Gallium oxide material and preparation method and preparation equipment thereof

Abstract

The invention belongs to the field of semiconductor materials, and discloses a gallium oxide material and a preparation method and preparation equipment thereof, gallium oxide particles are spherical or sphere-like, the particle size is 30-200nm, and the purity is 4N-5N. The narrow particle size interval and the uniform morphology of the gallium oxide material provided by the invention can meet the strict requirements of semiconductor device manufacturing on powder particle size uniformity, the coating thickness consistency and the ion transmission stability are effectively guaranteed, the device performance fluctuation is reduced, and the high-precision application suitability is improved; and meanwhile, the spherical morphology and narrow particle size distribution can improve the powder fluidity, so that dispersion in processing links such as slurry preparation and thin film deposition is more uniform, agglomeration and caking are reduced, the process control difficulty is reduced, the production efficiency is improved, and the defective rate is reduced.

Description

Technical Field

[0001] This invention belongs to the field of semiconductor materials, and relates to a gallium oxide material, specifically a gallium oxide material and its preparation method and preparation equipment. Background Technology

[0002] Gallium oxide (GaO), as a promising next-generation ultrawide bandgap semiconductor material, owes its core advantage to its ultrawide bandgap of approximately 4.9 eV. This endows the material with extremely high breakdown electric field strength, laying the foundation for the fabrication of high-voltage, low-conduction-loss, high-efficiency power devices. Its theoretical performance is significantly superior to that of currently widely used silicon, silicon carbide, and gallium nitride (GaN) materials. Furthermore, this material can be grown into single crystals using a low-cost melt method, providing favorable conditions for large-scale mass production. In addition, its excellent physicochemical stability and deep-ultraviolet light response characteristics make it a promising candidate for applications in next-generation power electronics, deep-ultraviolet detection, and extreme environment applications.

[0003] Patent CN120157172A discloses a method for preparing gallium oxide nanomaterials. This method uses gallium nitrate as the gallium source and combines hydrothermal treatment with high-temperature calcination to synthesize gallium oxide materials with excellent crystal quality and uniform phase formation. The technical path involves synthesizing GaOOH powder by adding different concentrations of the anionic surfactant sodium dodecylbenzenesulfonate (SDBS) solution, followed by high-temperature calcination at 900℃ to finally obtain β-Ga2O3 materials of different sizes. However, this process has significant particle size control defects: during the hydrothermal reaction stage, the concentration of SDBS in the solution is prone to local unevenness, leading to differences in the growth rate of the precursor GaOOH particles, and the initial particle size distribution already shows a tendency to broaden; during the subsequent 900℃ high-temperature calcination process, the precursor particles are prone to agglomeration or local over-sintering, further exacerbating the particle size differences.

[0004] Wide particle size distribution of gallium oxide (GaO) particles can lead to a series of application-level problems: First, it significantly reduces application adaptability. Semiconductor device manufacturing has stringent requirements for the uniformity of GaO powder particle size. Uniform particle size is necessary to ensure consistent coating thickness and ion transport stability. However, a wide particle size distribution can cause device performance fluctuations (such as unstable breakdown voltage), making it difficult to meet the needs of high-precision applications. Second, it results in poor process compatibility. In subsequent processing steps such as slurry preparation and thin film deposition, excessive particle size differences can lead to poor powder flowability, uneven dispersion, and easy agglomeration. This not only increases the difficulty of controlling the production process but also reduces production efficiency and increases the product defect rate. Summary of the Invention

[0005] In view of the defects and deficiencies of the existing technology, the present invention provides, in a first aspect, a gallium oxide material; in a second aspect, a method for preparing gallium oxide material; and in a third aspect, an apparatus for preparing gallium oxide.

[0006] In a first aspect, the present invention provides a gallium oxide material, wherein the gallium oxide particles are spherical or near-spherical in shape, the particle size is 30~200nm, and the purity is 4N~5N.

