozone, a gallium oxide target and a pulsed laser deposition method are used to deposit a gallium oxide thin film on a substrate. In the method, ozone is introduced in situ during the pulsed laser deposition process, and the construction of a peroxide atmosphere generates ionization inhibition and compensation effects, so that the prepared gallium oxide thin film has good electrical insulation characteristics. Compared with the method for realizing high insulation of the gallium oxide thin film through element doping, the preparation method provided by the application is simple in process, easy to implement, economical, practical, and has the prospect of large-scale production. In addition, the application further provides an electrical modulation method for donor-doped gallium oxide materials, so as to realize the regulation and control of the electrical insulation of the gallium oxide materials.

Description

Technical Field

[0001] This application belongs to the field of semiconductor materials technology, and relates to a gallium oxide thin film, its preparation method and application, specifically to a gallium oxide thin film, its preparation method and application, and an electrical modulation method for donor-doped gallium oxide materials. Background Technology

[0002] Gallium oxide (Ga₂O₃) is an emerging ultra-wide bandgap semiconductor material (~4.9 eV). Its bandgap can be continuously tunable throughout the entire solar-blind region, making it a promising material for natural solar-blind detectors and power electronics. Therefore, it is currently a key frontier area of ​​research and development for next-generation solar-blind ultraviolet photodetectors and power devices internationally. Due to unintentional doping, pure-phase gallium oxide exhibits intrinsic n-type conductivity. Doping with elements such as Si, Sn, Zr, and Hf can effectively achieve bandgap heights up to 10²⁰ cm⁻¹ in gallium oxide epitaxial films. -3 Carrier concentration regulation. Currently, the methods and preparation routes for regulating highly insulating gallium oxide materials are relatively simple and scarce, which severely limits the application of insulating and semi-insulating gallium oxide thin films in the field of electronic devices.

[0003] Currently, existing technologies typically prepare insulating and semi-insulating gallium oxide thin films or substrates by introducing cation vacancy defect compensation, such as by introducing acceptor dopants like Fe or Mg into the system. Different semiconductor materials have significantly different types of doping elements and doping processes, resulting in varying effects on carrier concentration in the crystal. Different doping elements can also exist in different doping forms, such as interstitial and substitutional sites, within the same crystal. Therefore, controlling the insulating properties of gallium oxide through elemental doping requires considering various factors such as element ionic radius, dopant ion valence state, and impurity energy level depth, making the preparation process complex and costly. It is evident that the preparation and growth processes of insulating and semi-insulating gallium oxide materials are currently a major challenge in gallium oxide research, representing a significant bottleneck in the development of high-performance gallium oxide-based optoelectronic and power devices, severely restricting further optimization and improvement of gallium oxide device performance. Summary of the Invention

[0004] To address all or part of the above objectives, this application provides the following technical solutions:

[0005] One objective of this application is to provide a method for preparing gallium oxide thin films, comprising: depositing a gallium oxide thin film on a substrate using a gallium oxide target and pulsed laser deposition in the presence of ozone. By introducing ozone to create a peroxidation atmosphere, ionization and compensation effects are suppressed, thereby enabling the prepared gallium oxide thin film to possess good insulation properties.

[0006] In some embodiments, the method for preparing the gallium oxide thin film specifically includes: placing a pretreated substrate and a gallium oxide target into a deposition chamber, and then evacuating the deposition chamber to a vacuum level of 10. -5 Below Pa; the substrate is heated to 550-650°C, and a gas containing ozone is introduced into the deposition chamber. A gallium oxide thin film is then deposited on the substrate using pulsed laser deposition, followed by annealing of the gallium oxide thin film at 400-800°C.

[0007] In some embodiments, the method for preparing the gallium oxide thin film specifically includes setting the distance between the gallium oxide target and the substrate to 3-7 cm when depositing the gallium oxide thin film.

[0008] In some embodiments, the gallium oxide target is doped with donor impurities. Preferably, the donor impurities include, but are not limited to, Si, Sn, Zr, or Hf. Preferably, the doping concentration of the dopant element in the gallium oxide target is 0.1-2% molar fraction.

[0009] In some embodiments, the gas pressure in the deposition chamber is set to 1 mTorr to 40 mTorr during the deposition of the gallium oxide thin film. Within this deposition gas pressure range, the feather size of the pulsed laser deposition can be kept within a suitable range, thereby ensuring good crystallinity of the gallium oxide thin film.

