Uniform high-quality multi-component semiconductor film mist chemical vapor deposition device

Abstract

The invention discloses a uniform high-quality multi-component semiconductor film mist chemical vapor deposition device which comprises an atomization device, a reaction cavity, a heating device, a porous double-layer structure conveying device, a motion sealing device, a substrate clamping device and a tail gas treatment device. The porous double-layer structure conveying device is used for conveying reaction raw materials of all components and comprises an outer-layer conveying channel, an outer-layer conveying hole ring belt, an inner-layer conveying channel, an inner-layer conveying hole ring belt and an inner-layer flow guide column. The motion sealing device comprises a lifting support and a motor. According to the porous double-layer structure transport device designed by the invention, the uniform thickness of the film is realized, the uniform distribution of radial components is realized, and the problems that the radial components of the multi-component semiconductor film are not uniformly distributed and the uniformity of the thickness is poor due to the defects of a conventional buffer structure are solved.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of semiconductor thin film growth, and particularly relates to a mist chemical vapor deposition device for growing uniform high-quality multi-component semiconductor thin films. BACKGROUND

[0002] Power electronics technology is an important cornerstone for improving people's quality of life, and its application covers fields such as information, new energy, aerospace, and power transmission. In order to support the development of new generation information, new energy vehicles, aerospace, large ships, high-speed rail, ultra-high voltage, and power transmission industries, the discovery and research of ultra-wide bandgap semiconductor materials have emerged as the times require. Among them, gallium oxide material has excellent application prospects in the fields of power devices and deep ultraviolet optoelectronic devices due to its large bandgap (4.9-5.5 eV), high breakdown field (8 MV / cm), large Baliga figure of merit (3400), and high stability.

[0003] At present, metastable phase gallium oxide thin films can only be prepared by heteroepitaxy. The gallium oxide thin films obtained directly by epitaxy method generally have high resistance due to low impurity content, and the thin films need to have certain conductivity in device preparation, so it is inevitable to develop multi-component gallium oxide semiconductor thin films.

[0004] Conventional multi-component semiconductor thin films can be prepared by in-situ growth method. However, during in-situ growth, due to the structure of the equipment and process reasons, there is a problem of uneven distribution of each component in the radial direction in the thin film. Among them, the mist chemical vapor deposition (Mist-CVD) equipment can realize in-situ growth of multi-component semiconductor thin films. The equipment generally uses a buffer structure to mix other component sources and gallium sources, and then transports them to the reaction chamber for thin film growth. However, in the existing mist chemical vapor deposition equipment, the defects of the conventional buffer structure lead to uneven radial component distribution and poor thickness uniformity of the grown multi-component semiconductor thin films. Therefore, it is necessary to develop a mist chemical vapor deposition device to realize uniform and high-quality production of multi-component semiconductor thin films. SUMMARY

[0005] In view of the deficiencies of the prior art, the present application provides a mist chemical vapor deposition device for growing uniform high-quality multi-component semiconductor thin films.

[0006] The technical solution for solving the technical problem of the present application is to provide a mist chemical vapor deposition device for growing uniform high-quality multi-component semiconductor thin films, which comprises an atomization device, a reaction chamber, a heating device, a porous double-layer structure transport device, a motion sealing device, a substrate clamping device, and an exhaust treatment device. A porous, double-layered transport device is used to transport various components of the reaction raw materials. It includes an outer transport channel, an outer transport hole ring, an inner transport channel, an inner transport hole ring, and an inner guide column. The moving sealing device includes a lifting support and a motor. The outer wall of the outer transport channel is detachably fixed to the inner wall of the reaction chamber; the outer ring of the outer transport hole ring is fixed to the inner wall of the outer transport channel; the outer wall of the inner transport channel is fixed to the inner ring of the outer transport hole ring; the outer ring of the inner transport hole ring is fixed to the inner wall of the inner transport channel; one end of the inner guide column is fixed to the inner ring of the inner transport hole ring; the outer transport hole ring has an outer transport ring hole; the inner transport hole ring has an inner transport ring hole. The outlets of the two atomizing devices are connected to the inlet ends of the outer and inner transport channels, respectively. The atomizing devices are used to atomize the reaction materials and transport the atomized reaction materials to the porous double-layer transport device via a carrier gas. The reaction chamber is completely sealed, with one end open for the substrate clamping device to pass through and the other end open for the extension of the outer and inner transport channels. The reaction chamber provides a uniform, high-quality growth environment for multi-component semiconductor films. The outlet of the reaction chamber is connected to a tail gas treatment device, which is used to treat reaction waste. A heating device is located outside the reaction chamber to provide the temperature conditions required for the growth of uniform, high-quality multi-component semiconductor films. The lifting bracket is installed outside the reaction chamber; the motor housing is fixed on the lifting bracket, and the motor moves up and down with the lifting bracket; the substrate clamping device passes through one end opening of the reaction chamber and extends into the interior of the reaction chamber; the beginning of the substrate clamping device is fixed on the output end of the motor, and the end is located in the outer transport channel, facing the outer transport hole ring and the inner transport hole ring, for receiving the atomized reaction raw materials transported by the carrier gas; the lifting bracket drives the substrate clamping device to move up and down, and the motor drives the substrate clamping device to rotate.