[0007] Secondly, the present invention provides a method for preparing the above-mentioned gallium oxide material, comprising the following steps: Step 1: Heat metallic gallium to obtain gallium vapor; Step 2: Gallium vapor is introduced into an oxygen-containing atmosphere for cooling, and the resulting solid particles are gallium oxide.

[0008] Preferably, in step 1, the purity of gallium is ≥99.99%.

[0009] Preferably, in step 1, the gallium metal is heated in an electric arc furnace; the heating electrode of the electric arc furnace is a graphite electrode; the current of the heating electrode is 240~260A; the voltage of the heating electrode is 100~150V; and the distance between the heating electrode and the gallium metal is 10~20mm.

[0010] Preferably, in step 2, the molar ratio of gallium vapor to oxygen entering the reaction system is 1:3 to 5.

[0011] Preferably, in step 2, gallium vapor is introduced into an oxygen-containing atmosphere at 100~200°C for cooling.

[0012] Preferably, the oxygen-containing atmosphere can be any one or more of air and oxygen.

[0013] Thirdly, the present invention provides a system for preparing the above-mentioned gallium oxide material, including an electric arc furnace, a settling chamber, and a fan. The electric arc furnace is provided with heating electrodes, and the settling chamber is provided with a cooling device. The electric arc furnace and the settling chamber are connected by a transmission pipe. The fan is disposed in the transmission pipe, with the air inlet of the fan facing the electric arc furnace and the air outlet of the fan facing the settling chamber. The settling chamber is provided with an air inlet pipe for conveying oxygen.

[0014] Preferably, the cooling device includes a circulating cooling pipe wound around the settling chamber.

[0015] Compared with the prior art, one or more technical solutions provided by the present invention have one of the following beneficial effects: (1) The narrow particle size range and uniform morphology of the gallium oxide material provided by the present invention can meet the stringent requirements of powder particle size uniformity in semiconductor device manufacturing, effectively ensure the consistency of coating thickness and ion transport stability, reduce device performance fluctuations, and improve the adaptability of high-precision applications; at the same time, the spherical morphology and narrow particle size distribution can improve powder flowability, make the slurry preparation, thin film deposition and other processing links more uniformly dispersed, reduce agglomeration and clumping, reduce the difficulty of process control, improve production efficiency and reduce the defect rate.

[0016] (2) This invention employs a dry synthesis method, first vaporizing metallic gallium, and then allowing the gallium vapor to settle in an oxygen-containing atmosphere to obtain spherical, nanoscale gallium oxide particles. The resulting gallium oxide particles have a narrow size distribution and high purity, which is beneficial for subsequent film fabrication processes. Furthermore, this method has simple process steps and low production costs, which is conducive to industrialization and marketization. Attached Figure Description

[0017] Figure 1 A schematic diagram of the gallium oxide preparation system provided in Example 1; Figure 2 The image shows the XRD pattern of the gallium oxide material prepared in Example 2. Figure 3 This is a SEM image of the gallium oxide material prepared in Example 2.

[0018] Reference numerals: 1. Electric arc furnace; 2. Transmission pipeline; 3. Settling chamber; 4. Cooling device. Detailed Implementation

[0019] The present invention provides the following specific technical solutions.

[0020] In a first aspect, the present invention provides a nano-spherical gallium oxide material, wherein the gallium oxide particles are spherical or near-spherical in shape, the particle size is 30~200nm, and the purity is 4N~5N.

[0021] Through research, the inventors discovered that the narrow particle size range and uniform morphology of the gallium oxide material provided by this invention can meet the stringent requirements for powder particle size uniformity in semiconductor device manufacturing, effectively ensuring coating thickness consistency and ion transport stability, suppressing performance fluctuations such as device breakdown voltage, and significantly improving the material's adaptability and device performance reliability in high-precision applications. On the other hand, the spherical or near-spherical morphology combined with the narrow particle size distribution can greatly improve powder flowability, making it easier to disperse evenly in subsequent processing steps such as slurry preparation and thin film deposition, reducing agglomeration and clumping, lowering the difficulty of production process control, improving production efficiency, reducing product defect rate, and optimizing process compatibility.

