Method for growing semiconductor substrates based on an hvpe apparatus, semiconductor substrate and hvpe apparatus

Abstract

The application provides a semiconductor substrate growth method based on an HVPE device, a semiconductor substrate and an HVPE device, which can be applied in the gallium nitride crystal growth field, and the method comprises the following steps: providing a metal-containing precursor gas and a nitrogen-containing precursor gas to the upper side of a seed crystal through a first gas outlet pipe and a second gas outlet pipe respectively, so that the metal-containing precursor gas and the nitrogen-containing precursor gas react to form a nitrogen-containing metal layer, and a semiconductor substrate is obtained; while the metal-containing precursor gas and the nitrogen-containing precursor gas are introduced into the upper side of the seed crystal, a shielding gas is introduced into the shielding pipe, so that the metal-containing precursor gas diffused from the sidewall of the first gas outlet pipe and the nitrogen-containing precursor gas diffused from the sidewall of the second gas outlet pipe are inhibited from pre-reacting to form a pre-reaction product. The application can inhibit pre-reaction, ensure the yield and performance of finished products, avoid pipeline blockage, prolong the growth time and maintenance period, and reduce production costs.

Description

Technical Field

[0001] This invention relates to the field of hydride vapor phase epitaxial growth technology, and in particular to a method for growing semiconductor substrates based on HVPE equipment, the semiconductor substrate, and the HVPE equipment. Background Technology

[0002] Hydride vapor phase epitaxy (HVPE) is the mainstream technology for the industrial-scale preparation of gallium nitride crystals due to its core advantages of fast growth rate, high crystal quality, and controllable cost. In conventional hydride vapor phase epitaxy growth processes, gallium chloride (GaN)... ) and ammonia ( Gallium nitride crystals are generated by the interaction reaction in the seed crystal growth region.

[0003] In related technologies, a coaxial dual-pipe structure is typically used, with one pipe transporting gallium chloride and the other transporting ammonia. However, both types of gas molecules have extremely high diffusivity, and gallium chloride and ammonia readily penetrate the walls of their respective pipes, causing premature pre-reactions in the gap between the outer walls of the two pipes and on the pipe surface, generating loose and porous polycrystalline parasitic gallium nitride particles.

[0004] As the growth process continues, the polycrystalline layer thickens and its adhesion decreases, causing it to continuously detach and fall into the seed crystal growth area below. This can lead to defects in the gallium nitride crystal, affecting the yield and performance of the finished product, as well as causing pipeline blockage, reducing the continuous growth time of the device, shortening the device maintenance cycle, and increasing production costs. Summary of the Invention

[0005] The semiconductor substrate growth method, semiconductor substrate, and HVPE equipment provided by this invention at least solve the problem that related pipelines are easily penetrated by reactive gases and premature pre-reaction occurs, effectively suppressing pre-reaction, ensuring product yield and performance, avoiding pipeline blockage, facilitating the extension of continuous growth time and maintenance cycle of the device, and reducing production costs.

[0006] In a first aspect, the present invention provides a method for growing a semiconductor substrate based on an HVPE (High-Voltage-Pressure Peeling) device. The HVPE device includes a growth chamber, a first gas outlet pipe, a second gas outlet pipe, and a protective tube. A seed crystal is disposed within the growth chamber. The second gas outlet pipe is arranged parallel to the first gas outlet pipe. The protective tube is disposed around the first and second gas outlet pipes. The method includes: providing a metal-containing precursor gas and a nitrogen-containing precursor gas respectively through the first and second gas outlet pipes to the surface above the seed crystal, such that the metal-containing precursor gas and the nitrogen-containing precursor gas... A nitrogen-containing metal layer is generated by a growth reaction to obtain a semiconductor substrate. While the metal-containing precursor gas and the nitrogen-containing precursor gas are introduced above the seed crystal, a protective gas is introduced into the protective tube to suppress the pre-reaction of the metal-containing precursor gas diffusing from the side wall of the first outlet pipe and the nitrogen-containing precursor gas diffusing from the side wall of the second outlet pipe to generate pre-reaction products. The lengths of the first outlet pipe and the second outlet pipe within the growth chamber are both less than or equal to the length of the protective tube within the growth chamber, and the protective tube is sealed relative to the area where the seed crystal is located.

[0007] In one embodiment of the present invention, the flow rate of the protective gas changes in a stepwise manner during the growth of the nitrogen-containing metal layer.

[0008] In one embodiment of the present invention, during the growth of the nitrogen-containing metal layer, the flow rate of the protective gas first increases and then decreases.

[0009] In one embodiment of the invention, the flow rate of the protective gas is 50 sccm to 200 sccm.

[0010] In one embodiment of the present invention, the growth process of the nitrogen-containing metal layer includes a sequential growth heating stage, an isothermal growth stage, and a cooling stage. Specifically, the method includes: in the growth heating stage, controlling the flow rate of the protective gas at a first set flow rate; wherein the first set flow rate is 50 sccm to 60 sccm; in the isothermal growth stage, controlling the flow rate of the protective gas at a second set flow rate; wherein the second set flow rate is 150 sccm to 200 sccm; and in the cooling stage, controlling the flow rate of the protective gas at a third set flow rate; wherein the third set flow rate is 80 sccm to 120 sccm.

[0011] In one embodiment of the present invention, the protective tube includes a first protective sub-tube and a second protective sub-tube, the first protective sub-tube being sleeved outside the first outlet pipe, and the second protective sub-tube being sleeved outside the second outlet pipe; the method specifically includes: introducing a protective gas into the first protective sub-tube to suppress the pre-reaction between the nitrogen-containing precursor gas and the metal-containing precursor gas diffusing from the side wall of the first outlet pipe; and introducing a protective gas into the second protective sub-tube to suppress the pre-reaction between the metal-containing precursor gas and the nitrogen-containing precursor gas diffusing from the side wall of the second outlet pipe.

[0012] In one embodiment of the present invention, the HVPE equipment further includes an air inlet chamber disposed above and communicating with the growth chamber. The air inlet chamber includes a first cavity and a second cavity separated by partitions. The first cavity includes a first precursor air cavity and a first protective air cavity separated by partitions. The second cavity includes a second precursor air cavity and a second protective air cavity separated by partitions. Multiple first outlet pipes are provided, with at least a portion of each first outlet pipe disposed within the second cavity. The inlet ends of all first outlet pipes are connected to the first precursor air cavity. Multiple second outlet pipes are provided, with the inlet ends of all second outlet pipes connected to the second precursor air cavity. The protective pipe includes multiple first protective sub-pipes and multiple second protective sub-pipes. The inlet ends of all the first protective sub-tubes are connected to the first protective gas chamber, and the inlet ends of all the second protective sub-tubes are connected to the second protective gas chamber. Before providing the metal-containing precursor gas and the nitrogen-containing precursor gas to the top of the seed crystal through the first and second outlet pipes respectively, the method further includes: introducing the metal-containing precursor gas into all the first outlet pipes through the first precursor gas chamber; introducing the nitrogen-containing precursor gas into all the second outlet pipes through the second precursor gas chamber; before introducing the protective gas into the protective tube, the method further includes: introducing the protective gas into all the first protective sub-tubes through the first protective gas chamber; introducing the protective gas into all the second protective sub-tubes through the second protective gas chamber.

[0013] In one embodiment of the present invention, the HVPE device further includes a first gas source cavity, which is disposed on one side of the air inlet cavity; the first gas source cavity includes a first gas source sub-cavity and a second gas source sub-cavity separated from each other, and a gallium boat is disposed in the first gas source sub-cavity; before introducing the metal-containing precursor gas into the first precursor gas cavity, the device further includes: introducing a reaction gas into the first gas source sub-cavity, wherein the reaction gas reacts with the liquid gallium metal in the gallium boat to generate the metal-containing precursor gas, and the metal-containing precursor gas in the first gas source sub-cavity is introduced into the first precursor gas cavity.

[0014] In one embodiment of the present invention, before introducing the protective gas into the first protective gas chamber, the method further includes: introducing the protective gas into the first protective gas chamber through the second gas source sub-chamber.

[0015] In one embodiment of the present invention, the HVPE device further includes a second gas source cavity, which is disposed on one side of the air inlet cavity; the second gas source cavity includes a separated third gas source sub-cavity and a fourth gas source sub-cavity; before introducing the nitrogen-containing precursor gas into the second precursor gas cavity, the device further includes: introducing the nitrogen-containing precursor gas into the second precursor gas cavity through the third gas source sub-cavity.

[0016] In one embodiment of the present invention, before introducing the protective gas into the second protective gas chamber, the method further includes: introducing the protective gas into the second protective gas chamber through the fourth gas source sub-chamber.

[0017] In a second aspect, the present invention also provides a semiconductor substrate, which is prepared by the semiconductor substrate growth method based on HVPE equipment as described in any one of the above claims.

[0018] Thirdly, the present invention also provides an HVPE apparatus for growing a semiconductor substrate, the semiconductor substrate comprising a seed crystal and a nitrogen-containing metal layer stacked together, the HVPE apparatus comprising: a growth chamber having the seed crystal disposed therein; a first gas outlet for providing a metal-containing precursor gas to the top of the seed crystal; a second gas outlet, arranged parallel to the first gas outlet for providing a nitrogen-containing precursor gas to the top of the seed crystal; wherein the metal-containing precursor gas and the nitrogen-containing precursor gas react to generate the nitrogen-containing metal layer; and a protective tube disposed around the first gas outlet and the second gas outlet; the first... The lengths of the vent pipe and the second vent pipe within the growth chamber are both less than or equal to the length of the protective pipe within the growth chamber. The protective pipe is sealed relative to the area where the seed crystal is located. The protective pipe is used to introduce a protective gas to suppress the pre-reaction of the metal-containing precursor gas diffusing from the side wall of the first vent pipe and the nitrogen-containing precursor gas diffusing from the side wall of the second vent pipe, thereby generating pre-reaction products. A controller is connected to the first vent pipe, the second vent pipe, and the protective pipe, respectively. The controller is used to control the flow rates of the metal-containing precursor gas, the nitrogen-containing precursor gas, and the protective gas, respectively.