[0007] Compared with the prior art, the beneficial effects of the present invention are as follows: (1) The present invention can realize the epitaxial growth of large-size (two inches and above), uniformly doped and uniformly thick semiconductor thin films of various crystal forms, and the components of the prepared multi-component semiconductor epitaxial thin film are uniformly distributed radially on the surface of the film.

[0008] (2) The porous double-layer structure transport device designed in this invention achieves uniform film thickness with a thickness standard deviation of only 30nm, and achieves uniform radial component distribution, thus solving the problems of uneven radial component distribution and poor thickness uniformity of multi-component semiconductor films caused by defects in conventional buffer structures.

[0009] (3) The present invention can achieve the growth of semiconductor thin films of different thicknesses by changing the growth time, achieve the growth of semiconductor thin films of different crystal types by changing the growth temperature, and achieve the growth of homoepitaxial and heteroepitaxial thin films by using different substrates respectively.

[0010] (4) The present invention can be used to epitaxially grow various uniform multicomponent oxide semiconductor thin films, such as gallium oxide, zinc oxide, aluminum oxide, etc. Attached Figure Description

[0011] Figure 1 This is a longitudinal sectional vertical schematic diagram of the overall structure of the present invention; Figure 2 This is a horizontal longitudinal cross-sectional schematic diagram of the overall structure of the present invention; Figure 3 This is a vertical longitudinal sectional view of the porous double-layer structure conveying device of the present invention; Figure 4 This is a cross-sectional schematic diagram of the porous double-layer structure conveying device of the present invention; Figure 5 This is an EDS characterization result diagram of the sample prepared in Example 1 of the present invention; Figure 6 The image shows the XRD characterization results of the sample prepared in Example 1 of this invention. Figure 7 The image shows the AFM characterization results of the sample prepared in Example 1 of this invention.

[0012] In the figure, 1 is the atomizing device, 2 is the reaction chamber, 3 is the heating device, 4 is the porous double-layer structure transport device, 5 is the moving sealing device, 6 is the substrate clamping device, and 7 is the exhaust gas treatment device. Atomizing can 1-1, atomizing can air inlet pipe 1-2, atomizing can air outlet pipe 1-3; cavity air outlet pipe 2-1; Outer transport channel 4-1, outer transport hole ring 4-2, inner transport channel 4-3, inner transport hole ring 4-4, inner guide column 4-5, lower outer buffer zone 4-6, upper outer buffer zone 4-7, lower inner buffer zone 4-8, upper inner buffer zone 4-9, outer transport ring hole 4-10, inner transport ring hole 4-11, lower outer buffer zone air inlet pipe 4-12, lower inner buffer zone air inlet pipe 4-13; 5-1 Lifting bracket, 5-2 Motor, 6-1 Substrate lifting rod, 6-2 Tray, 7-1 Exhaust gas inlet pipe, 7-2 Processing module, 7-3 Exhaust gas outlet pipe. Detailed Implementation

[0013] Specific embodiments of the present invention are given below. These specific embodiments are only used to further illustrate the present invention in detail and do not limit the scope of protection of the present invention.