[0010] In some embodiments, during the deposition of the gallium oxide thin film, the ozone-containing gas introduced into the deposition chamber comprises ozone and a carrier gas in a mass ratio of 0.1 to 0.2:1, wherein the carrier gas includes oxygen and / or an inert gas. If the proportion of ozone is low, the effect of suppressing ionization and generating a compensation effect cannot be achieved; if the proportion of ozone is high, the crystallinity of the gallium oxide single crystal thin film deteriorates.

[0011] Preferably, the carrier gas includes oxygen. More preferably, the ozone-containing gas comprises ozone and oxygen in a mass ratio of 0.1 to 0.2:1.

[0012] In some embodiments, the process conditions used in the pulsed laser deposition method include: a laser energy density of 1–2 mJ / cm². 2 The frequency is 1-10Hz, with 3000-20000 pulses; the pre-pulse is 50-200 pulses, with an interval of 30-180s and repeated 3-6 times, after which gallium oxide thin film is deposited.

[0013] In some embodiments, after the gallium oxide thin film is deposited, the gas pressure in the deposition chamber is maintained at 1 mTorr to 40 mTorr, and the temperature in the deposition chamber is reduced to 300-600°C at a rate of 5-20°C / min and held at that temperature for 0.5-2 hours to achieve annealing of the gallium oxide thin film.

[0014] In some embodiments, the method for preparing the gallium oxide thin film specifically includes: cleaning and drying the substrate, heating the substrate to 1000-1200°C at a rate of 5-10°C / min and holding it at that temperature for 1-2 hours to complete the annealing treatment of the substrate, and then cooling the substrate to room temperature at a rate of 5-10°C / min to achieve the pretreatment of the substrate.

[0015] In some embodiments, in the deposition chamber, the pretreated substrate is heated to 550-650°C at a rate of 5-20°C / min and held at that temperature for 0.5-1h, and then the gallium oxide thin film is deposited on the substrate using the pulsed laser deposition method.

[0016] The second objective of this application is to provide a gallium oxide thin film prepared by the above-described preparation method.

[0017] A third objective of this application is to provide the application of the aforementioned gallium oxide thin film in the fabrication of semiconductor devices. Preferably, the semiconductor device includes an electronic device or an optoelectronic device.

[0018] The fourth objective of this application is to provide an electrical modulation method for donor-doped gallium oxide materials, comprising: depositing a gallium oxide layer on a substrate in an ozone-containing environment using a gallium oxide target doped with donor impurities and a pulsed laser deposition method, thereby modulating the conductivity characteristics of the gallium oxide material.

[0019] In some embodiments, the electrical modulation method of the donor-doped gallium oxide material specifically includes: placing the pretreated substrate and the gallium oxide target into a deposition chamber, and then evacuating the deposition chamber to a vacuum level of 10. -5 Below Pa; the substrate is heated to 550-650°C, and a gas containing ozone is introduced into the deposition chamber. A gallium oxide layer is then deposited on the substrate using pulsed laser deposition, followed by annealing of the gallium oxide layer at 300-600°C.

[0020] In some embodiments, the electrical modulation method specifically includes setting the distance between the gallium oxide target and the substrate to 3-7 cm when depositing the gallium oxide layer.

[0021] In some embodiments, the donor impurity includes Si, Sn, Zr, or Hf. Preferably, the doping concentration of the dopant element in the gallium oxide target is 0.1-2% molar fraction.

[0022] In some embodiments, the gas pressure in the deposition chamber is set to 1 mTorr to 40 mTorr when depositing the gallium oxide layer.

[0023] In some embodiments, during the deposition of the gallium oxide layer, the ozone-containing gas introduced into the deposition chamber comprises ozone and a carrier gas in a mass ratio of 0.1 to 0.2:1, wherein the carrier gas includes oxygen and / or an inert gas.

[0024] Preferably, the carrier gas includes oxygen. More preferably, the ozone-containing gas comprises ozone and oxygen in a mass ratio of 0.1 to 0.2:1.

[0025] In some embodiments, the process conditions used in the pulsed laser deposition method include: a laser energy density of 1–2 mJ / cm². 2 The frequency is 1-10Hz, with 3000-20000 pulses; the pre-pulse is 50-200 pulses, with an interval of 30-180s and repeated 3-6 times, after which gallium oxide layer is deposited.