[0019] Compared with the prior art, the above-described technical solution of the present invention has the following advantages: The semiconductor substrate growth method based on HVPE equipment provided by this invention arranges a first gas outlet pipe and a second gas outlet pipe in parallel, increasing the difficulty of the pre-reaction of the metal-containing precursor gas diffusing from the sidewall of the first gas outlet pipe and the nitrogen-containing precursor gas diffusing from the sidewall of the second gas outlet pipe. Simultaneously, a protective tube is set outside the first and second gas outlet pipes, containing a protective gas. This protective gas isolates the metal-containing and nitrogen-containing precursor gases, suppressing the pre-reaction of the two precursor gases and preventing the formation of pre-reaction products. It can also perform an etching reaction with the polycrystalline gallium nitride particles generated during the pre-reaction, decomposing them in real time.

[0020] In this way, the formation of parasitic polycrystalline material can be blocked at the source, avoiding the problem of deposition and blockage on the outer wall of the pipeline, extending the continuous growth time of the equipment, reducing the frequency of downtime for cleaning and maintenance, reducing the operation and maintenance costs and time costs of industrial mass production, and adapting to long-term, large-scale industrial growth scenarios.

[0021] Secondly, it can stabilize the growth airflow field, eliminate defects such as pits, dislocations, stacking faults, and mixed crystals caused by polycrystalline particles falling off, improve the flatness of the crystal surface and the integrity of crystallization, reduce the dislocation density, ensure the yield, performance and mass production stability of finished products, and can meet the substrate requirements of high-end optoelectronic devices and power devices.

[0022] Finally, only adjustments to the piping and gas path structure are required; no modifications to the original furnace, temperature control, or growth process are necessary. It is compatible with conventional hydride vapor phase epitaxy equipment, resulting in low modification costs, strong feasibility, and high value for large-scale deployment. It is particularly suitable for the large-scale preparation of large-size, low-dislocation, high-quality gallium nitride single crystals and epitaxial thin films. Attached Figure Description

[0023] The accompanying drawings, which are provided to further illustrate the invention and constitute a part of this invention, are illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an undue limitation of the invention.

[0024] Figure 1 This is a schematic flowchart of the semiconductor substrate growth method based on HVPE equipment provided by the present invention.

[0025] Figure 2 This is a schematic diagram of the structure of the HVPE device provided by the present invention.

[0026] Figure 3 This is one of the structural schematic diagrams of the first vent pipe, the second vent pipe, and the protective pipe provided by the present invention.

[0027] Figure 4 This is a partial structural schematic diagram of the HVPE equipment provided by the present invention.

[0028] Figure 5This is the second schematic diagram of the structure of the first vent pipe, the second vent pipe, and the protective pipe provided by the present invention.

[0029] The above figures include the following reference numerals: 11. First vent pipe; 12. Second vent pipe; 20. Protective pipe; 21. First protective sub-pipe; 22. Second protective sub-pipe; 23. Flow guide; 24. Exhaust sub-pipe; 30. Growth chamber; 301. Gas outlet; 31. Base; 311. Seed crystal; 32. Heater; 40. Intake chamber; 401. First cavity; 4011. First front-drive air cavity; 4012. First protective air cavity; 402. Second cavity; 4021. Second front-drive air cavity; 4022. Second protective air cavity; 41. First partition; 42. Second partition; 43. Third partition; 50. First gas source cavity; 501. First gas source sub-cavity; 502. Second gas source sub-cavity; 51. Fourth partition; 52. Gallium boat; 60. Second air source cavity; 601. Third air source sub-cavity; 602. Fourth air source sub-cavity; 61. Fifth partition. Detailed Implementation

[0030] It should be noted that, unless otherwise specified, the embodiments and features described in the present invention can be combined with each other. The present invention will now be described in detail with reference to the accompanying drawings and embodiments.

[0031] It should be noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of exemplary embodiments according to the invention. As used herein, the singular form is intended to include the plural form as well, unless the context clearly indicates otherwise. Furthermore, it should be understood that when the terms "comprising" and / or "including" are used in this specification, they indicate the presence of features, steps, operations, devices, components, and / or combinations thereof.

[0032] Unless otherwise specifically stated, the relative arrangement, numerical expressions, and values ​​of the components and steps set forth in these embodiments do not limit the scope of the invention. It should also be understood that, for ease of description, the dimensions of the various parts shown in the drawings are not drawn to actual scale. Techniques, methods, and devices known to those skilled in the art may not be discussed in detail, but where appropriate, such techniques, methods, and devices should be considered part of the specification. In all examples shown and discussed herein, any specific values ​​should be interpreted as merely exemplary and not as limitations. Therefore, other examples of exemplary embodiments may have different values. It should be noted that similar reference numerals and letters in the following figures denote similar items; therefore, once an item is defined in one figure, it need not be further discussed in subsequent figures.

[0033] In the process of growing gallium nitride single crystals using hydride vapor phase epitaxy, a coaxial dual-pipe structure is usually adopted, with one pipe supplying gallium chloride and the other supplying ammonia.

[0034] Because the gas molecules of the two types of gas sources have extremely strong diffusivity, gallium chloride and ammonia can easily penetrate the pipe walls of their respective pipelines, and a pre-reaction occurs in the gap between the outer walls of the two pipelines and on the surface of the pipe walls, generating loose and porous polycrystalline parasitic particles of gallium nitride.

[0035] The specific reaction principle is as follows:

[0036] in, It is polycrystalline gallium nitride. It is hydrogen chloride.

[0037] This reaction is a spontaneous forward reaction and can easily continue under low temperature and low pressure conditions. As the growth process continues, the polycrystalline layer thickens and its adhesion decreases, causing it to continuously detach and fall into the seed crystal growth area below.

[0038] Detached gallium nitride polycrystalline parasitic particles can directly cause defects in single-crystal growth, resulting in surface pits, stacking faults, dislocation multiplication, grain mixing, and uneven local growth thickness, significantly reducing the yield and optoelectronic performance stability of gallium nitride single crystals. Simultaneously, frequent polycrystalline deposition in pipelines can cause localized pipeline blockages and airflow turbulence, shortening equipment maintenance cycles and increasing production costs.

[0039] It should be noted that some related technologies also employ inert gas purging and optimized pipe spacing to mitigate polycrystalline deposition problems. However, these methods have limited protective effects, cannot eradicate parasitic pre-reactions on the outer wall of the pipes from the perspective of reaction thermodynamics and kinetics, and are not suitable for long-term, large-scale industrial growth scenarios.

[0040] To address the issues of premature gas source reaction on the outer wall of the pipeline, parasitic polycrystalline deposition, and particle fallout contamination of the growth zone in existing gallium nitride hydride vapor phase epitaxial growth, this paper, in conjunction with reference to... Figures 1 to 4 As shown, the present invention provides a method for growing semiconductor substrates based on HVPE equipment.

[0041] In this embodiment, the HVPE apparatus includes a growth chamber 30, a first vent pipe 11, a second vent pipe 12, and a protective tube 20. A seed crystal 311 is disposed within the growth chamber 30. The semiconductor substrate growth method includes steps S130 and S160.

[0042] In step S130, a metal-containing precursor gas and a nitrogen-containing precursor gas are supplied to the top of the seed crystal 311 through the first gas outlet pipe 11 and the second gas outlet pipe 12, respectively, so that the metal-containing precursor gas and the nitrogen-containing precursor gas react to generate a nitrogen-containing metal layer, thereby obtaining a semiconductor substrate.

[0043] The first vent pipe 11 and the second vent pipe 12 are both located above the seed crystal 311, and the first vent pipe 11 and the second vent pipe 12 are arranged side by side. Arranging the first vent pipe 11 and the second vent pipe 12 side by side can effectively increase the difficulty of the pre-reaction of the metal-containing precursor gas diffusing from the first vent pipe 11 and the nitrogen-containing precursor gas diffusing from the second vent pipe 12.

[0044] The outlet ends of the first vent pipe 11 and the second vent pipe 12 are both located within the growth chamber 30. The first vent pipe 11 supplies the growth chamber 30 with a metal-containing precursor gas, and the second vent pipe 12 supplies the growth chamber 30 with a nitrogen-containing precursor gas. The metal-containing precursor gas and the nitrogen-containing precursor gas above the seed crystal 311 react to grow a nitrogen-containing metal layer on the upper surface of the seed crystal 311.

[0045] Preferably, the nitrogen-containing metal layer is a gallium nitride layer, the metal-containing precursor gas is gallium chloride, and the nitrogen-containing precursor gas is ammonia. Ammonia reacts with gallium chloride at high temperature to form single-crystal gallium nitride.

[0046] The specific reaction principle is as follows:

[0047] in, It is a single-crystal gallium nitride.

[0048] Preferably, before step S130, the above growth method further includes the step of placing a seed crystal 311 in the growth cavity 30.

[0049] For example, the seed crystal 311 can be placed on the base 31 inside the growth chamber 30, and the base 31 supports the seed crystal 311. The seed crystal 311 is a tiny crystal with a specific crystal orientation, which serves as a template to provide a structural basis for the subsequent growth of the nitrogen-containing metal layer.

[0050] In step S160, while introducing a metal-containing precursor gas and a nitrogen-containing precursor gas above the seed crystal 311, a protective gas is introduced into the protective tube 20 to suppress the metal-containing precursor gas diffusing from the side wall of the first outlet tube 11 and the nitrogen-containing precursor gas diffusing from the side wall of the second outlet tube 12 from undergoing a pre-reaction to generate pre-reaction products.

[0051] The protective tube 20 is positioned above the seed crystal 311 and is located around the first vent pipe 11 and the second vent pipe 12. The vent end of the protective tube 20 is also located within the growth chamber 30. The protective tube 20 contains a protective gas, which can isolate the metal-containing precursor gas and the nitrogen-containing precursor gas, and can suppress the pre-reaction of the metal-containing precursor gas diffusing from the side wall of the first vent pipe 11 and the nitrogen-containing precursor gas diffusing from the side wall of the second vent pipe 12 to generate pre-reaction products.

[0052] Preferably, the pre-reaction product is polycrystalline gallium nitride, and the protective gas is hydrogen chloride. Compared to nitrogen, choosing hydrogen chloride as the protective gas can suppress the pre-reaction without prolonged high-speed introduction, resulting in better protection.