[0014] The present invention provides a uniform and high-quality multi-component semiconductor thin film fog chemical vapor deposition apparatus (hereinafter referred to as the apparatus), which includes a fogging device 1, a reaction chamber 2, a heating device 3, a porous double-layer structure transport device 4, a moving sealing device 5, a substrate clamping device 6, and an exhaust gas treatment device 7. The porous double-layer structure conveying device 4 is used to convey the reaction raw materials of each component, including an outer conveying channel 4-1, an outer conveying hole ring 4-2, an inner conveying channel 4-3, an inner conveying hole ring 4-4, and an inner guide column 4-5; the moving sealing device 5 includes a lifting bracket 5-1 and a motor 5-2; The outer wall of the outer transport channel 4-1 is detachably fixed to the inner wall of the reaction chamber 2 via a sealing flange; the outer ring of the outer transport hole ring 4-2 is welded and fixed to the inner wall of the outer transport channel 4-1; the outer wall of the inner transport channel 4-3 is welded and fixed to the inner ring of the outer transport hole ring 4-2; the outer ring of the inner transport hole ring 4-4 ​​is welded and fixed to the inner wall of the inner transport channel 4-3; one end of the inner guide column 4-5 is welded and fixed to the inner ring of the inner transport hole ring 4-4; the outer transport hole ring 4-2 has an outer transport ring hole 4-10; the inner transport hole ring 4-4 ​​has an inner transport ring hole 4-11. The outlets of the two atomizing devices 1 are connected to the inlet of the outer transport channel 4-1 and the inlet of the inner transport channel 4-3, respectively. The atomizing devices 1 are used to atomize the reaction raw materials and transport the atomized reaction raw materials (i.e., reaction raw material mist) to the porous double-layer structure transport device 4 via a carrier gas. The reaction chamber 2 is completely sealed, with one end open for the substrate clamping device 6 to pass through and the other end open for the outer transport channel 4-1 and the inner transport channel 4-3 to extend out. The reaction chamber 2 is used to provide a uniform and high-quality multi-component semiconductor film growth environment. The outlet of the reaction chamber 2 is connected to the exhaust gas treatment device 7. The exhaust gas treatment device 7 is used to treat reaction waste. The heating device 3 is located on the outside of the reaction chamber 2 and is used to provide the temperature conditions required for the growth of uniform and high-quality multi-component semiconductor films. The lifting bracket 5-1 is installed outside the reaction chamber 2; the housing of the motor 5-2 is fixed on the lifting bracket 5-1, and the motor 5-2 moves up and down with the lifting bracket 5-1; the substrate clamping device 6 passes through one end opening of the reaction chamber 2 and extends into the interior of the reaction chamber 2; the beginning end of the substrate clamping device 6 is fixed on the output end of the motor 5-2, and the end end is located in the outer transport channel 4-1, facing the outer transport hole ring 4-2 and the inner transport hole ring 4-4, and is used to receive the atomized reaction raw materials transported by the carrier gas; the lifting bracket 5-1 drives the substrate clamping device 6 to move up and down, and the motor 5-2 drives the substrate clamping device 6 to rotate.

[0015] Preferably, the outer transport channel 4-1 and the inner transport channel 4-3 are hollow cylindrical buffer areas with a length of 100~800mm.

[0016] Preferably, according to the flow direction of the gas phase, the outer transport channel 4-1 is composed of an outer lower buffer region air inlet pipe 4-12, a narrower hollow columnar outer lower buffer region 4-6, and a wider hollow columnar outer upper buffer region 4-7 connected in sequence; the outer lower buffer region 4-6 and the outer upper buffer region 4-7 form a gradually thickening structure; the outer lower buffer region air inlet pipe 4-12 is connected to the air outlet of an atomizing device 1.

[0017] Preferably, the inner diameter of the lower outer buffer area 4-6 is 10~300mm, the length is 60~600mm, and the cross-sectional shape is circular, elliptical, or rectangular; the inner diameter of the upper outer buffer area 4-7 is 200~600mm, the length is 40~200mm, and the cross-sectional shape is circular, elliptical, or rectangular.

[0018] Preferably, according to the flow direction of the gas phase, the inner transport channel 4-3 is composed of an inner lower buffer region air inlet pipe 4-13, a narrower hollow columnar inner lower buffer region 4-8, and a wider hollow columnar inner upper buffer region 4-9 connected in sequence; the inner lower buffer region 4-8 and the inner upper buffer region 4-9 form a gradually thickening structure; the inner lower buffer region air inlet pipe 4-13 is connected to the air outlet of another atomizing device 1.

[0019] Preferably, the inner diameter of the lower inner buffer area 4-8 is 5~150mm, the length is 60~600mm, and the cross-sectional shape is circular, elliptical, or rectangular; the inner diameter of the upper inner buffer area 4-9 is 100~300mm, the length is 40~200mm, and the cross-sectional shape is circular, elliptical, or rectangular.

[0020] Preferably, the inner guide column 4-5 is a columnar structure; the inner guide column 4-5 is preferably located on the central axis of the porous double-layer structure transport device 4; the inner guide column 4-5 is used to reduce the formation of large-scale eddies in the buffer area (i.e., the lower inner buffer area 4-8 and the upper inner buffer area 4-9) of the inner transport channel 4-3, which helps the gas to pass through each inner transport ring hole 4-11 at an approximately uniform flow rate when it is ejected through the inner buffer, and then be obliquely sprayed onto the substrate surface. At the same time, the outer wall of the inner transport channel 4-3 has the same effect on the buffer area (i.e., the lower outer buffer area 4-6 and the upper outer buffer area 4-7) formed by the outer transport channel 4-1, so the gas flow rate distribution of the inner and outer layers is uniform, which is more conducive to the full mixing of the inner and outer gas on the substrate surface.