[0026] In some embodiments, after the gallium oxide layer is deposited, the gas pressure in the deposition chamber is maintained at 1 mTorr to 40 mTorr, and the temperature in the deposition chamber is cooled to 300-600°C at a rate of 5-20°C / min and held at that temperature for 0.5-2 hours to achieve annealing of the gallium oxide layer.

[0027] In some embodiments, the electrical modulation method specifically includes: cleaning and drying the substrate, heating the substrate to 1000-1200°C at a rate of 5-10°C / min and holding it at that temperature for 1-2 hours to complete the annealing treatment of the substrate, and then cooling the substrate to room temperature at a rate of 5-10°C / min to achieve the pretreatment of the substrate.

[0028] In some embodiments, the electrical modulation method specifically includes: heating the pretreated substrate to 550-650°C at a rate of 5-20°C / min and holding it at that temperature for 0.5-1h in the deposition chamber, and then depositing the gallium oxide layer on the substrate using the pulsed laser deposition method.

[0029] In some embodiments, the electrical modulation method further includes: at least by adjusting one or more of the concentration of ozone in the environment and the process conditions of the pulsed laser deposition method, to achieve controllable modulation of the gallium oxide material from conductive to insulating properties.

[0030] Compared with the prior art, this application has at least the following beneficial effects:

[0031] (1) This application introduces ozone in situ during the pulsed laser deposition of gallium oxide thin films, and generates ionization suppression and compensation effects by constructing a peroxidation atmosphere, thereby enabling the prepared gallium oxide thin films to have high electrical insulation properties, and in particular, realizes the transformation of N-type doped gallium oxide materials into high-insulation gallium oxide.

[0032] (2) Compared with the existing technology of achieving high insulation of gallium oxide thin films through element doping (e.g., Mg, Fe doping), the preparation method provided in this application is simple, easy to implement and economical, and has practicality and large-scale production prospects.

[0033] (3) The electrical modulation method provided in this application can regulate the electrical insulation of gallium oxide materials by adjusting the concentration of ozone in the environment or the process conditions of pulsed laser deposition. Attached Figure Description

[0034] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0035] Figure 1 These are the in-plane current-voltage curves of the Si-doped gallium oxide thin film prepared under ozone conditions in Example 1 of this application and the Si-doped gallium oxide thin film prepared under ozone-free conditions in Comparative Example 1.

[0036] Figure 2 These are the in-plane current-voltage curves of the Sn-doped gallium oxide thin film prepared under ozone conditions in Example 2 of this application and the Sn-doped gallium oxide thin film prepared under ozone-free conditions in Comparative Example 2.

[0037] Figure 3 These are the in-plane current-voltage curves of the Zr-doped gallium oxide thin film prepared under ozone conditions in Example 3 of this application and the Zr-doped gallium oxide thin film prepared under ozone-free conditions in Comparative Example 3.

[0038] Figure 4 These are the in-plane current-voltage curves of the Si-doped gallium oxide thin film prepared under ozone conditions in Example 4 of this application and the Si-doped gallium oxide thin film prepared under ozone-free conditions in Comparative Example 4.

[0039] Figure 5 These are the in-plane current-voltage curves of the Si-doped gallium oxide thin film prepared under ozone conditions in Example 5 of this application and the Si-doped gallium oxide thin film prepared under ozone-free conditions in Comparative Example 5. Detailed Implementation

[0040] The technical solutions of this application are described in detail below with reference to specific embodiments, so that those skilled in the art can better understand and implement the technical solutions of this application. Specific functional details disclosed herein should not be construed as limiting, but rather as the basis for the claims and as a representative basis for teaching those skilled in the art to employ the application differently in any appropriate detailed embodiment.

[0041] Example 1

[0042] (002) MgO substrate was selected, cleaned and dried with high-purity nitrogen, and then placed in a box furnace for annealing. The annealing temperature was 1000℃, the annealing time was 2 hours, the annealing atmosphere was air, and the heating rate and cooling rate were set to 10℃ / min.

[0043] The annealed substrate is fixed to the substrate holder and placed in the deposition chamber. A gallium oxide ceramic target with a Si doping concentration of 1% molar fraction is used, and the distance between the target and the substrate is adjusted to 5 cm.