[0053] On the one hand, the enrichment of hydrogen chloride in the protective gas cavity can isolate gallium chloride and ammonia. On the other hand, according to Le Chatelier's principle of chemical reactions, hydrogen chloride can also strongly inhibit the formation of pre-reaction products, significantly reducing the formation rate of primary polycrystalline material on the outer wall of the pipeline from the source, and essentially eliminating parasitic reactions.

[0054] On the other hand, even if a small amount of polycrystalline gallium nitride particles are generated due to diffusion, the hydrogen chloride in the protective gas cavity can still react with the newly formed, loosely packed polycrystalline gallium nitride particles, decomposing them in real time into gaseous gallium chloride and ammonia. The specific reaction principle is as follows:

[0055] It should be noted that the step of introducing protective gas into the protective tube 20 can be performed in advance before introducing the metal-containing precursor gas and the nitrogen-containing precursor gas above the seed crystal 311, or it can be performed after introducing the metal-containing precursor gas and the nitrogen-containing precursor gas, as long as it is ensured that the protective gas can isolate the two precursor gases and suppress the pre-reaction and etching pre-reaction products.

[0056] Preferably, the nitrogen-containing metal layer is gallium nitride, and correspondingly, the seed crystal 311 can be a gallium nitride seed crystal. Of course, the growth method provided by this invention can not only be used to grow gallium nitride, but also to grow other semiconductor materials, such as aluminum nitride (Al₂O₃). Gallium arsenide ( Indium phosphide ( ) or gallium oxide ( Materials such as metal-containing precursor gases, nitrogen-containing precursor gases, and protective gases can be selected according to specific application needs, and this invention does not impose any restrictions on them.

[0057] In summary, the semiconductor substrate growth method based on HVPE equipment provided by this invention arranges the first vent pipe 11 and the second vent pipe 12 side by side, increasing the difficulty of the pre-reaction of the metal-containing precursor gas diffusing from the sidewall of the first vent pipe 11 and the nitrogen-containing precursor gas diffusing from the sidewall of the second vent pipe 12. Simultaneously, a protective tube 20 is provided outside the first vent pipe 11 and the second vent pipe 12. The protective tube 20 contains a protective gas, which can isolate the metal-containing precursor gas and the nitrogen-containing precursor gas, suppressing the pre-reaction of the two precursor gases to form pre-reaction products. It can also undergo an etching reaction with the polycrystalline gallium nitride particles generated during the pre-reaction, decomposing them in real time.

[0058] In this way, the formation of parasitic polycrystalline material can be blocked at the source, avoiding the problem of deposition and blockage on the outer wall of the pipeline, extending the continuous growth time of the equipment, reducing the frequency of downtime for cleaning and maintenance, reducing the operation and maintenance costs and time costs of industrial mass production, and adapting to long-term, large-scale industrial growth scenarios.

[0059] Secondly, it can stabilize the growth airflow field, eliminate defects such as pits, dislocations, stacking faults, and mixed crystals caused by polycrystalline particles falling off, improve the flatness of the crystal surface and the integrity of crystallization, reduce the dislocation density, ensure the yield, performance and mass production stability of finished products, and can meet the substrate requirements of high-end optoelectronic devices and power devices.

[0060] Finally, only adjustments to the piping and gas path structure are required; no modifications to the original furnace, temperature control, or growth process are necessary. It is compatible with conventional hydride vapor phase epitaxy equipment, resulting in low modification costs, strong feasibility, and high value for large-scale deployment. It is particularly suitable for the large-scale preparation of large-size, low-dislocation, high-quality gallium nitride single crystals and epitaxial thin films.

[0061] In some embodiments, the flow rate of the protective gas varies in a stepwise manner during the growth of the nitrogen-containing metal layer.

[0062] The growth process of the nitrogen-containing metal layer includes a sequential heating stage, an isothermal growth stage, and a cooling stage. The heating stage establishes a stable high-temperature reaction environment for the growth of the nitrogen-containing metal layer; during this stage, the temperature within the growth chamber 30 is gradually increased to the preset growth temperature. The isothermal growth stage is the core step in growing the nitrogen-containing metal layer. In this stage, the metal-containing precursor gas and the nitrogen-containing precursor gas react and deposit orderly on the surface of the seed crystal 311, thus growing the nitrogen-containing metal layer. The cooling stage alleviates thermal stress and ensures the structural integrity of the grown nitrogen-containing metal layer. During this stage, the temperature within the growth chamber 30 is gradually decreased to prevent problems such as cracking of the nitrogen-containing metal layer.

[0063] The stepped flow rate variation of the protective gas refers to dividing the flow rate of the protective gas into multiple levels according to different stages of the nitrogen-containing metal layer. When the stage of the nitrogen-containing metal layer changes, the flow rate of the protective gas is directly adjusted to the corresponding level, rather than keeping the flow rate constant or continuously linearly varying throughout. This ensures a precise and dynamic match between the protective gas's isolation effect, pre-reaction inhibition effect, and etching effect. Control valves can be installed in the pipeline to achieve flow control of the protective gas.

[0064] Preferably, in some embodiments, during the growth of the nitrogen-containing metal layer, the flow rate of the protective gas first increases and then decreases. That is, the flow rate of the protective gas during the heating stage of growth is less than the flow rate during the cooling stage, and the flow rate of the protective gas during the cooling stage is less than the flow rate during the isothermal growth stage.

[0065] During the growth and heating phase, a protective atmosphere can be established in advance using a low-flow protective gas. The protective gas can preferentially react with any gallium nitride or gallium residue that may remain on the pipe wall, forming a protective environment and preventing these residues from contaminating or clogging the pipe during heating.

[0066] During the growth heating stage, a certain amount of hydrogen chloride can be introduced into the growth chamber 30 to perform micro-cleaning or activation on the surface of the seed crystal 311, in preparation for subsequent high-quality growth.

[0067] During the isothermal growth stage, a large flow of protective gas can provide stable protection, suppress unwanted N-face polar nucleation, promote the growth of high-quality Ga-face polar thin films, and help improve the growth rate and crystal quality.

[0068] During the cooling phase, residual nascent polycrystalline material in the pipeline can be removed using a medium-flow protective gas. At the beginning of cooling, the temperature is relatively high, resulting in a relatively large amount of gallium nitride polycrystalline products formed by gas diffusion. Therefore, setting the flow rate of the protective gas during the cooling phase to be greater than that during the growth heating phase but less than that during the isothermal growth phase effectively achieves corrosion without introducing excessive risks during cooling due to excessive flow.

[0069] Preferably, the flow rate of the protective gas is between 50 sccm and 200 sccm. Wherein, sccm is standard cubic centimeters per minute, and 1 sccm equals 1 milliliter per minute.

[0070] In one embodiment, the above-mentioned growth method specifically includes steps S1631, S1632 and S1633.

[0071] Step S1631: During the growth heating stage, the flow rate of the protective gas is controlled at the first set flow rate.

[0072] The initial set flow rate is 50 to 60 sccm. In this way, a protective environment can be formed in advance with the protective gas at the initial set flow rate, avoiding any impact on subsequent gas transmission.

[0073] For example, the first set flow rate can be set to 50 sccm, 51 sccm, 52 sccm, 53 sccm, 54 sccm, 55 sccm, 56 sccm, 57 sccm, 58 sccm, 59 sccm, or 60 sccm, etc.

[0074] In step S1632, during the isothermal growth stage, the flow rate of the protective gas is controlled at the second set flow rate.

[0075] The second set flow rate is 150 sccm to 200 sccm. In this way, stable protection can be provided by the protective gas at the second set flow rate.

[0076] For example, the second set flow rate can be set to 150 sccm, 160 sccm, 170 sccm, 180 sccm, 190 sccm or 200 sccm, etc.

[0077] In step S1633, during the cooling stage, the flow rate of the protective gas is controlled at the third set flow rate.

[0078] The third set flow rate is 80 sccm to 120 sccm. In this way, effective etching can be achieved with the protective gas at the third set flow rate.

[0079] For example, the flow rate can be set to 80 sccm, 90 sccm, 100 sccm, 110 sccm, or 120 sccm, etc.

[0080] In some embodiments, refer to Figure 2 and Figure 3 As shown, the protective tube 20 includes a first protective sub-tube 21 and a second protective sub-tube 22. The first protective sub-tube 21 is sleeved outside the first vent pipe 11, and the second protective sub-tube 22 is sleeved outside the second vent pipe 12.

[0081] Based on this, step S160 specifically includes steps S161 and S162.

[0082] Step S161: A protective gas is introduced into the first protective sub-tube 21 to suppress the pre-reaction between the nitrogen-containing precursor gas and the metal-containing precursor gas diffusing from the side wall of the first outlet tube 11.

[0083] Step S162: A protective gas is introduced into the second protective sub-tube 22 to suppress the pre-reaction between the metal-containing precursor gas and the nitrogen-containing precursor gas diffusing from the side wall of the second outlet tube 12.

[0084] In this way, protective sub-tubes are independently set up for the two gas outlets. The protective sub-tubes themselves have a certain physical isolation effect, which can suppress the pre-reaction of the two precursor gases. In addition, this structure can also regulate the airflow distribution, so that the gases do not cross-contaminate and the flow rate is independently controllable. This avoids gas source disturbance and local airflow unevenness caused by gas diffusion, and achieves a high degree of consistency in the thickness and performance of gallium nitride growth across the entire wafer and furnace, thereby improving the yield and batch stability of finished products.

[0085] Preferably, in some embodiments, reference is made to Figure 3 As shown, at least one of the four types of pipe walls—the outer wall of the first vent pipe 11, the inner wall of the first protective sub-pipe 21, the outer wall of the second vent pipe 12, and the inner wall of the second protective sub-pipe 22—is provided with a flow guide 23.

[0086] Based on the fact that at least one of the two pipe walls, the outer pipe wall of the first vent pipe 11 and the inner pipe wall of the first protective sub-pipe 21, is provided with a guide member 23, step S161 includes: based on the guide member 23 provided on the outer pipe wall of the first vent pipe 11 and / or the guide member 23 provided on the inner pipe wall of the first protective sub-pipe 21, providing guidance for the protective gas in the first protective sub-pipe 21, so that the protective gas uniformly covers the first vent pipe 11.