[0021] Preferably, the outer transport hole ring 4-2 and the inner transport hole ring 4-4 ​​are porous columnar structures so that the atomized reaction raw materials can reach the substrate surface on the tray 6-2 for epitaxial growth under the transport of the carrier gas through the porous double-layer structure transport device 4; Preferably, the outer transport ring holes 4-10 are arrayed on the outer transport ring 4-2, and the array arrangement is a close hexagonal arrangement or a rectangular array; the diameter of the outer transport ring holes 4-10 is 1~30mm, and the number is 2~1000; the outer transport ring holes 4-10 are inclined towards the normal to the surface of the outer transport ring 4-2 (i.e., the central axis of the outer transport ring 4-2), and the angle between them and the normal to the surface of the outer transport ring 4-2 is 30~70° (preferably, the angle of each outer transport ring hole 4-10 can be different), so that the reaction raw material mist reaches the substrate surface at a certain angle.

[0022] Preferably, the inner transport ring holes 4-11 are arrayed on the inner transport ring 4-4, and the array arrangement is a close hexagonal arrangement or a rectangular array; the diameter of the inner transport ring holes 4-11 is 1~30mm, and the number is 2~1000; the inner transport ring holes 4-11 are inclined in the direction away from the normal of the surface of the inner transport ring 4-4 ​​(i.e., the central axis of the inner transport ring 4-4), and the angle between them and the normal of the surface of the inner transport ring 4-4 ​​is 110~150° (preferably, the angle of each inner transport ring hole 4-11 can be different), so that the reaction raw material mist reaches the substrate surface at a certain angle.

[0023] The outer transport ring with holes 4-10 is inclined inward and the inner transport ring with holes 4-11 is inclined outward. This relative arrangement facilitates the thorough mixing of the reaction raw material mist.

[0024] Preferably, the two atomizing devices 1 have the same structure, each including an atomizing tank 1-1, an atomizing tank inlet pipe 1-2, and an atomizing tank outlet pipe 1-3; one end of the atomizing tank inlet pipe 1-2 is used for the entry of carrier gas, and the other end is connected to the inlet end of the atomizing tank 1-1; the atomizing tank 1-1 is used to hold the reaction raw materials and atomize the reaction raw materials; one end of the atomizing tank outlet pipe 1-3 is connected to the outlet end of the atomizing tank 1-1, and the other end is connected to the inlet pipe 4-12 of the outer lower buffer area or the inlet pipe 4-13 of the inner lower buffer area.

[0025] Preferably, the atomizing device 1 employs high-pressure airless atomization, gas atomization, ultrasonic atomization, or electrostatic atomization.

[0026] Preferably, according to the flow direction of the gas phase, the gas outlet of the reaction chamber 2 is located behind the tray 6-2 of the substrate clamping device 6; the gas outlet of the reaction chamber 2 is provided with a cavity gas outlet pipe 2-1 for connecting with the exhaust gas inlet pipe 7-1 of the exhaust gas treatment device 7.

[0027] Preferably, the reaction chamber 2 can be arranged horizontally, vertically, or at any angle, and the temperature environment provided by the reaction chamber 2 is -196~1800℃, and the vacuum degree is 1×10⁻⁶. -4 Pa ~ 2 atmospheres of pressure. Preferably, the reaction chamber 2 can provide an environment such as electron irradiation and neutron irradiation, and can provide physical fields such as electric fields and magnetic fields.

[0028] Preferably, the porous double-layer structure conveying device 4 is made of a high-temperature resistant material, preferably quartz, graphite, stainless steel or high-temperature alloy.

[0029] Preferably, the substrate clamping device 6 includes a substrate lifting rod 6-1 and a tray 6-2; the substrate lifting rod 6-1 passes through one end opening of the reaction chamber 2 and extends into the interior of the reaction chamber 2; the beginning end of the substrate lifting rod 6-1 is fixedly connected to the output end of the motor 5-2; the tray 6-2 is fixed to the end of the substrate lifting rod 6-1; the tray 6-2 is located in the outer transport channel 4-1, facing the outer transport hole ring 4-2 and the inner transport hole ring 4-4, and is used to receive the atomized reaction raw materials transported by the carrier gas; the receiving distance is adjusted by adjusting the distance between the outer transport hole ring 4-2, the inner transport hole ring 4-4 ​​and the tray 6-2.

