Gallium oxide growth method and device capable of repairing oxygen vacancies

Abstract

The invention provides a gallium oxide growth method and device capable of repairing oxygen vacancies, and the method comprises the steps: spraying plasmas to a growth region of a gallium oxide crystal in the growth process of the gallium oxide crystal, and repairing the oxygen vacancies in the growth process of the gallium oxide crystal through the plasmas; wherein the plasma comprises oxygen atoms and oxygen ions.

Description

Technical Field

[0001] The present invention belongs to the field of gallium oxide preparation, and particularly relates to a method and device for growing gallium oxide capable of repairing oxygen vacancies. Background Art

[0002] Gallium oxide ( ) is a wide-bandgap semiconductor material with high breakdown electric field, excellent ultraviolet detection performance, and good high-temperature resistance characteristics, and has broad application prospects in the fields of high-power electronic devices, photodetectors, etc. However, in the process of traditional gallium oxide crystal growth, due to the generation of oxygen vacancies, it is easy to cause the decline of the electrical properties of the material, affecting the stability and reliability of the device. Oxygen vacancies not only introduce additional defect energy levels but also reduce the carrier mobility of the material, thereby affecting the performance and lifespan of the device.

[0003] The existing technology mainly relies on post-treatment methods (such as high-temperature annealing or oxygen atmosphere treatment) to reduce oxygen vacancies, but these methods usually have difficulty in synchronously repairing defects during the crystal growth process, resulting in a large number of oxygen vacancies still existing inside the material, affecting the final crystal quality. In addition, the post-treatment methods increase the production cost and process complexity and cannot completely eliminate the influence of oxygen vacancies.

[0004] Relevant scientific research institutions at home and abroad have carried out related research on the growth of gallium oxide using a variety of growth methods. For example, in Chinese Patent CN118308779A, a gallium oxide single crystal and its growth device and growth method are proposed. This patent realizes the growth of high-quality gallium oxide single crystals by optimizing the thermal field structure of the growth furnace. Specifically, this method effectively reduces the defects during the crystal growth process by precisely controlling the temperature distribution and growth rate inside the growth furnace, improving the electrical and optical properties of the crystal. In addition, Chinese Patent CN117552089A provides a monitoring system for growing gallium oxide single crystals by the guiding mode method. This system is electrically connected to an external computer through an infrared camera and a pressure sensor and can monitor the temperature distribution and crystal weight during the crystal growth process in real time. By analyzing and comparing these data by the computer, it can be judged whether the crystal growth meets the expected requirements and the growth parameters can be adjusted in time.

[0005] However, although these studies have improved the growth quality of gallium oxide crystals and the controllability of the growth process to a certain extent, they still cannot repair oxygen vacancy defects in real time during the crystal growth process. Oxygen vacancies are one of the common defects in the process of gallium oxide crystal growth, and their existence will lead to the decline of the electrical properties of the material, affecting the stability and reliability of the device. The existing technology mainly relies on post-treatment methods (such as high-temperature annealing or oxygen atmosphere treatment) to reduce oxygen vacancies, but these methods usually have difficulty in synchronously repairing defects during the crystal growth process, resulting in a large number of oxygen vacancies still existing inside the material, affecting the final crystal quality.

[0006] Therefore, there is an urgent need for a method and device that can repair oxygen vacancies in real time during the growth of gallium oxide crystals and improve the crystal quality. Summary of the Invention

[0007] The purpose of the present invention is to provide a method and device for growing gallium oxide that can repair oxygen vacancies, realizing the on-line repair of oxygen vacancies in gallium oxide crystals during the growth process of gallium oxide crystals, so as to obtain high-quality gallium oxide crystals.

[0008] On the one hand, a method for growing gallium oxide that can repair oxygen vacancies is provided, including: During the growth of gallium oxide crystals, plasma is sprayed towards the growth region of the gallium oxide crystals, and the oxygen vacancies during the growth of the gallium oxide crystals are repaired by the plasma; wherein, the plasma includes oxygen atoms and oxygen ions.

[0009] On the other hand, a device for growing gallium oxide that can repair oxygen vacancies is provided. The device for growing gallium oxide that can repair oxygen vacancies includes: An iridium crucible; A heating unit for heating the gallium oxide growth raw material in the iridium crucible; A lifting unit for growing gallium oxide crystals according to the growth raw material in the iridium crucible; An oxygen vacancy repair component for spraying plasma towards the growth region of the gallium oxide crystals and repairing the oxygen vacancies during the growth of the gallium oxide crystals by the plasma; wherein, the plasma includes oxygen atoms and oxygen ions.