[0087] Accordingly, based on the fact that at least one of the two pipe walls, the outer pipe wall of the second outlet pipe 12 and the inner pipe wall of the second protective sub-pipe 22, is provided with a guide member 23, step S162 includes: based on the guide member 23 provided on the outer pipe wall of the second outlet pipe 12 and / or the guide member 23 provided on the inner pipe wall of the second protective sub-pipe 22, providing guidance for the protective gas in the second protective sub-pipe 22, so that the protective gas uniformly covers the second outlet pipe 12.

[0088] Based on this, prior to step S161, the above-mentioned growth method further includes: replacing the first protective sub-tube 21 according to the radius of the first vent pipe 11, so that the difference between the radius of the first protective sub-tube 21 and the radius of the first vent pipe 11 meets the requirements; and replacing the tube where the guide member 23 is located, so that the radial dimension of the tube where the guide member 23 is located meets the requirements.

[0089] Accordingly, prior to step S162, the above-mentioned growth method further includes: replacing the second protective sub-tube 22 according to the radius of the second vent pipe 12, so that the difference between the radius of the second protective sub-tube 22 and the radius of the second vent pipe 12 meets the requirements; and replacing the tube where the guide member 23 is located, so that the radial dimension along the tube where the guide member 23 is located meets the requirements.

[0090] In some embodiments, refer to Figure 2 and Figure 4 As shown, the HVPE equipment also includes an air intake chamber 40, which is located above and communicates with the growth chamber 30.

[0091] The intake chamber 40 includes a separate first cavity 401 and a second cavity 402. The first cavity 401 includes a separate first precursor air cavity 4011 and a separate first protective air cavity 4012, and the second cavity 402 includes a separate second precursor air cavity 4021 and a separate protective air cavity 4022. In this way, different gases can be introduced into independent air cavities, avoiding leakage and contamination of individual gases, while also preventing pre-reaction of the precursor gas.

[0092] Multiple first exhaust pipes 11 are provided, and at least partially disposed within the second cavity 402. The inlet ends of all first exhaust pipes 11 are connected to the first precursor gas cavity 4011. Multiple second exhaust pipes 12 are provided, and the inlet ends of all second exhaust pipes 12 are connected to the second precursor gas cavity 4021. This allows for a more uniform distribution of the two precursor gases, thereby improving substrate quality.

[0093] Correspondingly, the protective tube 20 includes multiple first protective sub-tubes 21 and multiple second protective sub-tubes 22. Each first protective sub-tube 21 corresponds to a first outlet tube 11, and each second protective sub-tube 22 corresponds to a second outlet tube 12. The inlet end of all first protective sub-tubes 21 is connected to the first protective gas chamber 4012, and the inlet end of all second protective sub-tubes 22 is connected to the second protective gas chamber 4022. In this way, the two precursor gases can be effectively isolated by the protective gas, and the pre-reaction of the two precursor gases can be suppressed.

[0094] Based on this, before step S130, the above growth method further includes steps S111 and S121.

[0095] In step S111, the metal-containing precursor gas is introduced into all the first outlet pipes 11 through the first precursor gas chamber 4011.

[0096] The first precursor gas chamber 4011 is relatively independent of the other gas chambers. It can receive metal-containing precursor gas and then introduce it into different first outlet pipes 11, and finally into the growth chamber 30 to react with nitrogen-containing precursor gas. In this way, the metal-containing precursor gas in the gas chamber and outlet pipe can be effectively prevented from diffusing outward, while also effectively isolating external stray atmosphere, stabilizing the airflow field around the pipeline, and helping to reduce the probability of parasitic reactions.

[0097] In step S121, nitrogen-containing precursor gas is introduced into all the second outlet pipes 12 through the second precursor gas chamber 4021.

[0098] The second precursor gas chamber 4021 is relatively independent of the other gas chambers. It receives nitrogen-containing precursor gas and then introduces it into different second outlet pipes 12 before finally entering the growth chamber 30 to react with the metal-containing precursor gas. This effectively prevents the nitrogen-containing precursor gas in the gas chambers and outlet pipes from diffusing outwards, while also effectively isolating external stray atmospheres, stabilizing the airflow field around the pipeline, and helping to reduce the probability of parasitic reactions.

[0099] Similarly, prior to step S160, the above growth method further includes steps S141 and S151.

[0100] Step S141: The protective gas is introduced into all the first protective sub-tubes 21 through the first protective gas chamber 4012.

[0101] The first protective gas chamber 4012 is relatively independent of the other gas chambers. It can receive protective gas and then introduce the protective gas into different first protective sub-tubes 21 to achieve isolation, suppression, and etching. In this way, the protective gas in the gas chamber and protective sub-tubes can be effectively prevented from diffusing outward, while also effectively isolating external stray atmospheres, stabilizing the airflow field around the pipeline, and helping to reduce the probability of parasitic reactions.

[0102] Step S151: The protective gas is introduced into all the second protective sub-tubes 22 through the second protective gas chamber 4022.

[0103] The second protective gas chamber 4022 is relatively independent of the other gas chambers. It can receive protective gas and then introduce the protective gas into different second protective sub-tubes 22 to achieve isolation, suppression, and etching. In this way, the protective gas in the gas chamber and protective sub-tubes can be effectively prevented from diffusing outward, while also effectively isolating external stray atmospheres, stabilizing the airflow field around the pipeline, and helping to reduce the probability of parasitic reactions.

[0104] During growth, the gases do not cross-contaminate each other, effectively isolating the protective function from the gas transport function.

[0105] Furthermore, in some embodiments, reference is made to... Figure 2 and Figure 4 As shown, the HVPE equipment also includes a first gas source chamber 50, which is located on one side of the air inlet chamber 40. The first gas source chamber 50 includes a separated first gas source sub-chamber 501 and a second gas source sub-chamber 502. The first gas source sub-chamber 501 is used to generate a metal-containing gas chamber, and a gallium boat 52 is disposed in the first gas source sub-chamber 501. The second gas source sub-chamber 502 is used to introduce protective gas.

[0106] Based on this, before introducing the metal-containing precursor gas into the first precursor gas chamber 4011, the above growth method further includes step S110.

[0107] In step S110, the reaction gas is introduced into the first gas source sub-cavity 501. The reaction gas reacts with the liquid gallium metal in the gallium boat 52 to generate a metal-containing precursor gas. The metal-containing precursor gas in the first gas source sub-cavity 501 is then introduced into the first precursor gas cavity 4011.

[0108] Preferably, the reactant gas is hydrogen chloride, which reacts with liquid gallium to produce gallium chloride. The specific reaction principle is as follows:

[0109] in, It is liquid gallium. It is hydrogen gas.

[0110] The first gas source sub-cavity 501 is relatively independent from the other cavities, providing a favorable reaction environment for the generation of metal-containing precursor gas. Simultaneously, the volume of the first gas source sub-cavity 501 can be set relatively small, thereby extending the residence time of the reactant gas in the first gas source sub-cavity 501, allowing the reactant gas to fully react with liquid gallium and improving gas utilization.

[0111] Preferably, a heater 32 is provided outside the first gas source cavity 501. While performing step S110, the material is heated by the heater 32, thereby increasing the material temperature, accelerating the chemical reaction rate between the two, and improving the overall growth efficiency.

[0112] Preferably, while performing step S110, the growth method further includes introducing a carrier gas into the first gas source cavity 501, so that the carrier gas carries the metal-containing precursor gas into the first precursor gas cavity 4011. Thus, by controlling the flow rate of the carrier gas, the rate and concentration of the metal-containing precursor gas delivered to the growth cavity 30 can be adjusted, stabilizing the gas flow field and avoiding localized gas flow turbulence. Preferably, the carrier gas is an inert gas or nitrogen to avoid reaction with gallium chloride.

[0113] Before introducing the protective gas into the first protective gas chamber 4012, the above growth method further includes step S140.

[0114] In step S140, the protective gas is introduced into the first protective gas chamber 4012 through the second gas source chamber 502.

[0115] Thus, after the protective gas is introduced into the first protective gas chamber 4012, it is introduced into all the first protective sub-tubes 21 respectively, and provides isolation protection for the first outlet pipe 11 in the first protective sub-tube 21, suppressing the pre-reaction between the nitrogen-containing precursor gas and the metal-containing precursor gas diffused from the side wall of the first outlet pipe 11.

[0116] In some embodiments, refer to Figure 2 and Figure 4 As shown, the HVPE equipment also includes a second gas source chamber 60, which is located on one side of the air inlet chamber 40. The second gas source chamber 60 includes a separated third gas source sub-chamber 601 and a fourth gas source sub-chamber 602. The third gas source sub-chamber 601 is used to introduce nitrogen-containing precursor gas, and the fourth gas source sub-chamber 602 is used to introduce protective gas.

[0117] Based on this, before introducing the nitrogen-containing precursor gas into the second precursor gas chamber 4021, the above growth method further includes step S120.

[0118] In step S120, nitrogen-containing precursor gas is introduced into the second precursor gas chamber 4021 through the third gas source chamber 601.

[0119] The third gas source chamber 601 is relatively independent from the other chambers, which can effectively prevent the nitrogen-containing precursor gas inside from diffusing outward, and can also effectively isolate the external stray atmosphere.

[0120] Preferably, a heater 32 is provided outside the third gas source sub-cavity 601. During step S120, the heater 32 heats the gas to increase the gas activity of the nitrogen-containing precursor gas, so that the subsequent nitrogen-containing precursor gas can fully react with the metal-containing precursor gas. At the same time, it can also reduce the impact of temperature difference on the airflow stability.

[0121] Before introducing the protective gas into the second protective gas chamber 4022, the above growth method further includes step S150.

[0122] In step S150, the protective gas is introduced into the second protective gas chamber 4022 through the fourth gas source chamber 602.

[0123] Thus, after the protective gas is introduced into the second protective gas chamber 4022, it is introduced into all the second protective sub-tubes 22 respectively, and provides isolation protection for the second outlet pipe 12 in the second protective sub-tube 22, suppressing the metal-containing precursor gas from reacting with the nitrogen-containing precursor gas diffused from the side wall of the second outlet pipe 12.