[0022] Secondly, the present invention provides a method for preparing gallium oxide material, comprising the following steps: Step 1: Heat metallic gallium to obtain gallium vapor; Step 2: Gallium vapor is introduced into an oxygen-containing atmosphere for cooling, and the resulting solid particles are gallium oxide.

[0023] Through research, the inventors discovered that the gallium oxide material preparation method provided by this invention involves heating metallic gallium to obtain gallium vapor, and then cooling the gallium vapor in an oxygen-containing atmosphere to directly generate gallium oxide particles. This method has simple process steps, does not require the use of complex precursors, and does not require cumbersome post-processing steps. It can reduce the introduction of impurities from the source and ensure high purity of the product. At the same time, by adjusting the heating, cooling, and atmosphere parameters, the particle morphology and particle size distribution can be precisely controlled, and spherical or near-spherical gallium oxide with a narrow distribution of 30~200nm particle size can be stably obtained. It has the advantages of process controllability, production efficiency, and material quality.

[0024] Preferably, in step 1, the purity of gallium is ≥99.99%.

[0025] Preferably, in step 1, the gallium metal is heated in an electric arc furnace; the heating electrode of the electric arc furnace is a graphite electrode; the current of the heating electrode is 240~260A; the voltage of the heating electrode is 100~150V; and the distance between the heating electrode and the gallium metal is 10~20mm.

[0026] Through research, the inventors discovered that electric arc furnaces can rapidly achieve high-temperature heating, efficiently vaporizing metallic gallium into stable and controllable gallium vapor, providing a sufficient and stable concentration of gaseous precursor for subsequent vapor oxidation nucleation growth. At the same time, the heating power and temperature field distribution of the electric arc furnace can be precisely controlled, facilitating precise control of the gallium vaporization rate and vapor concentration, laying the foundation for subsequent control of the particle size, morphology, and particle size distribution of gallium oxide particles. Furthermore, the electric arc furnace has high high-temperature heating efficiency and fast thermal response, which helps to improve the overall preparation efficiency and adapt to the needs of large-scale production.

[0027] By controlling the heating parameters of the electric arc furnace (current and voltage of the heating electrodes), the gasification rate and concentration of gallium vapor can be precisely controlled, providing stable gaseous precursor conditions for subsequent oxidation nucleation growth, and ultimately achieving precise control over the particle size, morphology and particle size distribution of gallium oxide particles.

[0028] Preferably, in step 2, the molar ratio of gallium vapor to oxygen entering the reaction system is 1:3 to 5.

[0029] Through research, the inventors discovered that controlling the molar ratio of gallium vapor to oxygen at 1:3 to 5 ensures that oxygen is in excess, allowing the gallium vapor to be fully oxidized during cooling and completely converted into gallium oxide. This reduces the formation of unreacted metallic gallium and low-valence gallium oxide impurities, which is beneficial for improving the purity and crystal quality of gallium oxide products. At the same time, it can make the nucleation and growth of gallium oxide particles more uniform, improving the morphology and dispersibility of the products.

[0030] Preferably, in step 2, gallium vapor is introduced into an oxygen-containing atmosphere at 100~200°C for cooling.

[0031] Through research, the inventors discovered that controlling the cooling temperature between 100 and 200°C can ensure that gallium vapor and oxygen react fully to generate gallium oxide particles, avoiding incomplete crystallization or particle agglomeration due to excessively high temperatures. It can also prevent excessively low temperatures from causing rapid condensation, impurity adsorption, or uneven morphology, thus facilitating the production of gallium oxide materials with high crystallinity, uniform particle size, and excellent purity.