[0010] Optionally, the oxygen vacancy repair component includes: A plasma generation unit and a plurality of nozzles arranged around the growth region of the gallium oxide crystals.

[0011] Optionally, the plasma generation unit generates plasma in a pulse mode.

[0012] Optionally, the duty cycle of the pulse mode is 20% - 50%.

[0013] Optionally, the radio frequency power of the plasma generation unit is 50 - 300W, the ion energy is 20 - 100eV, and the processing time is 5 - 30 minutes.

[0014] Optionally, the gas introduced into the plasma generation unit includes a mixed gas of oxygen, ozone, oxygen, and argon.

[0015] Optionally, the ratio of oxygen to argon is between 4:1 and 1:1.

[0016] Optionally, the heating unit includes: Annular heating coil and temperature control module; wherein, the annular heating coil is arranged around the side of the iridium crucible, and the temperature control module is used to control the heating power of the annular heating coil.

[0017] Optionally, the temperature of the gallium oxide crystal is 300 - 600 °C.

[0018] The unexpectedly technical effects achieved by the technical method provided by the present invention are: The present invention provides a method for growing gallium oxide with repairable oxygen vacancies. During the growth process of the gallium oxide crystal, plasma (plasma oxygen atoms and plasma oxygen ions) is sprayed into the growth region of the gallium oxide crystal to repair the oxygen vacancies. The oxygen atoms and oxygen ions generated by the plasma have higher activity than oxygen molecules (that is, compared with directly introducing oxygen, the oxygen atoms and oxygen ions generated by the plasma have higher activity), so the reaction energy of the plasma oxygen atoms and plasma oxygen ions will be higher. Secondly, the high-energy particles generated by the plasma hit the growing crystal. At the atomic level, they can automatically find the oxygen vacancies inside the crystal and fill the oxygen vacancies. The automatic repair of oxygen vacancies during the growth process of the gallium oxide crystal can be realized through the plasma, ensuring the quality of the grown crystal. Description of the Drawings

[0019] In order to more clearly illustrate the technical solutions in the present invention or the prior art, the following will briefly introduce the drawings required for use in the description of the embodiments or the prior art. Obviously, the drawings in the following description are some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0020] Figure 1 It is a flowchart of a method for growing gallium oxide with repairable oxygen vacancies provided by the present invention; Figure 2 It is a structural block diagram of a device for growing gallium oxide with repairable oxygen vacancies provided by the present invention; Figure 3 It is a structural block diagram of a device for growing gallium oxide with repairable oxygen vacancies provided by the present invention; Figure 4 It is a cross-sectional view of an oxygen vacancy repair component provided by the present invention.

[0021] The reference numerals are as follows: 1: housing; 11: support; 12: gallium oxide crystal; 2: iridium crucible; 3: heating unit; 31: annular heating coil; 32: temperature control unit; 4: lifting unit; 41: lifting member; 42: seed crystal rod; 5: Oxygen vacancy repair component; 51: Plasma generation unit; 52: Nozzle; 53: Gas supply pipeline. Detailed implementation manners

[0022] To make the objectives, technical solutions and advantages of the present invention clearer, the technical solutions in the present invention will be clearly and completely described below with reference to the accompanying drawings in the present invention. Apparently, the described embodiments are some but not all of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments in the present invention without creative efforts shall fall within the protection scope of the present invention.

[0023] Figure 1 It is a flowchart of a method for growing gallium oxide capable of repairing oxygen vacancies provided by the present invention. Refer to Figure 1 , including: S101. During the process of growing gallium oxide crystals, spray plasma towards the growth region of the gallium oxide crystals to repair the oxygen vacancies during the growth process of the gallium oxide crystals; wherein, the plasma includes oxygen atoms and oxygen ions.