[0124] In some embodiments, refer to Figure 2 As shown, the HVPE equipment also includes an exhaust sub-pipe 24, the inlet end of which is connected to the outlet end of the protective pipe 20, and the outlet end of the exhaust sub-pipe 24 is connected to the outside of the growth chamber 30. Based on this, after step S160, step S170 is also included.

[0125] In step S170, the protective gas is discharged from the growth chamber 30 through the exhaust sub-pipe 24.

[0126] In this way, the growth chamber 30 and the two protective sub-tubes can be isolated by the exhaust sub-tube 24, preventing the protective gas from entering the growth chamber 30 and corroding the nitrogen-containing metal layer, thus ensuring the high quality of the final product.

[0127] On the other hand, the present invention provides a semiconductor substrate prepared by a semiconductor substrate growth method based on an HVPE device as described in any of the above embodiments.

[0128] The semiconductor substrate described in this invention is prepared using the semiconductor substrate growth method based on HVPE equipment described in the above embodiments, and therefore the semiconductor substrate has the beneficial effects imparted by the above growth method.

[0129] Specifically, during the preparation process, the first vent pipe 11 and the second vent pipe 12 are arranged side by side, which increases the difficulty of the pre-reaction of the metal-containing precursor gas diffusing from the sidewall of the first vent pipe 11 and the nitrogen-containing precursor gas diffusing from the sidewall of the second vent pipe 12. Simultaneously, a protective pipe 20 is installed outside the first vent pipe 11 and the second vent pipe 12. The protective pipe 20 contains a protective gas, which can isolate the metal-containing precursor gas and the nitrogen-containing precursor gas, inhibit the pre-reaction of the two precursor gases to form pre-reaction products, and can also undergo an etching reaction with the polycrystalline gallium nitride particles generated in the pre-reaction, decomposing them in real time.

[0130] In this way, defects such as pits, dislocations, stacking faults, and mixed crystals caused by polycrystalline particles falling off can be effectively eliminated, thereby improving the flatness of the crystal surface and the integrity of crystallization, reducing the dislocation density, ensuring the yield, performance and mass production stability of finished products, and adapting to the substrate requirements of high-end optoelectronic devices and power devices.

[0131] On the other hand, refer to Figure 2As shown, the present invention also provides an HVPE apparatus for growing a semiconductor substrate, the semiconductor substrate comprising a seed crystal 311 and a nitrogen-containing metal layer stacked together. The HVPE apparatus includes a growth chamber 30, a first vent pipe 11, a second vent pipe 12, a protective tube 20, and a controller (not shown in the figure).

[0132] The growth chamber 30 provides a growth environment for the nitrogen-containing metal layer, and a seed crystal 311 is disposed inside the growth chamber 30. Preferably, a base 31 is disposed inside the growth chamber 30 to support the seed crystal 311.

[0133] Preferably, heaters 32 are provided on both the outside of the growth chamber 30 and the lower surface of the base 31 to provide heat for the growth of the nitrogen-containing metal layer, thereby meeting the high-temperature conditions required for growth. An outlet 301 is provided at the bottom of the growth chamber 30 to discharge excess gas.

[0134] The first vent pipe 11 is disposed above the base 31. The number of first vent pipes 11 can be one or more. When multiple first vent pipes 11 are disposed, the axial directions of each first vent pipe 11 can be arranged parallel to each other, or the axial directions of a portion of the first vent pipes 11 can be set to have an included angle, so that this portion of the first vent pipes 11 is relatively inclined.

[0135] Alternatively, the first vent pipe 11 can be placed inside the growth chamber 30, and the first vent pipe 11 can be directly or indirectly connected and fixed to the chamber wall of the growth chamber 30, so that the first vent pipe 11 and the base 31 are arranged sequentially from high to low in the vertical direction. Alternatively, the main body of the first vent pipe 11 can be placed outside the growth chamber 30, with only the vent end of the first vent pipe 11 placed inside the growth chamber 30, so that the first vent pipe 11 and the base 31 are arranged sequentially from high to low in the vertical direction.

[0136] The outlet end of the first vent pipe 11 is positioned facing the base 31 to provide a metal-containing precursor gas above the seed crystal 311 on the base 31. Preferably, the first vent pipe 11 is made of quartz material to avoid the reaction between the first vent pipe 11 and the metal-containing precursor gas, while suppressing the diffusion of the metal-containing precursor gas from the first vent pipe 11 to the outside as much as possible.

[0137] The first vent pipe 11 can be set perpendicular to the upper surface of the seed crystal 311, or it can be set at an angle so that the axial direction of the first vent pipe 11 is at an angle to the upper surface of the seed crystal 311.

[0138] For example, the inlet end of the first outlet pipe 11 can be directly or indirectly connected to a metal-containing precursor gas source, which provides metal-containing precursor gas, and the metal-containing precursor gas is transported to the top of the seed crystal 311 through the first outlet pipe 11.

[0139] Preferably, the metal precursor gas is gallium chloride. An additional carrier gas can be provided to transport the gallium chloride through the first outlet pipe 11 and above the seed crystal 311, stabilizing the airflow field and preventing localized airflow turbulence. Preferably, the carrier gas is an inert gas or nitrogen to avoid reaction with gallium chloride.

[0140] Gallium chloride can be formed by reacting a reaction gas with liquid gallium metal in gallium boat 52 at high temperature, and the reaction gas is preferably hydrogen chloride.

[0141] In this embodiment, the second vent pipe 12 is also disposed above the base 31. The second vent pipe 12 can be disposed within the growth chamber 30, and directly or indirectly connected and fixed to the chamber wall of the growth chamber 30, so that the second vent pipe 12 and the base 31 are arranged vertically from high to low. Alternatively, the main body of the second vent pipe 12 can be disposed outside the growth chamber 30, with only the vent end of the second vent pipe 12 disposed within the growth chamber 30, so that the second vent pipe 12 and the base 31 are arranged vertically from high to low.

[0142] The number of second vent pipes 12 can be one or more. When multiple second vent pipes 12 are provided, the axial directions of each second vent pipe 12 can be arranged parallel to each other, or the axial directions of a portion of the second vent pipes 12 can be set to have an included angle, so that this portion of the second vent pipes 12 is relatively inclined.

[0143] The outlet end of the second vent pipe 12 is positioned facing the base 31 to provide nitrogen-containing precursor gas above the seed crystal 311 on the base 31. Preferably, the second vent pipe 12 is made of quartz material to avoid reaction between the second vent pipe 12 and the nitrogen-containing precursor gas, while suppressing the diffusion of the nitrogen-containing precursor gas from the second vent pipe 12 to the outside as much as possible.

[0144] The second vent pipe 12 can be set perpendicular to the upper surface of the seed crystal 311, or it can be set at an angle so that the axial direction of the second vent pipe 12 is at an angle to the upper surface of the seed crystal 311.

[0145] For example, the inlet end of the second outlet pipe 12 can be directly or indirectly connected to a nitrogen-containing precursor gas source. The nitrogen-containing precursor gas source provides nitrogen-containing precursor gas, which is transported through the second outlet pipe 12 to the top of the seed crystal 311 and reacts with the metal-containing precursor gas to grow a nitrogen-containing metal layer.

[0146] Preferably, the nitrogen-containing metal layer is a gallium nitride layer, the metal-containing precursor gas is gallium chloride, and the nitrogen-containing precursor gas is ammonia. Ammonia reacts with gallium chloride at high temperature to form single-crystal gallium nitride.

[0147] In this embodiment, the second exhaust pipe 12 is arranged side by side with the first exhaust pipe 11. This effectively increases the difficulty of the pre-reaction between the metal-containing precursor gas diffusing from the first exhaust pipe 11 and the nitrogen-containing precursor gas diffusing from the second exhaust pipe 12.

[0148] Preferably, the second vent pipe 12 is disposed on one radial side of the first vent pipe 11. At least a portion of the two vent pipes can be configured to have an included angle along their axial directions. Preferably, the two vent pipes are arranged parallel to each other along their axial directions, extending in parallel throughout their lengths, with their ends aligned with the seed crystal 311 on the base 31, achieving a fixed-point convergence reaction of the gas sources. The axial lengths of the two vent pipes can be equal or unequal.

[0149] In this embodiment, the protective tube 20 is also disposed above the base 31. The protective tube 20 can be disposed inside the growth chamber 30 and directly or indirectly connected and fixed to the chamber wall of the growth chamber 30. Alternatively, the main body of the protective tube 20 can be disposed outside the growth chamber 30, with only the air outlet end of the protective tube 20 disposed inside the growth chamber 30.

[0150] Reference Figure 3 and Figure 5 As shown, the protective pipe 20 is disposed outside the first vent pipe 11 and the second vent pipe 12. There can be one or more protective pipes 20, and there are various ways to arrange the protective pipes 20.

[0151] Taking a first vent pipe 11 and a second vent pipe 12 as an example: a protective pipe 20 with a larger inner diameter can be set up to house both types of vent pipes; alternatively, a separate protective pipe 20 can be set up for each type of vent pipe.

[0152] Taking two first vent pipes 11 and two second vent pipes 12 as examples: a protective pipe 20 with a larger inner diameter can be set up, and all two types of vent pipes can be placed inside the protective pipe 20; a protective pipe 20 can be set outside the two first vent pipes 11; a protective pipe 20 can be set outside the two second vent pipes 12; a protective pipe 20 can be set outside one first vent pipe 11 and one second vent pipe 12; a protective pipe 20 can be set outside one first vent pipe 11; a protective pipe 20 can be set outside one second vent pipe 12.

[0153] Preferably, the axial directions of each tube are set to be parallel to each other. The axial length of the protective tube 20 may be equal to or different from the length of its internal tube.

[0154] In this embodiment, the protective tube 20 is used to introduce a protective gas. The protective gas can isolate the metal-containing precursor gas and the nitrogen-containing precursor gas, and can suppress the metal-containing precursor gas diffusing from the side wall of the first outlet tube 11 and the nitrogen-containing precursor gas diffusing from the side wall of the second outlet tube 12 from undergoing a pre-reaction to generate pre-reaction products.

[0155] For example, protective gas can be pre-filled into the protective tube 20; or the air inlet of the protective tube 20 can be directly or indirectly connected to a protective gas source, which continuously provides protective gas.