[0044] Evacuate the deposition chamber to a vacuum level of 10. -5 Below Pa;

[0045] The substrate was heated to 600°C at a heating rate of 20°C / min and held at that temperature for 1800s.

[0046] A pulsed laser deposition (PLD) system was used, high-purity oxygen was introduced, and the gas pressure was controlled at 20 mTorr. An ozone generator was used to control the ozone ratio in the oxygen pipeline to be 10%.

[0047] Set laser energy density to 1 mJ / cm 2 The frequency is 5Hz, the pulse is 10,000 times, the pre-pulse is 100 times, the interval is 60s and the cycle is repeated 3 times before the epitaxial film begins;

[0048] After deposition, the cooling rate was set to 20℃ / min, and annealing was performed in the deposition chamber under the same oxygen pressure as during deposition. The gallium oxide film was then removed after cooling to below 100℃. The in-plane current-voltage curves of the prepared Si-doped gallium oxide film (with ozone) are shown below. Figure 1 As shown.

[0049] Example 2

[0050] (002) MgO substrate was selected, cleaned and dried with high-purity nitrogen, and then placed in a box furnace for annealing. The annealing temperature was 1000℃, the annealing time was 2 hours, the annealing atmosphere was air, and the heating rate and cooling rate were set to 10℃ / min.

[0051] The annealed substrate is fixed to the substrate holder and placed in the deposition chamber. A gallium oxide ceramic target with a Sn doping concentration of 1% molar fraction is used, and the distance between the target and the substrate is adjusted to 5 cm.

[0052] Evacuate the deposition chamber to a vacuum level of 10. -5 Below Pa;

[0053] The substrate was heated to 600°C at a heating rate of 20°C / min and held at that temperature for 1800s.

[0054] A pulsed laser deposition (PLD) system was used, high-purity oxygen was introduced, and the gas pressure was controlled at 20 mTorr. An ozone generator was used to control the ozone ratio in the oxygen pipeline to be 10%.

[0055] Set laser energy density to 1 mJ / cm 2 The frequency is 5Hz, the pulse is 10,000 times, the pre-pulse is 100 times, the interval is 60s and the cycle is repeated 3 times before the epitaxial film begins;

[0056] After deposition, the cooling rate was set to 20℃ / min, and annealing was performed in the deposition chamber under the same oxygen pressure as during deposition. The gallium oxide film was then removed after cooling to below 100℃. The in-plane current-voltage curves of the prepared Sn-doped gallium oxide film (with ozone) are shown below. Figure 2 As shown.

[0057] Example 3

[0058] (002) MgO substrate was selected, cleaned and dried with high-purity nitrogen, and then placed in a box furnace for annealing. The annealing temperature was 1000℃, the annealing time was 2 hours, the annealing atmosphere was air, and the heating rate and cooling rate were set to 10℃ / min.

[0059] The annealed substrate is fixed to the substrate holder and placed in the deposition chamber. A gallium oxide ceramic target with a Zr doping concentration of 1% molar fraction is used, and the distance between the target and the substrate is adjusted to 5 cm.

[0060] Evacuate the deposition chamber to a vacuum level of 10. -5 Below Pa;

[0061] The substrate was heated to 600°C at a heating rate of 20°C / min and held at that temperature for 1800s.

[0062] A pulsed laser deposition (PLD) system was used, high-purity oxygen was introduced, and the gas pressure was controlled at 20 mTorr. An ozone generator was used to control the ozone ratio in the oxygen pipeline to be 10%.

[0063] Set laser energy density to 1 mJ / cm 2The frequency is 5Hz, the pulse is 10,000 times, the pre-pulse is 100 times, the interval is 60s and the cycle is repeated 3 times before the epitaxial film begins;

[0064] After deposition, the cooling rate was set to 20℃ / min, and annealing was performed in the deposition chamber under the same oxygen pressure as during deposition. The gallium oxide film was then removed after cooling to below 100℃. The in-plane current-voltage curves of the prepared Zr-doped gallium oxide film (with ozone) are shown below. Figure 3 As shown.

[0065] Example 4

[0066] (002) MgO substrate was selected, cleaned and dried with high-purity nitrogen, and then placed in a box furnace for annealing. The annealing temperature was 1000℃, the annealing time was 2 hours, the annealing atmosphere was air, and the heating rate and cooling rate were set to 10℃ / min.