[0024] The present invention provides a method for growing gallium oxide capable of repairing oxygen vacancies. During the growth process of gallium oxide crystals, oxygen vacancies are repaired by spraying plasma (plasma oxygen atoms and plasma cations) towards the growth region of the gallium oxide crystals. The oxygen atoms and oxygen ions generated by the plasma will have higher activities, higher than those of oxygen molecules, so the reaction energy of the plasma oxygen atoms and plasma oxygen ions will be more efficient. Secondly, the high-energy particles generated by the plasma hit the growing crystals. At the atomic level, the oxygen vacancies inside the crystals can be automatically found and filled. The oxygen vacancies during the growth process of gallium oxide crystals can be automatically repaired by the plasma, ensuring the quality of the grown crystals.

[0025] Refer to Figures 2 to 4 , Figure 2 and Figure 3 It is a structural block diagram of a device for growing gallium oxide capable of repairing oxygen vacancies provided by the present invention. Figure 4 It is a cross-sectional view of an oxygen vacancy repair component 5 provided by the present invention (along the Figure 2 dotted line A-A' in Iridium crucible 2; Heating unit 3, used to heat the gallium oxide growth raw material in the iridium crucible; Lifting unit 4, used to grow gallium oxide crystals according to the growth raw material in the iridium crucible; The oxygen vacancy repair component 5 is used to inject plasma towards the growth region of the gallium oxide crystal, and repair the oxygen vacancies during the growth of the gallium oxide crystal through the plasma; wherein, the plasma includes oxygen atoms and oxygen ions.

[0026] In this embodiment, the gallium oxide growth device capable of repairing oxygen vacancies further includes a housing 1 and a fixing member 11 disposed inside the housing 1.

[0027] In this embodiment, the heating unit 3 includes: An annular heating coil 31 and a temperature control module 32; wherein, the annular heating coil 31 is disposed around the side of the iridium crucible 2, and the temperature control module 32 is used to control the heating power of the annular heating coil 31.

[0028] In this embodiment, the heating unit adopts an annular heating coil arranged around the iridium crucible, the heating temperature can be continuously adjusted, the control range is 1600°C to 2200°C, and the heating power is dynamically adjusted through the temperature control module to maintain a stable molten state of gallium oxide.

[0029] In this embodiment, the lifting unit 4 includes a lifting member 41 and a seed crystal rod 42, and the gallium oxide crystal 12 is stretched and grown through the lifting member 41 and the seed crystal rod 42. The size, quality and structural stability of the gallium oxide crystal can be ensured by precisely controlling the crystal growth rate and direction. Among them, the growth rate can be controlled within the range of 0.1 mm / h to 10 mm / h, and it can adapt to the crystal growth requirements of different sizes and specifications.

[0030] In this embodiment, the oxygen vacancy repair component 5 includes: A plasma generation unit 51, a plurality of nozzles 52 disposed around the gallium oxide crystal growth region, and a gas supply pipeline 53 for supplying gas to the plasma generation unit 51.

[0031] In this embodiment, the plasma generation unit 51 generates plasma in a pulse mode. Among them, generating plasma in a pulse mode can eliminate the problem of temperature rise on the surface of the gallium oxide crystal easily caused by continuous bombardment.

[0032] In this embodiment, the duty cycle of the pulse mode is 20% - 50%. For example, the duty cycle of the pulse mode is 25%.

[0033] In this embodiment, the radio frequency power of the plasma generation unit is 50 - 300 W, the ion energy is 20 - 100 eV, and the processing time is 5 - 30 minutes.

[0034] Exemplarily, the radio frequency power of the plasma generation unit is 100 W, the ion energy is 50 eV, and the processing time is 10 minutes.

[0035] In this embodiment, the gases introduced into the plasma generation unit include a mixed gas of oxygen, ozone, oxygen, and argon.

[0036] In this embodiment, the ratio of oxygen to argon is between 4:1 and 1:1.

[0037] Exemplarily, the ratio of oxygen to argon is 2:1.

[0038] In this embodiment, the temperature of the gallium oxide crystal is 300 - 600 °C.

[0039] Exemplarily, the temperature of the gallium oxide crystal is 400 °C.

[0040] Example 1: Verification of Plasma In-situ Repair Function In an embodiment of the present invention, first, place the iridium crucible 2 on the heating unit 3, and add gallium oxide powder into the iridium crucible 2. The initial loading amount is 500 g. Turn on the heating unit 3, set the heating rate to 10 °C / min, heat to 1450 °C to melt the gallium oxide powder, and keep the temperature constant for 30 min to ensure that the gallium oxide is completely melted. After the gallium oxide is melted, start the lifting unit, set the growth rate of the gallium oxide crystal to 0.3 mm / h, and start growing the gallium oxide crystal.