[0156] Preferably, the pre-reaction product is polycrystalline gallium nitride, and the protective gas is hydrogen chloride. Compared to nitrogen, choosing hydrogen chloride as the protective gas can suppress the pre-reaction without prolonged high-speed introduction, resulting in better protection.

[0157] On the one hand, the enrichment of hydrogen chloride in the protective gas cavity can isolate gallium chloride and ammonia. On the other hand, according to Le Chatelier's principle of chemical reactions, hydrogen chloride can also strongly inhibit the formation of pre-reaction products, significantly reducing the formation rate of primary polycrystalline material on the outer wall of the pipeline from the source, and essentially eliminating parasitic reactions.

[0158] On the other hand, even if a small amount of polycrystalline gallium nitride particles are generated due to diffusion, the hydrogen chloride in the protective gas cavity can still react with the newly formed loose polycrystalline gallium nitride particles to decompose them into gaseous gallium chloride and ammonia in real time.

[0159] Preferably, the protective tube 20 is made of quartz material to avoid the reaction between the protective tube 20 and the metal-containing precursor gas, the nitrogen-containing precursor gas, and the protective gas.

[0160] In this embodiment, the protective tube 20 is sealed relative to the area where the seed crystal 311 is located to prevent unreacted protective gas from corroding the nitrogen-containing metal layer on the seed crystal 311, ensuring that it will not affect the single crystal growth reaction in the growth area of ​​the seed crystal 311 and has no negative interference with the final gallium nitride single crystal quality.

[0161] For example, the protective tube 20 can be connected to a conduit, and the protective gas in the protective tube 20 can be directly led to the outside of the growth chamber 30 through the conduit. In the case of multiple protective tubes 20, each protective tube 20 can be provided with an independent conduit, or the conduit can be provided with multiple interfaces, each interface being connected to one protective tube 20.

[0162] In this embodiment, the lengths of the first vent pipe 11 and the second vent pipe 12 within the growth chamber 30 are both less than or equal to the length of the protective pipe 20 within the growth chamber 30. This can be understood as the venting end of the protective pipe 20 being flush with or protruding from the venting end of the first vent pipe 11, and the venting end of the protective pipe 20 being flush with or protruding from the venting end of the second vent pipe 12. This ensures that the venting ends of both vent pipes are protected by a protective gas, preventing pre-reaction of the metal-containing precursor gas and the nitrogen-containing precursor gas near the venting ends.

[0163] The controller, not shown in the figure, is connected to the first outlet pipe 11, the second outlet pipe 12, and the protective pipe 20. The controller is used to control the flow rates of the metal-containing precursor gas, the nitrogen-containing precursor gas, and the protective gas, respectively. For example, a control valve can be installed on the protective pipe 20 or the pipeline containing the protective pipe 20, and the controller can be electrically connected to it. The controller can then adjust the opening of the control valve to achieve flow regulation.

[0164] In summary, the HVPE equipment provided by this invention arranges the first outlet pipe 11 and the second outlet pipe 12 side by side, increasing the difficulty of the pre-reaction of the metal-containing precursor gas diffusing from the side wall of the first outlet pipe 11 and the nitrogen-containing precursor gas diffusing from the side wall of the second outlet pipe 12. Simultaneously, a protective pipe 20 is provided outside the first outlet pipe 11 and the second outlet pipe 12. The protective pipe 20 contains a protective gas, which can isolate the metal-containing precursor gas and the nitrogen-containing precursor gas, inhibiting the pre-reaction of the two precursor gases to form pre-reaction products. It can also undergo an etching reaction with the polycrystalline gallium nitride particles generated during the pre-reaction, decomposing them in real time.

[0165] In this way, the formation of parasitic polycrystalline material can be blocked at the source, avoiding the problem of deposition and blockage on the outer wall of the pipeline, extending the continuous growth time of the equipment, reducing the frequency of downtime for cleaning and maintenance, reducing the operation and maintenance costs and time costs of industrial mass production, and adapting to long-term, large-scale industrial growth scenarios.

[0166] Secondly, it can stabilize the growth airflow field, eliminate defects such as pits, dislocations, stacking faults, and mixed crystals caused by polycrystalline particles falling off, improve the flatness of the crystal surface and the integrity of crystallization, reduce the dislocation density, ensure the yield, performance and mass production stability of finished products, and can meet the substrate requirements of high-end optoelectronic devices and power devices.

[0167] Finally, only adjustments to the piping and gas path structure are required; no modifications to the original furnace, temperature control, or growth process are necessary. It is compatible with conventional hydride vapor phase epitaxy equipment, resulting in low modification costs, strong feasibility, and high value for large-scale deployment. It is particularly suitable for the large-scale preparation of large-size, low-dislocation, high-quality gallium nitride single crystals and epitaxial thin films.

[0168] In some embodiments, refer to Figure 3As shown, the protective pipe 20 includes a first protective sub-pipe 21 and a second protective sub-pipe 22. The first protective sub-pipe 21 is sleeved outside the first vent pipe 11, and the second protective sub-pipe 22 is sleeved outside the second vent pipe 12.

[0169] Compared to the structure in which the first exhaust pipe 11 and the second exhaust pipe 12 are set in the protective pipe 20, the two exhaust pipes are set with independent protective sub-pipes. The protective sub-pipes themselves have a certain physical isolation effect, which can suppress the pre-reaction of the two precursor gases.

[0170] In addition, this structure can regulate the airflow distribution, so that the gases do not cross-contaminate and the flow rate is independently controllable. This avoids gas source disturbance and local airflow unevenness caused by gas diffusion, and achieves high consistency in thickness and performance of gallium nitride growth across the entire wafer and furnace, thereby improving the yield and batch stability of finished products.

[0171] Preferably, the first protective sub-tube 21 is coaxially arranged with the first vent pipe 11, and the second protective sub-tube 22 is coaxially arranged with the second vent pipe 12.

[0172] Specifically, the outlet pipe of the first protective sub-pipe 21 can be flush with or protrude from the outlet end of the first outlet pipe 11, thereby protecting the outlet end of the first outlet pipe 11 and preventing the metal-containing precursor gas from undergoing pre-reaction near the outlet end of the first outlet pipe 11, thus ensuring good finished product yield, performance, and mass production stability.

[0173] Similarly, the outlet pipe of the second protective sub-pipe 22 can be flush with or protrude from the outlet end of the second outlet pipe 12, thereby protecting the outlet end of the second outlet pipe 12 and preventing the nitrogen-containing precursor gas from undergoing pre-reaction near the outlet end of the second outlet pipe 12, ensuring good product yield, performance and mass production stability.

[0174] Preferably, the vent pipe of the first protective sub-pipe 21 is flush with the vent end of the first vent pipe 11, and the vent pipe of the second protective sub-pipe 22 is flush with the vent end of the second vent pipe 12 to achieve a better protective effect.

[0175] In some embodiments, refer to Figure 3 As shown, at least one of the four types of pipe walls—the outer wall of the first vent pipe 11, the inner wall of the first protective sub-pipe 21, the outer wall of the second vent pipe 12, and the inner wall of the second protective sub-pipe 22—is provided with a flow guide 23.

[0176] For example, the guide 23 can be provided only on the outer wall of the first vent pipe 11, only on the inner wall of the first protective sub-pipe 21, only on the outer wall of the second vent pipe 12, or only on the inner wall of the second protective sub-pipe 22; the guide 23 can also be provided on two or three of the four types of pipe walls; of course, the guide 23 can also be provided on all four types of pipe walls.

[0177] The guide element 23 can be configured as a raised structure, a grooved structure, or a spiral structure. In this way, the guide element 23 can be used to guide the protective gas, so that the protective gas evenly covers the corresponding gas outlet pipe, eliminates protection dead corners, and ensures that all outer wall areas of the gas outlet pipe are within the coverage of the protective gas.

[0178] Preferred, refer to Figure 3 As shown, the difference a1 between the radius of the first protective sub-pipe 21 and the radius of the first outlet pipe 11 satisfies the relationship: 1mm≤a1≤2mm. The difference a1 should not be too small to avoid affecting the flow rate of the protective gas; nor should the difference a1 be too large to avoid affecting the pipe diameter of the first outlet pipe 11 and thus the flow rate of the metal-containing precursor gas.

[0179] For example, the difference a1 can be set to 1mm, 1.1mm, 1.2mm, 1.3mm, 1.4mm, 1.5mm, 1.6mm, 1.7mm, 1.8mm, 1.9mm or 2mm, etc.

[0180] Similarly, the difference a2 between the radius of the second protective sub-pipe 22 and the radius of the second outlet pipe 12 satisfies the relationship: 1mm≤a2≤2mm. The difference a2 should not be too small to avoid affecting the flow rate of the protective gas; nor should it be too large to avoid affecting the diameter of the second outlet pipe 12 and thus the flow rate of the nitrogen-containing precursor gas.

[0181] For example, the difference a2 can be set to 1mm, 1.1mm, 1.2mm, 1.3mm, 1.4mm, 1.5mm, 1.6mm, 1.7mm, 1.8mm, 1.9mm or 2mm, etc.

[0182] Preferred, refer to Figure 3 As shown, along the radial direction of the pipe containing the guide element 23, the dimension b of the guide element 23 satisfies the relationship: 0.2mm ≤ b ≤ 0.5mm. The dimension b should not be too small to avoid failing to provide an effective flow guiding effect; nor should the dimension b be too large to avoid affecting the flow rate of the protective gas.

[0183] For example, the dimension b can be set to 0.2mm, 0.3mm, 0.4mm or 0.5mm, etc.

[0184] In some embodiments, refer to Figure 2 and Figure 4 As shown, the HVPE device also includes an intake chamber 40.

[0185] The air intake chamber 40 is located above and connected to the growth chamber 30. The air intake ends of the first air outlet pipe 11, the second air outlet pipe 12, and the protective pipe 20 are all located inside the air intake chamber 40.

[0186] It is understood that the HVPE equipment described in this invention requires at least one first outlet pipe 11, one second outlet pipe 12, and one protective pipe 20. In actual production, the number of each pipe is usually set to multiple. Based on this, the air inlet end of each pipe is set inside the air inlet chamber 40 for integrated processing.