[0067] The annealed substrate is fixed to the substrate holder and placed in the deposition chamber. A gallium oxide ceramic target with a Si doping concentration of 1% molar fraction is used, and the distance between the target and the substrate is adjusted to 5 cm.

[0068] Evacuate the deposition chamber to a vacuum level of 10. -5 Below Pa;

[0069] The substrate was heated to 600°C at a heating rate of 20°C / min and held at that temperature for 1800s.

[0070] A pulsed laser deposition (PLD) system was used, high-purity oxygen was introduced, and the gas pressure was controlled at 20 mTorr. An ozone generator was used to control the ozone ratio in the oxygen pipeline to be 15%.

[0071] Set laser energy density to 1 mJ / cm 2 The frequency is 5Hz, the pulse is 10,000 times, the pre-pulse is 100 times, the interval is 60s and the cycle is repeated 3 times before the epitaxial film begins;

[0072] After deposition, the cooling rate was set to 20℃ / min, and annealing was performed in the deposition chamber under the same oxygen pressure as during deposition. The gallium oxide film was then removed after cooling to below 100℃. The in-plane current-voltage curves of the prepared Si-doped gallium oxide film (with ozone) are shown below. Figure 4 As shown.

[0073] Example 5

[0074] (002) MgO substrate was selected, cleaned and dried with high-purity nitrogen, and then placed in a box furnace for annealing. The annealing temperature was 1000℃, the annealing time was 2 hours, the annealing atmosphere was air, and the heating rate and cooling rate were set to 10℃ / min.

[0075] The annealed substrate is fixed to the substrate holder and placed in the deposition chamber. A gallium oxide ceramic target with a Si doping concentration of 1% molar fraction is used, and the distance between the target and the substrate is adjusted to 5 cm.

[0076] Evacuate the deposition chamber to a vacuum level of 10. -5 Below Pa;

[0077] The substrate was heated to 600°C at a heating rate of 20°C / min and held at that temperature for 1800s.

[0078] A pulsed laser deposition (PLD) system was used, high-purity oxygen was introduced, and the gas pressure was controlled at 20 mTorr. An ozone generator was used to control the ozone ratio in the oxygen pipeline to be 20%.

[0079] Set laser energy density to 1 mJ / cm 2 The frequency is 5Hz, the pulse is 10,000 times, the pre-pulse is 100 times, the interval is 60s and the cycle is repeated 3 times before the epitaxial film begins;

[0080] After deposition, the cooling rate was set to 20℃ / min, and annealing was performed in the deposition chamber under the same oxygen pressure as during deposition. The gallium oxide film was then removed after cooling to below 100℃. The in-plane current-voltage curves of the prepared Si-doped gallium oxide film (with ozone) are shown below. Figure 5 As shown.

[0081] Comparative Example 1

[0082] The only difference between this comparative example and Example 1 is that ozone is not introduced during pulsed laser deposition:

[0083] (002) MgO substrate was selected, cleaned and dried with high-purity nitrogen, and then placed in a box furnace for annealing. The annealing temperature was 1000℃, the annealing time was 2 hours, the annealing atmosphere was air, and the heating rate and cooling rate were set to 10℃ / min.

[0084] The annealed substrate is fixed to the substrate holder and placed in the deposition chamber. A gallium oxide ceramic target with a Si doping concentration of 1% molar fraction is used, and the distance between the target and the substrate is adjusted to 5 cm.

[0085] Evacuate the deposition chamber to a vacuum level of 10. -5 Below Pa;

[0086] The substrate was heated to 600°C at a heating rate of 20°C / min and held at that temperature for 1800s.

[0087] A pulsed laser deposition (PLD) system was used, with high-purity oxygen introduced and the gas pressure controlled at 20 mTorr;

[0088] Set laser energy density to 1 mJ / cm 2 The frequency is 5Hz, the pulse is 10,000 times, the pre-pulse is 100 times, the interval is 60s and the cycle is repeated 3 times before the epitaxial film begins;

[0089] After deposition, the cooling rate was set to 20℃ / min, and annealing was performed in the deposition chamber under the same oxygen pressure as during deposition. The gallium oxide film was then removed after cooling to below 100℃. The in-plane current-voltage curves of the prepared Si-doped gallium oxide film (ozone-free) are shown below. Figure 1 As shown.