[0030] Preferably, the exhaust gas treatment device 7 includes an exhaust gas inlet pipe 7-1, a treatment module 7-2, and an exhaust gas outlet pipe 7-3; one end of the exhaust gas inlet pipe 7-1 is connected to the outlet end of the reaction chamber 2, and the other end is connected to the inlet end of the treatment module 7-2; the treatment module 7-2 is used to treat reaction byproducts and unreacted raw materials; the outlet end of the treatment module 7-2 is connected to one end of the exhaust gas outlet pipe 7-3; the other end of the exhaust gas outlet pipe 7-3 is connected to the atmospheric environment for discharging exhaust gas.

[0031] Preferably, the outer transport hole ring 4-2, the inner transport hole ring 4-4 ​​are at the same distance from the end of the substrate clamping device 6; the distance between the end of the substrate clamping device 6 (i.e., the tray 6-2) and the outer transport hole ring 4-2 is less than 5 cm; the rotation speed of the tray 6-2 is 1~10 rpm, and the diameter of the receiving surface of the tray 6-2 is 10~200 mm.

[0032] Example 1: This embodiment involves epitaxially growing a two-inch Sn / Al co-doped α-Ga2O3 thin film on a sapphire substrate. The specific steps are as follows: (1) Substrate cleaning: Place the substrate into an ultrasonic cleaner containing cleaning solution and ultrasonically clean for 30 seconds at a frequency of 40kHz and a temperature of 50℃; then remove the substrate and use nitrogen to blow dry the residual cleaning solution on the substrate surface; the substrate is a sapphire substrate. (2) The device is placed vertically. Select a suitable quartz tray 6-2 according to the substrate size, clamp the substrate horizontally on the tray 6-2, and then place it in the reaction chamber 2. (3) Adjust and fix the position of the substrate clamping device 6 by lifting bracket 5-1 so that the outer transport hole ring 4-2 and the inner transport hole ring 4-4 ​​are located 3cm directly below the substrate, the upper ends of the outer transport hole ring 4-2 and the inner transport hole ring 4-4 ​​are parallel to the substrate, the angle between the outer transport ring hole 4-10 and the normal of the surface of the outer transport ring ring 4-2 is 40°, and the angle between the inner transport ring hole 4-11 and the normal of the surface of the inner transport ring ring 4-4 ​​is 140°, so that the reaction raw material mist is obliquely sprayed onto the substrate surface; (4) Preparation of reaction raw materials: Dissolve 18.5g of gallium acetylacetonate powder in 2L of deionized water to prepare a gallium source solution of 0.025mol / L; dissolve 16.3g of aluminum acetylacetonate powder in 2L of deionized water to prepare an aluminum source solution of 0.025mol / L; dissolve 5.64g of stannous chloride dihydrate powder in 1L of deionized water to prepare a tin source solution of 0.025mol / L. (5) Atomization of reaction raw materials: The aluminum source solution and the tin source solution are placed in one atomization device 1, and the gallium source solution is placed in another atomization device 1; (6) Growth of Sn-doped α-Ga2O3 epitaxial layer: Use carrier gas to purge the residual gas in reaction chamber 2; Temperature setting and preheating of reaction chamber 2: The temperature of reaction chamber 2 is set to 550℃ and preheated for 10 minutes by heating device 3. Turn on the atomizing device 1 and atomize it into uniform droplets by ultrasonic atomization at a frequency of 3MHz. The reaction material is atomized into uniform droplets. The atomized reaction material is transported to the outer transport channel 4-1 and the inner transport channel 4-3 by carrier gas and then enters the porous double-layer structure transport device 4. Turn on the carrier gas, which can be nitrogen, argon or air, with a total flow rate of 4000 sccm. The carrier gas flow rate of the atomizing tank 1-1 for gallium source solution is 3000 sccm, and the carrier gas flow rate of the atomizing tank 1-1 for aluminum and tin source solutions is 1000 sccm. Spray onto the substrate, with the tray 6-2 rotating at 5 rpm. Maintain the growth temperature in reaction chamber 2 and begin growing gallium oxide film. The growth time, i.e., the spraying time, is set to 30 min. (7) After the gallium oxide thin film growth is completed, the atomizing device 1 and the carrier gas are turned off and kept warm for 3 minutes. Then the carrier gas is turned on and continuously introduced to empty the residual reactants and by-products in the reaction chamber 2 and slowly cool down to room temperature. The sample is taken out and then the motor 5-2 is turned off and the tray 6-2 stops rotating. During the entire thin film growth process, the exhaust gas after the reaction enters the processing module 7-2 from the chamber outlet pipe 2-1 through the exhaust gas inlet pipe 7-1. After the exhaust gas is processed, it is discharged to the atmospheric environment through the exhaust gas outlet pipe 7-3.