[0032] Thirdly, the present invention provides the above-mentioned gallium oxide preparation system, including an electric arc furnace, a settling chamber, and a blower. The electric arc furnace is provided with heating electrodes, and the settling chamber is provided with a cooling device. The electric arc furnace and the settling chamber are connected by a transmission pipe. The blower is disposed in the transmission pipe, with the air inlet of the blower facing the electric arc furnace and the air outlet of the blower facing the settling chamber. The settling chamber is provided with an air inlet pipe for conveying oxygen.

[0033] Preferably, the cooling device includes a circulating cooling pipe wound around the settling chamber.

[0034] To make the technical problems, technical solutions and technical advantages of the present invention clearer, a detailed description will be given below with reference to specific examples. However, the scope of protection of the present invention is not limited to the following specific embodiments.

[0035] Unless otherwise defined, all technical terms used herein have the same meaning as commonly understood by those skilled in the art. The technical terms used herein are for the purpose of describing particular embodiments only and are not intended to limit the scope of the invention.

[0036] Unless otherwise specified, all raw materials, reagents, instruments and equipment used in this invention can be purchased from the market or prepared by existing methods.

[0037] Example 1: A gallium oxide preparation system includes an electric arc furnace 1, a settling chamber 3, and a blower. The electric arc furnace 1 is equipped with heating electrodes, and the settling chamber 3 is equipped with a cooling device 4. The electric arc furnace 1 and the settling chamber 3 are connected by a transmission pipe 2. The blower is installed in the transmission pipe 2, with the air inlet of the blower facing the electric arc furnace 1 and the air outlet of the blower facing the settling chamber 3.

[0038] The cooling device 4 includes a circulating cooling pipe that is wound around the settling chamber 3, and the settling chamber 3 is provided with an air inlet pipe for supplying oxygen (not shown in the figure).

[0039] The use of an electric arc furnace 1 for heating can instantly generate a high-temperature heat source, with rapid heating and high energy density, which can quickly heat gallium raw materials to the vaporization temperature, meeting the process requirements for the gas phase preparation of gallium oxide. At the same time, the electric arc heating area is concentrated and the temperature can be easily and precisely controlled by the heating electrodes, which helps to reduce the introduction of impurities and improve the purity of gallium oxide products. With the help of a fan and transmission pipeline 2, continuous production of high-temperature gasification of raw materials, airflow transportation and subsequent cooling and sedimentation can be realized. The overall structure is simple, the heating is stable and reliable, and it is suitable for the industrial preparation of high-purity gallium oxide.

[0040] The working process of the gallium oxide preparation system described above is as follows: When the equipment is running, the heating electrodes in the electric arc furnace 1 generate a high-temperature electric arc, which heats and vaporizes the metallic gallium in the furnace to form gallium vapor. The fan forms a directional airflow in the transmission pipe 2, which transports the gallium vapor in the electric arc furnace 1 to the settling chamber 3. At the same time, oxygen is introduced into the settling chamber 3 through the air inlet pipe. The circulating cooling pipe wrapped around the outside of the settling chamber 3 achieves cooling through circulating heat exchange, so that the gallium vapor completes the cooling and oxidation reaction in the settling chamber 3 to generate gallium oxide solid particles, thereby realizing the continuous preparation and collection of gallium oxide.

[0041] Example 2: A method for preparing gallium oxide, using the preparation system provided in Example 1, includes the following steps: Step 1: Place the gallium metal in a crucible, then place the crucible in an electric arc furnace, start the electric arc furnace to heat the gallium metal, so that the gallium metal vaporizes into gallium vapor, control the current of the heating electrode to be 250A, the voltage to be 130V, and the distance between the heating electrode and the gallium metal to be 15mm. Step 2: Turn on the cooling device to maintain the temperature in the settling chamber at 150°C; then turn on the fan to deliver gallium vapor into the settling chamber, and at the same time introduce air into the settling chamber, controlling the molar ratio of gallium vapor to oxygen to be 1:4. The solid particles that settle at the bottom of the settling chamber are gallium oxide materials.