[0090] Comparative Example 2

[0091] The only difference between this comparative example and Example 2 is that ozone is not introduced during pulsed laser deposition:

[0092] (002) MgO substrate was selected, cleaned and dried with high-purity nitrogen, and then placed in a box furnace for annealing. The annealing temperature was 1000℃, the annealing time was 2 hours, the annealing atmosphere was air, and the heating rate and cooling rate were set to 10℃ / min.

[0093] The annealed substrate is fixed to the substrate holder and placed in the deposition chamber. A gallium oxide ceramic target with a Sn doping concentration of 1% molar fraction is used, and the distance between the target and the substrate is adjusted to 5 cm.

[0094] Evacuate the deposition chamber to a vacuum level of 10. -5 Below Pa;

[0095] The substrate was heated to 600°C at a heating rate of 20°C / min and held at that temperature for 1800s.

[0096] A pulsed laser deposition (PLD) system was used, with high-purity oxygen introduced and the gas pressure controlled at 20 mTorr;

[0097] Set laser energy density to 1 mJ / cm 2 The frequency is 5Hz, the pulse is 10,000 times, the pre-pulse is 100 times, the interval is 60s and the cycle is repeated 3 times before the epitaxial film begins;

[0098] After deposition, the cooling rate was set to 20℃ / min, and annealing was performed in the deposition chamber under the same oxygen pressure as during deposition. The gallium oxide film was then removed after cooling to below 100℃. The in-plane current-voltage curves of the prepared Sn-doped gallium oxide film (ozone-free) are shown below. Figure 2 As shown.

[0099] Comparative Example 3

[0100] The only difference between this comparative example and Example 3 is that ozone is not introduced during pulsed laser deposition:

[0101] (002) MgO substrate was selected, cleaned and dried with high-purity nitrogen, and then placed in a box furnace for annealing. The annealing temperature was 1000℃, the annealing time was 2 hours, the annealing atmosphere was air, and the heating rate and cooling rate were set to 10℃ / min.

[0102] The annealed substrate is fixed to the substrate holder and placed in the deposition chamber. A gallium oxide ceramic target with a Zr doping concentration of 1% molar fraction is used, and the distance between the target and the substrate is adjusted to 5 cm.

[0103] Evacuate the deposition chamber to a vacuum level of 10. -5 Below Pa;

[0104] The substrate was heated to 600°C at a heating rate of 20°C / min and held at that temperature for 1800s.

[0105] A pulsed laser deposition (PLD) system was used, with high-purity oxygen introduced and the gas pressure controlled at 20 mTorr;

[0106] Set laser energy density to 1 mJ / cm 2 The frequency is 5Hz, the pulse is 10,000 times, the pre-pulse is 100 times, the interval is 60s and the cycle is repeated 3 times before the epitaxial film begins;

[0107] After deposition, the cooling rate was set to 20℃ / min, and annealing was performed in the deposition chamber under the same oxygen pressure as during deposition. The gallium oxide film was then removed after cooling to below 100℃. The in-plane current-voltage curves of the prepared Zr-doped gallium oxide film (ozone-free) are shown below. Figure 3 As shown.

[0108] Comparative Example 4

[0109] The only difference between Comparative Example 4 and Example 4 is that ozone was not introduced in Comparative Example 4; all other aspects are the same. The in-plane current-voltage curves of the prepared Si-doped gallium oxide thin film (ozone-free) are shown below. Figure 4 As shown.

[0110] The only difference between Comparative Example 5 and Example 5 is that ozone was not introduced in Comparative Example 5; all other aspects are the same. The in-plane current-voltage curves of the prepared Si-doped gallium oxide thin film (ozone-free) are shown below. Figure 5 As shown.