[0033] Depend on Figure 5 It can be seen that the components of the prepared two-inch sample are evenly distributed.

[0034] Depend on Figure 6 It can be seen that the prepared two-inch sample has high crystal quality.

[0035] Depend on Figure 7 It can be seen that the prepared two-inch sample has a flat, high-quality surface.

[0036] Example 2: This embodiment involves epitaxially growing a four-inch Sn / Al-doped α-Ga2O3 thin film on a sapphire substrate. The specific steps are as follows: (1) Substrate cleaning: Place the substrate into an ultrasonic cleaner containing cleaning solution and ultrasonically clean for 1 minute at a frequency of 40 kHz and a temperature of 50 ℃; then remove the substrate and use nitrogen to blow dry the residual cleaning solution on the substrate surface; the substrate is a sapphire substrate. (2) The device is placed vertically. Select a suitable quartz tray 6-2 according to the substrate size, clamp the substrate horizontally on the tray 6-2, and then place it in the reaction chamber 2. (3) Adjust and fix the position of the substrate clamping device 6 by lifting bracket 5-1 so that the outer transport hole ring 4-2 and the inner transport hole ring 4-4 ​​are located 2cm directly below the substrate, the upper ends of the outer transport hole ring 4-2 and the inner transport hole ring 4-4 ​​are parallel to the substrate, the angle between the outer transport ring hole 4-10 and the normal of the surface of the outer transport ring ring 4-2 is 45°, and the angle between the inner transport ring hole 4-11 and the normal of the surface of the inner transport ring ring 4-4 ​​is 135°, so that the reaction raw material mist is obliquely sprayed onto the substrate surface; (4) Preparation of reaction raw materials: Dissolve 18.5g of gallium acetylacetonate powder in 2L of deionized water to prepare a gallium source solution of 0.025mol / L; dissolve 16.3g of aluminum acetylacetonate powder in 2L of deionized water to prepare an aluminum source solution of 0.025mol / L; dissolve 5.64g of stannous chloride dihydrate powder in 1L of deionized water to prepare a tin source solution of 0.025mol / L. (5) Atomization of reaction raw materials: The aluminum source solution and the tin source solution are placed in one atomization device 1, and the gallium source solution is placed in another atomization device 1; (6) Growth of Sn-doped α-Ga2O3 epitaxial layer: Use carrier gas to purge the residual gas in reaction chamber 2; Temperature setting and preheating of reaction chamber 2: The temperature of reaction chamber 2 is set to 550℃ and preheated for 10 minutes by heating device 3. Turn on the atomizing device 1 and atomize it into uniform droplets by ultrasonic atomization at a frequency of 3MHz. The reaction material is atomized into uniform droplets. The atomized reaction material is transported to the outer transport channel 4-1 and the inner transport channel 4-3 by carrier gas and then enters the porous double-layer structure transport device 4. Turn on the carrier gas, which can be nitrogen, argon or air, with a total flow rate of 8000 sccm. The carrier gas flow rate of the atomizing tank 1-1 for gallium source solution is 6000 sccm, and the carrier gas flow rate of the atomizing tank 1-1 for aluminum and tin source solutions is 2000 sccm. Spray onto the substrate, with the tray 6-2 rotating at 5 rpm. Maintain the growth temperature in reaction chamber 2 and begin growing gallium oxide film. The growth time, i.e., the spraying time, is set to 30 min. (7) After the gallium oxide thin film growth is completed, the atomizing device 1 and the carrier gas are turned off and kept warm for 3 minutes. Then the carrier gas is turned on and continuously introduced to empty the residual reactants and by-products in the reaction chamber 2 and slowly cool down to room temperature. The sample is taken out and then the motor 5-2 is turned off and the tray 6-2 stops rotating. During the entire thin film growth process, the exhaust gas after the reaction enters the processing module 7-2 from the chamber outlet pipe 2-1 through the exhaust gas inlet pipe 7-1. After the exhaust gas is processed, it is discharged to the atmospheric environment through the exhaust gas outlet pipe 7-3.

[0037] In Examples 1 and 2, the raw materials for the gallium source solution can also be gallium bromide, gallium sulfate, or gallium hydroxide.

[0038] Any aspects not covered in this invention are applicable to existing technologies.