[0042] Figure 2 The image shows the XRD pattern of the gallium oxide material prepared in Example 2. Figure 2 It can be seen that the XRD spectrum of the gallium oxide material prepared in Example 2 shows sharp and high-intensity characteristic diffraction peaks with no obvious impurity peaks, indicating that the product has high crystallinity and excellent purity. The positions of all characteristic peaks are highly consistent with the standard PDF card (PDF#43-1012) of β-Ga2O3, confirming that the product is pure phase gallium oxide without the introduction of other impurity phases.

[0043] Figure 3 Here is a SEM image of the gallium oxide material prepared in Example 2. Figure 3As can be seen from the SEM images of the gallium oxide material folded in Example 2, it mainly exhibits a spherical or near-spherical morphology, with particle sizes distributed in the range of 100~300nm. The overall particle size is relatively uniform, with no obvious agglomeration or clumping, showing good dispersibility.

[0044] Example 3: A method for preparing gallium oxide, using the preparation system provided in Example 1, includes the following steps: Step 1: Place the gallium metal in a crucible, then place the crucible in an electric arc furnace, start the electric arc furnace to heat the gallium metal, so that the gallium metal vaporizes into gallium vapor, control the current of the heating electrode to be 240A, the voltage to be 100V, and the distance between the heating electrode and the gallium metal to be 10mm. Step 2: Turn on the cooling device to maintain the temperature in the settling chamber at 100°C; then turn on the fan to deliver gallium vapor into the settling chamber, and at the same time introduce air into the settling chamber, controlling the molar ratio of gallium vapor to oxygen to be 1:3. The solid particles that settle at the bottom of the settling chamber are gallium oxide materials.

[0045] Example 4: A method for preparing gallium oxide, using the preparation system provided in Example 1, includes the following steps: Step 1: Place the gallium metal in a crucible, then place the crucible in an electric arc furnace, start the electric arc furnace to heat the gallium metal, so that the gallium metal vaporizes into gallium vapor. Control the current of the heating electrode to be 260A, the voltage to be 150V, and the distance between the heating electrode and the gallium metal to be 20mm. Step 2: Turn on the cooling device to maintain the temperature in the settling chamber at 200°C; then turn on the fan to deliver gallium vapor into the settling chamber, and at the same time introduce air into the settling chamber, controlling the molar ratio of gallium vapor to oxygen to be 1:5. The solid particles that settle at the bottom of the settling chamber are gallium oxide materials.

[0046] Comparative Example 1: A method for preparing gallium oxide differs from Example 2 in that, in step 1, metallic gallium is placed in a crucible, and then the crucible is placed in an electric arc furnace. The electric arc furnace is started to heat the metallic gallium, and the current of the heating electrode is controlled to be 200A, the voltage to be 80V, and the distance between the heating electrode and the metallic gallium is 10mm.

[0047] Comparative Example 2: A method for preparing gallium oxide differs from Example 2 in that, in step 1, metallic gallium is placed in a crucible, and then the crucible is placed in an electric arc furnace. The electric arc furnace is started to heat the metallic gallium, and the current of the heating electrode is controlled to be 280A, the voltage to be 180V, and the distance between the heating electrode and the metallic gallium is 10mm.

[0048] Comparative Example 3: A method for preparing gallium oxide differs from Example 2 in that, in step 2, a cooling device is turned on to control the temperature in the settling chamber to be maintained at 80°C; then a fan is turned on to transport gallium vapor to the settling chamber, while air is introduced into the settling chamber at the same time, and the molar ratio of gallium vapor to oxygen is controlled to be 1:4. The solid particles that settle at the bottom of the settling chamber are gallium oxide materials.