[0111] pass Figure 1-5It is evident that gallium oxide films prepared without ozone during the fabrication process exhibit significantly higher electrical insulation properties compared to gallium oxide films prepared by introducing ozone during pulsed laser deposition. This indicates that this application utilizes pulsed laser deposition technology to introduce ozone in situ during film deposition to create a peroxidation atmosphere, generating ionization suppression and compensation effects, thereby achieving high electrical insulation characteristics in donor-doped gallium oxide films. This application achieves a significant reduction in the conductivity of gallium oxide films and thus the fabrication of high-insulation gallium oxide films simply by introducing ozone into the film deposition atmosphere. Compared to existing methods for achieving insulation properties in gallium oxide films through Mg and Fe doping, this method is simpler, easier to implement, and more economical. Furthermore, it allows for controllable modulation of the film's properties from conductivity to insulation through process control in undoped or N-type doped films, demonstrating promising application prospects.

[0112] All aspects, embodiments, features, and examples of this application are to be regarded as illustrative in all respects and are not intended to limit the application; the scope of this application is defined only by the claims. Other embodiments, modifications, and uses will become apparent to those skilled in the art without departing from the spirit and scope of this application as claimed.

[0113] In addition, the inventors of this case also conducted experiments with other raw materials, process operations, and process conditions described in this specification, referring to the aforementioned embodiments, and obtained relatively ideal results in all cases.

[0114] Although this application has been described with reference to illustrative embodiments, those skilled in the art will understand that various other changes, omissions, and / or additions can be made without departing from the spirit and scope of this application, and that elements of the described embodiments can be substituted with substantially equivalents. Furthermore, many modifications can be made without departing from the scope of this application to adapt particular situations or materials to the teachings of this application. Therefore, this application is not intended to be limited to the specific embodiments disclosed for carrying out this application, but rather is intended to include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated otherwise, any use of the terms first, second, etc., does not indicate any order or importance, but is used to distinguish one element from another.

Claims

1. A method for preparing a gallium oxide thin film, characterized in that, include: In an environment where ozone is present, gallium oxide thin films are deposited on a substrate using a gallium oxide target and pulsed laser deposition.

2. The method for preparing gallium oxide thin films according to claim 1, characterized in that, Specifically, it includes: After placing the pretreated substrate and gallium oxide target into the deposition chamber, the deposition chamber is evacuated to a vacuum level of 10. -5 Below Pa; The substrate is heated to 550-650°C, and an ozone-containing gas is introduced into the deposition chamber. A gallium oxide thin film is then deposited on the substrate using pulsed laser deposition, followed by annealing of the gallium oxide thin film at 400-800°C.

3. The method for preparing gallium oxide thin films according to claim 1 or 2, characterized in that, When depositing the gallium oxide thin film, the distance between the gallium oxide target and the substrate is set to 3-7 cm.

4. The method for preparing gallium oxide thin films according to claim 1 or 2, characterized in that, When depositing the gallium oxide thin film, the gas pressure in the deposition chamber is set to 1 mTorr ~ 40 mTorr.

5. The method for preparing gallium oxide thin films according to claim 1 or 2, characterized in that, During the deposition of the gallium oxide thin film, the ozone-containing gas introduced into the deposition chamber comprises ozone and a carrier gas in a mass ratio of 0.1 to 0.2:1, wherein the carrier gas includes oxygen and / or an inert gas.

6. The method for preparing gallium oxide thin films according to claim 1 or 2, characterized in that, The process conditions used in the pulsed laser deposition method include: a laser energy density of 1~2 mJ / cm². 2 The frequency is 1-10Hz, with 3000-20000 pulses; the pre-pulse is 50-200 pulses, with an interval of 30-180s and repeated 2-6 times, after which gallium oxide thin film deposition is performed.

7. The method for preparing gallium oxide thin films according to claim 1 or 2, characterized in that, After the gallium oxide thin film is deposited, the gas pressure in the deposition chamber is maintained at 1 mTorr ~ 40 mTorr, and the temperature in the deposition chamber is reduced to 300-600°C at a rate of 5-20°C / min and held at that temperature for 0.5-2 hours to achieve the annealing treatment of the gallium oxide thin film.

8. The method for preparing gallium oxide thin films according to claim 1 or 2, characterized in that, The gallium oxide target is doped with donor impurities.

9. The method for preparing gallium oxide thin films according to claim 8, characterized in that, The donor impurities include Si, Sn, Zr, or Hf.

10. The method for preparing gallium oxide thin films according to claim 8, characterized in that, The doping concentration of donor impurities in the gallium oxide target is 0.1-2% molar fraction.