Claims

1. A uniform high quality multi-component semiconductor thin film mist chemical vapor deposition apparatus, characterized by, The device comprises atomization devices (1), a reaction cavity (2), a heating device (3), a porous double-layer structure transport device (4), a motion sealing device (5), a substrate clamping device (6), and a tail gas treatment device (7); The porous double-layer structure transport device (4) is used for realizing the transport of the reaction raw materials of various components, and comprises an outer transport channel (4-1), an outer transport hole ring belt (4-2), an inner transport channel (4-3), an inner transport hole ring belt (4-4), and an inner flow guide column (4-5); the motion sealing device (5) comprises a lifting support (5-1) and a motor (5-2); The outer wall of the outer transport channel (4-1) is detachably fixed to the inner wall of the reaction cavity (2); the outer ring of the outer transport hole ring belt (4-2) is fixed to the inner wall of the outer transport channel (4-1); the outer wall of the inner transport channel (4-3) is fixed to the inner ring of the outer transport hole ring belt (4-2); the outer ring of the inner transport hole ring belt (4-4) is fixed to the inner wall of the inner transport channel (4-3); one end of the inner flow guide column (4-5) is fixed to the inner ring of the inner transport hole ring belt (4-4); the outer transport ring belt hole (4-10) is formed in the outer transport hole ring belt (4-2); the inner transport ring belt hole (4-11) is formed in the inner transport hole ring belt (4-4); The gas outlet ends of the two atomization devices (1) are respectively communicated with the gas inlet ends of the outer transport channel (4-1) and the inner transport channel (4-3); the atomization device (1) is used for atomizing the reaction raw materials and transporting the atomized reaction raw materials to the porous double-layer structure transport device (4) through the carrier gas; the reaction cavity (2) is integrally sealed, one end is opened for the substrate clamping device (6) to pass through, and the other end is opened for the outer transport channel (4-1) and the inner transport channel (4-3) to extend out; the reaction cavity (2) is used for providing a growth environment for a uniform and high-quality multi-component semiconductor thin film; the gas outlet end of the reaction cavity (2) is communicated with the tail gas treatment device (7); the tail gas treatment device (7) is used for realizing the treatment of reaction waste; the heating device (3) is arranged outside the reaction cavity (2) and is used for providing a temperature condition required for the growth of a uniform and high-quality multi-component semiconductor thin film; The lifting support (5-1) is installed outside the reaction cavity (2); the shell of the motor (5-2) is fixed to the lifting support (5-1), and the motor (5-2) is lifted along with the lifting support (5-1); one end of the substrate clamping device (6) passes through the opening of the reaction cavity (2) and extends into the inside of the reaction cavity (2); the initial end of the substrate clamping device (6) is fixed to the output end of the motor (5-2), and the terminal end is located in the outer transport channel (4-1) and faces the outer transport hole ring belt (4-2) and the inner transport hole ring belt (4-4), and is used for receiving the atomized reaction raw materials transported through the carrier gas; the lifting support (5-1) drives the substrate clamping device (6) to realize lifting, and the motor (5-2) drives the substrate clamping device (6) to realize rotation.

2. The uniform high-quality multi-component semiconductor thin film mist chemical vapor deposition apparatus according to claim 1, wherein The outer layer transport channel (4-1) is composed of the outer layer lower part buffer area gas inlet pipe (4-12), the outer layer lower part buffer area (4-6) and the outer layer upper part buffer area (4-7) connected in sequence in the flow direction of the gas phase; the outer layer lower part buffer area (4-6) and the outer layer upper part buffer area (4-7) form a gradually thickening structure; the outer layer lower part buffer area gas inlet pipe (4-12) is in communication with the gas outlet end of one atomizing device (1); The inner diameter of the outer layer lower part buffer area (4-6) is 10-300 mm, the length is 60-600 mm, and the cross-sectional shape is circular, oval or rectangular; the inner diameter of the outer layer upper part buffer area (4-7) is 200-600 mm, the length is 40-200 mm, and the cross-sectional shape is circular, oval or rectangular.

3. The uniform high-quality multi-component semiconductor thin film mist-chemical vapor deposition apparatus according to claim 1, wherein The inner layer transport channel (4-3) is composed of the inner layer lower part buffer area gas inlet pipe (4-13), the inner layer lower part buffer area (4-8) and the inner layer upper part buffer area (4-9) connected in sequence in the flow direction of the gas phase; the inner layer lower part buffer area (4-8) and the inner layer upper part buffer area (4-9) form a gradually thickening structure; the inner layer lower part buffer area gas inlet pipe (4-13) is in communication with the gas outlet end of another atomizing device (1); The inner diameter of the inner layer lower part buffer area (4-8) is 5-150 mm, the length is 60-600 mm, and the cross-sectional shape is circular, oval or rectangular; the inner diameter of the inner layer upper part buffer area (4-9) is 100-300 mm, the length is 40-200 mm, and the cross-sectional shape is circular, oval or rectangular.