[0049] Comparative Example 4: A method for preparing gallium oxide differs from Example 2 in that, in step 2, a cooling device is turned on to control the temperature in the settling chamber to be maintained at 220°C; then a fan is turned on to transport gallium vapor to the settling chamber, while air is introduced into the settling chamber at the same time, and the molar ratio of gallium vapor to oxygen is controlled to be 1:4. The solid particles that settle at the bottom of the settling chamber are gallium oxide materials.

[0050] The purity and particle size distribution of gallium oxide prepared in Examples 2-4 and Comparative Examples 1-4 were tested. The test data are shown in Table 1.

[0051] Table 1. Properties of gallium oxide prepared in Examples 2-4 and Comparative Examples 1-4 As shown in Table 1, under the preferred process parameters of this invention, the gallium oxide obtained in Examples 2-4 has a purity of 5N, a particle size distribution controlled within the range of 30-200nm, and uniform morphology with good dispersibility. In Comparative Example 1, the heating power was insufficient, resulting in incomplete vaporization and reaction, with a purity of only 4N, small particle size, and uneven distribution, with most particles smaller than 30nm. In Comparative Example 2, the heating power was too high, easily generating impurities and introducing impurities, reducing the purity to 3N, with excessive particle growth and severe agglomeration, and particle size mostly greater than 200nm. In Comparative Example 3, the cooling temperature was too low, resulting in insufficient oxidation reaction, with a purity of only 4N, small particles with uneven morphology, and a size usually less than 30nm. In Comparative Example 4, the cooling temperature was too high, easily causing particle agglomeration and sintering, reducing the purity to 3N, with large particle size and wide distribution, mostly greater than 200nm.

[0052] The above-described embodiments are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the technical scope of the present invention, based on the technical solution and concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A gallium oxide material, characterized in that, The gallium oxide particles are spherical or near-spherical in shape, with a particle size of 30~200nm and a purity of 4N~5N.

2. The method for preparing gallium oxide material as described in claim 1, characterized in that, Includes the following steps: Step 1: Heat metallic gallium to obtain gallium vapor; Step 2: Gallium vapor is introduced into an oxygen-containing atmosphere for cooling, and the resulting solid particles are gallium oxide.

3. The method for preparing gallium oxide material as described in claim 2, characterized in that, In step 1, the purity of gallium metal is ≥99.99%.

4. The method for preparing gallium oxide material as described in claim 2, characterized in that, In step 1, metallic gallium is heated in an electric arc furnace; the heating electrode of the electric arc furnace is a graphite electrode; the current of the heating electrode is 240~260A; the voltage of the heating electrode is 100~150V; and the distance between the heating electrode and the metallic gallium is 10~20mm.

5. The method for preparing gallium oxide material as described in claim 2, characterized in that, In step 2, the molar ratio of gallium vapor to oxygen entering the reaction system is 1:3~5.

6. The method for preparing gallium oxide material as described in claim 2, characterized in that, In step 2, gallium vapor is introduced into an oxygen-containing atmosphere at 100~200℃ for cooling.

7. The method for preparing gallium oxide material according to claim 2, characterized in that, The oxygen-containing atmosphere can be any one or both of air and oxygen.

8. The gallium oxide material preparation system as described in claim 1, characterized in that, The device includes an electric arc furnace (1), a settling chamber (3), and a blower. The electric arc furnace (1) is equipped with heating electrodes, and the settling chamber (3) is equipped with a cooling device (4). The electric arc furnace (1) and the settling chamber (3) are connected by a transmission pipe (2). The blower is located in the transmission pipe (2). The air inlet of the blower faces the electric arc furnace (1), and the air outlet of the blower faces the settling chamber (3). The settling chamber (3) is equipped with an air inlet pipe for transporting oxygen.

9. The gallium oxide material preparation system as described in claim 8, characterized in that, The cooling device (4) includes a circulating cooling pipe that is wound around the settling chamber (3).

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