[0187] In some embodiments, refer to Figure 2 and Figure 4 As shown, a first partition 41 is provided inside the air intake cavity 40, which divides the air intake cavity 40 into a first cavity 401 and a second cavity 402. The first partition 41 can be integrally formed with the air intake cavity 40; alternatively, the air intake cavity 40 and the first partition 41 can be separate parts, then assembled to achieve a sealed connection.

[0188] Multiple first exhaust pipes 11 are provided to ensure a more uniform distribution of the metal-containing precursor gas. For each first exhaust pipe 11, the first exhaust pipe 11 is at least partially disposed within the second cavity 402, the first exhaust pipe 11 is sealed to the first partition 41, and the air inlet end of the first exhaust pipe 11 is connected to the first cavity 401.

[0189] For example, the first vent pipe 11 can be entirely disposed within the second cavity 402; or a portion of the first vent pipe 11 can be disposed within the second cavity 402 along its axial direction, and the other portion can be disposed within the growth cavity 30; or the first vent pipe 11 can be sequentially divided into three parts along its axial direction, with the first part disposed within the first cavity 401, the second part disposed within the second cavity 402, and the third part disposed within the growth cavity 30.

[0190] A sealing ring can be installed at the connection between the first vent pipe 11 and the corresponding component to achieve a seal and prevent gas leakage.

[0191] Similarly, multiple second exhaust pipes 12 are provided to ensure a more uniform distribution of the nitrogen-containing precursor gas. For each second exhaust pipe 12, the second exhaust pipe 12 is sealed to the air inlet chamber 40, and the air inlet end of the second exhaust pipe 12 is connected to the second cavity 402.

[0192] For example, the second vent pipe 12 can be entirely disposed within the growth chamber 30; alternatively, a portion of the second vent pipe 12 can be disposed axially within the second cavity 402, and the other portion can be disposed axially within the growth chamber 30.

[0193] A sealing ring can be installed at the connection between the second vent pipe 12 and the corresponding component to achieve a seal and prevent gas leakage.

[0194] In some embodiments, refer to Figure 2 and Figure 4 As shown, the protective tube 20 includes multiple first protective sub-tubes 21 and multiple second protective sub-tubes 22. The first protective sub-tubes 21 are configured in a one-to-one correspondence with the first vent tube 11, and the second protective sub-tubes 22 are configured in a one-to-one correspondence with the second vent tube 12.

[0195] A second partition 42 is provided inside the first cavity 401, dividing the first cavity 401 into a first front-drive air cavity 4011 and a first protective air cavity 4012. The second partition 42 can be integrally formed with the air intake cavity 40; alternatively, the air intake cavity 40 and the second partition 42 can be separate parts, then assembled to achieve a sealed connection.

[0196] In this embodiment, the inlet end of the first pre-drive air chamber 4011 is used to receive metal-containing pre-drive gas, and the inlet ends of all the first outlet pipes 11 are connected to the first pre-drive air chamber 4011. The inlet end of the first protective air chamber 4012 is used to receive protective gas, and the inlet ends of all the first protective sub-pipes 21 are connected to the first protective air chamber 4012.

[0197] Preferably, the first precursor gas chamber 4011 is disposed above the first protective gas chamber 4012 so as to isolate the first precursor gas chamber 4011 and the second cavity 402 through the first protective gas chamber 4012, thereby preventing the metal-containing precursor gas from diffusing from the cavity wall of the first precursor gas chamber 4011 and reacting with the nitrogen-containing precursor gas.

[0198] For example, the first vent pipe 11 can be divided into four parts along the axial direction. The first part includes the air inlet end of the first vent pipe 11, and the fourth part includes the air outlet end of the first vent pipe 11. Specifically, the first part can be set in the first pre-drive air chamber 4011, the second part can be set in the first protective air chamber 4012, the third part can be set in the second cavity 402, and the fourth part can be set in the growth chamber 30.

[0199] During operation, the metal-containing precursor gas is introduced into the first precursor gas chamber 4011, then into different first gas outlet pipes 11, and finally into the growth chamber 30 to react with the nitrogen-containing precursor gas.

[0200] Similarly, the first protective sub-tube 21 can be divided into three parts along the axial direction. The first part includes the air inlet end of the first protective sub-tube 21, and the third part includes the air outlet end of the first protective sub-tube 21. The first part can be set in the first protective air chamber 4012, the second part can be set in the second cavity 402, and the third part can be set in the growth chamber 30.

[0201] During operation, the protective gas is introduced into the first protective gas chamber 4012, and then into different first protective sub-tubes 21 to isolate the two precursor gases and inhibit the pre-reaction of the two precursor gases.

[0202] Similarly, a third partition 43 is provided inside the second cavity 402, which divides the second cavity 402 into a second front-drive air chamber 4021 and a second protective air chamber 4022. The third partition 43 can be integrally formed with the air intake chamber 40; alternatively, the air intake chamber 40 and the second partition 42 can be separate parts, then assembled to achieve a sealed connection.

[0203] In this embodiment, the inlet end of the second precursor gas chamber 4021 is used to receive nitrogen-containing precursor gas, and the inlet ends of all the second outlet pipes 12 are connected to the second precursor gas chamber 4021. The inlet end of the second protective gas chamber 4022 is used to receive protective gas, and the inlet ends of all the second protective sub-pipes 22 are connected to the second protective gas chamber 4022.

[0204] Preferably, the second precursor gas chamber 4021 is disposed above the second protective gas chamber 4022 so as to isolate the second precursor gas chamber 4021 and the growth chamber 30 through the second protective gas chamber 4022, thereby preventing the nitrogen-containing precursor gas from diffusing from the cavity wall of the second precursor gas chamber 4021 and pre-reacting with the metal-containing precursor gas in the growth chamber 30.

[0205] For example, the second vent pipe 12 can be divided into three parts along the axial direction. The first part includes the air inlet of the second vent pipe 12, and the third part includes the air outlet of the second vent pipe 12. The first part can be located in the second pre-drive air chamber 4021, the second part can be located in the second protective air chamber 4022, and the third part can be located in the growth chamber 30.

[0206] During operation, nitrogen-containing precursor gas is introduced into the second precursor gas chamber 4021, then into different second outlet pipes 12, and finally into the growth chamber 30 to react with the metal-containing precursor gas.

[0207] Similarly, the second protective sub-tube 22 can be divided into two parts along the axial direction. The first part includes the air inlet end of the second protective sub-tube 22, and the second part includes the air outlet end of the second protective sub-tube 22. The first part can be set inside the second protective air chamber 4022, and the second part can be set inside the growth chamber 30.

[0208] During operation, the protective gas is introduced into the second protective gas chamber 4022, and then into different second protective sub-tubes 22 to isolate the two precursor gases and inhibit the pre-reaction of the two precursor gases.

[0209] This structure effectively prevents the gas inside the intake chamber 40 and each pipe from diffusing outwards, while also effectively isolating external stray atmospheres, stabilizing the airflow field around the pipeline, and further helping to reduce the probability of parasitic reactions. During operation, the gases do not cross-contaminate, effectively achieving isolation between the protective function and the gas transport function.

[0210] It should be noted that the first exhaust pipe 11 can be integrally formed with the air intake chamber 40 and each partition, or the components can be set separately and then assembled to achieve a sealed connection.

[0211] Similarly, the second exhaust pipe 12 can be integrally formed with the intake chamber 40 and each partition, or the components can be set separately and then assembled to achieve a sealed connection.

[0212] In some embodiments, the first protective sub-tube 21 in the protective tube 20 is detachably connected to the air intake chamber 40.

[0213] For example, the first protective sub-tube 21 can be detachably connected to the second partition 42, the first partition 41, the third partition 43, and the air intake chamber 40, respectively. Detachability can be achieved through snap-fit ​​connections, fasteners, or other methods.

[0214] Based on this, the diameter of the first protective sub-pipe 21 can be flexibly adjusted according to actual needs to achieve flow restriction. Preferably, sealing rings are provided at the connection points between the first protective sub-pipe 21 and each component to achieve a sealed connection.

[0215] Similarly, in some embodiments, the second protective sub-tube 22 in the protective tube 20 is detachably connected to the air intake chamber 40. For example, the bottom plate of the air intake chamber 40 can be detachably connected to the first protective sub-tube 21. This detachability can be achieved through snap-fit ​​connections, fasteners, or other methods.

[0216] Based on this, the diameter of the second protective sub-pipe 22 can be flexibly adjusted according to actual needs to achieve flow restriction. Preferably, a sealing ring is provided at the connection between the second protective sub-pipe 22 and the air intake chamber 40 to achieve a sealed connection.

[0217] In some embodiments, refer to Figure 2As shown, the protective tube 20 also includes an exhaust sub-tube 24. The air inlet of the exhaust sub-tube 24 is connected to the air outlet of the first protective sub-tube 21 and the air outlet of the second protective sub-tube 22, respectively, and the air outlet of the exhaust sub-tube 24 is connected to the outside of the growth chamber 30.

[0218] In this embodiment, by providing an exhaust sub-pipe 24, the two protective sub-pipes can be isolated from the growth chamber 30, preventing protective gas from entering the growth chamber 30 and corroding the nitrogen-containing metal layer, thus ensuring high quality of the final product. In other embodiments, independent conduits can be provided for the two protective sub-pipes to achieve exhaust.

[0219] In some embodiments, the HVPE equipment of the present invention further includes a control valve electrically connected to the controller. The control valve is not shown in the figures; exemplarily, the control valve can be located in the protective tube 20. For example, an independent control valve can be provided for each first protective sub-tube 21 and each second protective sub-tube 22. In this way, the flow rate of the protective gas can be controlled by the control valve to achieve a constant flow input.

[0220] For example, the flow rate of the protective gas can be controlled within the range of 50 to 200 sccm, and dynamically adjusted according to actual needs. Here, sccm stands for standard cubic centimeters per minute, and 1 sccm equals 1 milliliter per minute. Requirements related to the adjustment of the protective gas flow rate include pipe spacing, gas source flow rate, and the stage of the nitrogen-containing metal layer growth process.

[0221] The growth process of the nitrogen-containing metal layer includes a growth heating stage, an isothermal growth stage, and a cooling stage connected in sequence.