4. The uniform high-quality multi-component semiconductor thin film mist-chemical vapor deposition apparatus according to claim 1, wherein The inner layer flow guide column (4-5) is in a columnar structure; the inner layer flow guide column (4-5) is located on the central axis of the multi-hole double-layer structure transport device (4).

5. The uniform high-quality multi-component semiconductor thin film mist-chemical vapor deposition apparatus according to claim 1, wherein The outer layer transport ring belt holes (4-10) are arranged in an array on the outer layer transport hole ring belt (4-2), and the array arrangement form is close hexagonal arrangement or rectangular array; the diameter of the outer layer transport ring belt holes (4-10) is 1-30 mm, and the number is 2-1000; the outer layer transport ring belt holes (4-10) are inclined to the direction away from the normal line of the surface of the outer layer transport hole ring belt (4-2), and the included angle with the normal line of the surface of the outer layer transport hole ring belt (4-2) is 30-70°.

6. The uniform high-quality multi-component semiconductor thin film mist-chemical vapor deposition apparatus according to claim 1, wherein The inner layer transport ring belt holes (4-11) are arranged in an array on the inner layer transport hole ring belt (4-4), and the array arrangement form is close hexagonal arrangement or rectangular array; the diameter of the inner layer transport ring belt holes (4-11) is 1-30 mm, and the number is 2-1000; the inner layer transport ring belt holes (4-11) are inclined to the direction away from the normal line of the surface of the inner layer transport hole ring belt (4-4), and the included angle with the normal line of the surface of the inner layer transport hole ring belt (4-4) is 110-150°.

7. The uniform high-quality multi-component semiconductor thin film mist-chemical vapor deposition apparatus according to claim 1, wherein The two atomization devices (1) are identical in structure and each comprises an atomization tank (1-1), an atomization tank gas inlet pipe (1-2) and an atomization tank gas outlet pipe (1-3); one end of the atomization tank gas inlet pipe (1-2) is used for the entry of carrier gas, and the other end is in communication with the gas inlet end of the atomization tank (1-1); the atomization tank (1-1) is used for containing and atomizing reaction raw materials; one end of the atomization tank gas outlet pipe (1-3) is in communication with the gas outlet end of the atomization tank (1-1), and the other end is in communication with the outer lower part buffer area gas inlet pipe (4-12) or the inner lower part buffer area gas inlet pipe (4-13).

8. The uniform high-quality multi-component semiconductor thin film mist chemical vapor deposition apparatus according to claim 1, wherein According to the flow direction of the gas phase, the gas outlet end of the reaction cavity (2) is located behind the tray (6-2) of the substrate clamping device (6); the gas outlet end of the reaction cavity (2) is provided with a cavity gas outlet pipe (2-1) for being in communication with the tail gas inlet pipe (7-1) of the tail gas treatment device (7).

9. The uniform high-quality multi-component semiconductor thin film mist-chemical vapor deposition apparatus according to claim 1, wherein The substrate clamping device (6) comprises a substrate pulling rod (6-1) and a tray (6-2); one end of the substrate pulling rod (6-1) passes through the open end of the reaction cavity (2) and extends into the interior of the reaction cavity (2); the initial end of the substrate pulling rod (6-1) is fixedly connected with the output end of the motor (5-2); the tray (6-2) is fixed on the terminal end of the substrate pulling rod (6-1); the tray (6-2) is located in the outer layer transport channel (4-1) and faces the outer layer transport hole ring belt (4-2) and the inner layer transport hole ring belt (4-4) for receiving the atomized reaction raw materials transported by the carrier gas.

10. The uniform high-quality multi-component semiconductor thin film mist-chemical vapor deposition apparatus according to claim 1, wherein The tail gas treatment device (7) comprises a tail gas inlet pipe (7-1), a treatment module (7-2) and a tail gas outlet pipe (7-3); one end of the tail gas inlet pipe (7-1) is in communication with the gas outlet end of the reaction cavity (2), and the other end is in communication with the gas inlet end of the treatment module (7-2); the treatment module (7-2) is used for treating reaction by-products and unreacted raw materials; the gas outlet end of the treatment module (7-2) is in communication with one end of the tail gas outlet pipe (7-3); the other end of the tail gas outlet pipe (7-3) is connected with the atmospheric environment for discharging tail gas.

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