[0041] During the crystal growth process, start the oxygen vacancy repair component. This component includes four plasma nozzles in different orientations, which can process the surface of the growing gallium oxide crystal from multiple angles. Set the power of the plasma nozzle to 100 W, the gas is a mixed gas of oxygen and argon, the ratio is 3:1, and the flow rate is 10 sccm. Inject high-energy plasma onto the surface of the gallium oxide crystal through the plasma nozzle to supplement oxygen atoms in real time and reduce the oxygen vacancies in the gallium oxide crystal.

[0042] The experimental results show that the plasma repair device of the present invention can effectively supplement oxygen atoms during the crystal growth process, reduce oxygen vacancies, and improve the optical and electrical properties of the crystal structure.

[0043] Example 2 In another embodiment of the present invention, first, place the iridium crucible in an electric heating device and add 600 g of gallium oxide powder. Set the heating rate of the heating unit to 15 °C / min, heat to 1450 °C, and keep this temperature for 40 min to ensure that the gallium oxide is fully melted. After the gallium oxide is melted, start the lifting unit and set the growth rate of the gallium oxide crystal to 0.6 mm / h respectively.

[0044] In each set of experiments, start the oxygen vacancy repair component, set the power of the plasma nozzle to 200 W, the gas to a mixture of oxygen and argon with a ratio of 2:1, and the gas flow rate to 12 sccm. Inject high-energy plasma onto the crystal surface through the plasma nozzle to repair oxygen vacancy defects in real time.

[0045] By comparing the results of the two sets of experiments, it is found that the plasma nozzle device can effectively repair oxygen vacancy defects at different growth rates and improve the crystal quality.

[0046] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some of the technical features; and these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for growing gallium oxide capable of repairing oxygen vacancies, characterized in that, Including: During the process of growing gallium oxide crystals, plasma is ejected towards the growth region of the gallium oxide crystals, and oxygen vacancies during the growth process of the gallium oxide crystals are repaired by the plasma; wherein, the plasma includes oxygen atoms and oxygen ions.

2. A gallium oxide growth device capable of repairing oxygen vacancies, characterized in that, A gallium oxide growth device capable of repairing oxygen vacancies includes: An iridium crucible; A heating unit for heating the gallium oxide growth raw material in the iridium crucible; A lifting unit for growing gallium oxide crystals according to the growth raw material in the iridium crucible; An oxygen vacancy repair component for ejecting plasma towards the growth region of the gallium oxide crystals to repair oxygen vacancies during the growth process of the gallium oxide crystals by the plasma; wherein, the plasma includes oxygen atoms and oxygen ions.

3. The method for growing gallium oxide with repairable oxygen vacancies according to claim 2, wherein, The oxygen vacancy repair component includes: A plasma generation unit and a plurality of nozzles arranged around the gallium oxide crystal growth region.

4. The gallium oxide growth device capable of repairing oxygen vacancies according to claim 2, wherein, The plasma generation unit generates plasma in a pulse mode.

5. The gallium oxide growth device capable of repairing oxygen vacancies according to claim 4, characterized in that, The duty ratio of the pulse mode is 20% - 50%.

6. The gallium oxide growth device capable of repairing oxygen vacancies according to claim 2, characterized in that, The radio frequency power of the plasma generation unit is 50 - 300 W, the ion energy is 20 - 100 eV, and the processing time is 5 - 30 minutes.

7. The gallium oxide growth device capable of repairing oxygen vacancies according to claim 2, characterized in that, The gas introduced into the plasma generation unit includes a mixed gas of oxygen, ozone, oxygen, and argon.

8. The gallium oxide growth device capable of repairing oxygen vacancies according to claim 2, characterized in that, The ratio of oxygen to argon is between 4:1 and 1:

1.

9. The method for growing gallium oxide with repairable oxygen vacancies according to any one of claims 2 to 8, characterized in that, The heating unit includes: An annular heating coil and a temperature control module; wherein, the annular heating coil is arranged around the side of the iridium crucible, and the temperature control module is used to control the heating power of the annular heating coil.

10. The gallium oxide growth device capable of repairing oxygen vacancies according to any one of claims 2 to 8, characterized in that, The temperature of the gallium oxide crystal is 300 - 600 °C.

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