11. The method for preparing gallium oxide thin films according to claim 2, characterized in that, The preprocessing specifically includes: After cleaning and drying the substrate, the substrate is heated to 1000-1200℃ at a rate of 5-10℃ / min and held at that temperature for 1-2 hours to perform annealing treatment on the substrate. Then, the substrate is cooled to room temperature at a rate of 5-10℃ / min to achieve pretreatment of the substrate.

12. The method for preparing gallium oxide thin films according to claim 2, characterized in that, Specifically, it includes: In the deposition chamber, the pretreated substrate is heated to 550~650°C at a rate of 5-20°C / min and held at that temperature for 0.5-1h. Then, the gallium oxide thin film is deposited on the substrate using the pulsed laser deposition method.

13. The gallium oxide thin film prepared by the preparation method according to any one of claims 1-12.

14. The application of the gallium oxide thin film of claim 13 in the fabrication of semiconductor devices.

15. The application according to claim 14, characterized in that, The semiconductor device includes electronic devices or optoelectronic devices.

16. An electrical modulation method for a donor-doped gallium oxide material, characterized in that, include: In the presence of ozone, gallium oxide layers are deposited on a substrate using a gallium oxide target doped with donor impurities and pulsed laser deposition, thereby modulating the conductivity of gallium oxide materials.

17. The electrical modulation method according to claim 16, characterized in that, Specifically, it includes: After placing the pretreated substrate and the gallium oxide target into the deposition chamber, the deposition chamber is evacuated to a vacuum level of 10. -5 Below Pa; The substrate is heated to 550-650°C, and a gas containing ozone is introduced into the deposition chamber. A gallium oxide layer is then deposited on the substrate using pulsed laser deposition, followed by annealing of the gallium oxide layer at 400-800°C.

18. The electrical modulation method according to claim 16 or 17, characterized in that, The donor impurities include Si, Sn, Zr, or Hf.

19. The electrical modulation method according to claim 16 or 17, characterized in that, The doping concentration of donor impurities in the gallium oxide target is 0.1-2% molar fraction.

20. The electrical modulation method according to claim 16 or 17, characterized in that, When depositing the gallium oxide layer, the distance between the gallium oxide target and the substrate is set to 3-7 cm.

21. The electrical modulation method according to claim 16 or 17, characterized in that, When depositing the gallium oxide layer, the gas pressure in the deposition chamber is set to 1 mTorr ~ 40 mTorr.

22. The electrical modulation method according to claim 16 or 17, characterized in that, During the deposition of the gallium oxide layer, the ozone-containing gas introduced into the deposition chamber comprises ozone and a carrier gas in a mass ratio of 0.1 to 0.2:1, wherein the carrier gas includes oxygen and / or an inert gas.

23. The electrical modulation method according to claim 16 or 17, characterized in that, The process conditions used in the pulsed laser deposition method include: a laser energy density of 1~2 mJ / cm². 2 The frequency is 1-10Hz, with 3000-20000 pulses; the pre-pulse is 50-200 pulses, with an interval of 30-180s and repeated 3-6 times, after which gallium oxide layer is deposited.

24. The electrical modulation method according to claim 16 or 17, characterized in that, After the gallium oxide layer is deposited, the gas pressure in the deposition chamber is maintained at 1 mTorr ~ 40 mTorr, and the temperature in the deposition chamber is reduced to 300-600°C at a rate of 5-20°C / min and held at that temperature for 0.5-2 hours to achieve the annealing treatment of the gallium oxide layer.

25. The electrical modulation method according to claim 17, characterized in that, The pretreatment specifically includes: cleaning and drying the substrate, heating the substrate to 1000-1200°C at a rate of 5-10°C / min and holding it at that temperature for 1-2 hours to anneal the substrate, and then cooling the substrate to room temperature at a rate of 5-10°C / min to achieve the pretreatment of the substrate.

26. The electrical modulation method according to claim 17, characterized in that, Specifically, it includes: In the deposition chamber, the pretreated substrate is heated to 550~650°C at a rate of 5-20°C / min and held at that temperature for 0.5-1h. Then, the gallium oxide layer is deposited on the substrate using the pulsed laser deposition method.

27. The electrical modulation method according to claim 16, characterized in that, Also includes: The controllable modulation of the gallium oxide material's properties from conductive to insulating can be achieved by adjusting at least one or more of the ozone concentration in the environment and the process conditions of the pulsed laser deposition method.

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