[0222] During the growth and heating phase, the control valve is used to control the flow rate of the protective gas between 50 sccm and 60 sccm. For example, the flow rate can be set to 50 sccm, 51 sccm, 52 sccm, 53 sccm, 54 sccm, 55 sccm, 56 sccm, 57 sccm, 58 sccm, 59 sccm, 60 sccm, etc.

[0223] In this way, by establishing a protective atmosphere in advance with a low flow rate of protective gas, the protective gas can preferentially react with gallium nitride or gallium that may remain on the pipe wall, forming a protective environment and preventing these residues from contaminating or clogging the pipeline when the temperature rises.

[0224] Preferably, a certain amount of hydrogen chloride can also be introduced into the growth chamber 30 to perform micro-cleaning or activation on the surface of the seed crystal 311, in preparation for subsequent high-quality growth.

[0225] During the isothermal growth stage, the control valve is used to control the flow rate of the protective gas between 150 sccm and 200 sccm. For example, the flow rate can be set to 150 sccm, 160 sccm, 170 sccm, 180 sccm, 190 sccm, 200 sccm, etc.

[0226] Thus, by providing stable protection through a large flow of protective gas, unwanted N-face polar nucleation is suppressed, promoting the growth of high-quality Ga-face polar thin films, which helps to improve the growth rate and crystal quality.

[0227] During the cooling phase, the control valve is used to control the flow rate of the protective gas between 80 sccm and 120 sccm. For example, the flow rate can be set to 80 sccm, 90 sccm, 100 sccm, 110 sccm, 120 sccm, etc.

[0228] Thus, residual nascent polycrystalline material in the pipeline is removed by a medium flow rate of protective gas. At the beginning of cooling, the temperature is relatively high, resulting in a relatively large amount of gallium nitride polycrystalline products formed by gas diffusion. Therefore, setting the flow rate of the protective gas introduced during the cooling stage to be greater than that introduced during the growth heating stage, but less than that introduced during the isothermal growth stage, effectively achieves corrosion without introducing excessive risks during cooling due to excessive flow rate.

[0229] In some embodiments, refer to Figure 2 and Figure 4 As shown, the HVPE device also includes a first air source chamber 50 and a second air source chamber 60, both of which are located on one side of the air intake chamber 40.

[0230] Preferably, two gas source chambers are placed outside the growth chamber 30, and heaters 32 are placed outside the two gas source chambers so that heating can be carried out by the heaters 32 to meet the high temperature conditions required for the reaction.

[0231] A fourth partition 51 is provided inside the first air source cavity 50, which divides the first air source cavity 50 into a first air source sub-cavity 501 and a second air source sub-cavity 502. Alternatively, the fourth partition 51 can be integrally formed with the first air source cavity 50; or the first air source cavity 50 and the fourth partition 51 can be separate parts, then assembled to achieve a sealed connection.

[0232] In this embodiment, a gallium boat 52 is provided inside the first gas source cavity 501. For example, the gallium boat 52 can be placed on the fourth partition 51.

[0233] Gallium boat 52 is used to hold liquid gallium metal. A reaction gas is introduced into the first gas source cavity 501, and the reaction gas reacts with the liquid gallium metal in gallium boat 52 to generate a metal precursor gas. Preferably, the reaction gas is hydrogen chloride.

[0234] Thus, the metal-containing precursor gas is introduced into the inlet end of the first precursor gas chamber 4011 so that the metal-containing precursor gas flows through the first outlet pipe 11 and is discharged, reacting with the nitrogen-containing precursor gas.

[0235] Correspondingly, the second gas source chamber 502 is used to introduce protective gas into the first protective gas chamber 4012 in order to provide isolation protection for the first gas outlet pipe 11.

[0236] Similarly, a fifth partition 61 is provided inside the second air source cavity 60, which divides the second air source cavity 60 into a third air source sub-cavity 601 and a fourth air source sub-cavity 602. The fifth partition 61 can be integrally formed with the second air source cavity 60; alternatively, the second air source cavity 60 and the fifth partition 61 can be separate parts, then assembled to achieve a sealed connection.

[0237] The third gas source chamber 601 is used to introduce nitrogen-containing precursor gas to the inlet end of the second precursor gas chamber 4021 so that the nitrogen-containing precursor gas flows through the second outlet pipe 12 and is discharged, reacting with the metal-containing precursor gas.

[0238] Correspondingly, the fourth gas source chamber 602 is used to introduce protective gas into the second protective gas chamber 4022 in order to provide isolation protection for the second gas outlet pipe 12.

[0239] The working principle of the solution provided by this invention will be explained below using gallium chloride as the metal precursor gas, ammonia as the nitrogen precursor gas, and hydrogen chloride as the protective gas as an example: A seed crystal 311 is placed on a base 31 in the growth chamber 30, while two precursor gases are prepared. On one hand, a gallium boat 52 containing liquid gallium is placed in the first gas source sub-cavity 501. Hydrogen chloride and a carrier gas are introduced into the first gas source sub-cavity 501. The hydrogen chloride reacts with the liquid gallium under the heating of the heater 32 to generate gallium chloride. The gallium chloride flows into the first precursor gas chamber 4011 under the action of the carrier gas and enters different first outlet pipes 11. On the other hand, ammonia is introduced into the third gas source sub-cavity 601. The ammonia flows into the second precursor gas chamber 4021 and enters different second outlet pipes 12.

[0240] Simultaneously, hydrogen chloride is introduced into the second gas source sub-cavity 502 and the fourth gas source sub-cavity 602, respectively. The hydrogen chloride from the second gas source sub-cavity 502 flows into the first protective gas cavity 4012 and enters different first protective sub-pipes 21, providing isolation protection for the corresponding first outlet pipes 11. The hydrogen chloride from the fourth gas source sub-cavity 602 flows into the second protective gas cavity 4022 and enters different second protective sub-pipes 22, providing isolation protection for the corresponding second outlet pipes 12.

[0241] In this way, hydrogen chloride can isolate gallium chloride and ammonia, and inhibit the pre-reaction of the two precursor gases. Even if the two pre-react and form polycrystalline gallium nitride, hydrogen chloride can still perform an etching reaction to decompose the polycrystalline gallium nitride into gaseous gallium chloride and ammonia. The hydrogen chloride discharged from the first protective sub-tube 21 and the second protective sub-tube 22 is discharged from the growth chamber 30 through the exhaust sub-tube 24 to prevent it from corroding the gallium nitride layer.

[0242] Gallium chloride discharged from the first outlet pipe 11 reacts with ammonia gas discharged from the second outlet pipe 12, growing a gallium nitride layer on the upper surface of the seed crystal 311. During this process, the heater 32 outside the growth chamber 30 and the heater 32 on the lower surface of the base 31 are controlled to meet the required growth temperature conditions. At different stages of the gallium nitride layer growth process, the flow rate of the protective gas can be adjusted by controlling valves.

[0243] After the gallium nitride layer grows to the required thickness, the heater 32 is controlled to cool down and anneal until it reaches room temperature, at which point the finished product is obtained.

[0244] For ease of description, spatial relative terms such as "above," "on top of," "on the upper surface of," "above," etc., are used herein to describe the spatial positional relationship of a device or feature as shown in the figures to other devices or features. It should be understood that spatial relative terms are intended to encompass different orientations in use or operation beyond the orientation of the device as described in the figures. For example, if the device in the figures were inverted, a device described as "above" or "on top of" other devices or structures would subsequently be positioned as "below" or "under" other devices or structures. Thus, the exemplary term "above" can include both "above" and "below." The device may also be positioned in other different ways (rotated 90 degrees or in other orientations), and the spatial relative descriptions used herein will be interpreted accordingly.

[0245] Furthermore, it should be noted that the use of terms such as "first" and "second" to define components is merely for the purpose of distinguishing the corresponding components. Unless otherwise stated, the above terms have no special meaning and therefore should not be construed as limiting the scope of protection of this invention.

[0246] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for growing a semiconductor substrate based on an HVPE device, characterized in that, The HVPE equipment includes a growth chamber, a first vent pipe, a second vent pipe, and a protective tube. A seed crystal is disposed within the growth chamber. The second vent pipe is arranged parallel to the first vent pipe. The protective tube is disposed around the first and second vent pipes. The method includes: Metal-containing precursor gas and nitrogen-containing precursor gas are respectively supplied to the top of the seed crystal through the first gas outlet pipe and the second gas outlet pipe, so that the metal-containing precursor gas and the nitrogen-containing precursor gas react to generate a nitrogen-containing metal layer, thereby obtaining a semiconductor substrate; While the metal-containing precursor gas and the nitrogen-containing precursor gas are introduced above the seed crystal, a protective gas is introduced into the protective tube to suppress the pre-reaction of the metal-containing precursor gas diffusing from the side wall of the first outlet pipe and the nitrogen-containing precursor gas diffusing from the side wall of the second outlet pipe to generate pre-reaction products; wherein, the lengths of the first outlet pipe and the second outlet pipe within the growth chamber are both less than or equal to the length of the protective tube within the growth chamber, and the protective tube is sealed relative to the area where the seed crystal is located.

2. The growth method according to claim 1, characterized in that, During the growth of the nitrogen-containing metal layer, the flow rate of the protective gas changes in a stepwise manner.

3. The growth method according to claim 2, characterized in that, During the growth of the nitrogen-containing metal layer, the flow rate of the protective gas first increases and then decreases; And / or, the flow rate of the protective gas is from 50 sccm to 200 sccm.

4. The growth method according to claim 3, characterized in that, The growth process of the nitrogen-containing metal layer includes a sequential growth heating stage, an isothermal growth stage, and a cooling stage. The method specifically includes: During the growth and heating stage, the flow rate of the protective gas is controlled at a first set flow rate; wherein, the first set flow rate is 50 sccm to 60 sccm. During the isothermal growth stage, the flow rate of the protective gas is controlled at a second set flow rate; wherein the second set flow rate is 150 sccm to 200 sccm. During the cooling phase, the flow rate of the protective gas is controlled at a third set flow rate; wherein the third set flow rate is 80 sccm to 120 sccm.

5. The growth method according to claim 1, characterized in that, The protective tube includes a first protective sub-tube and a second protective sub-tube, the first protective sub-tube being sleeved outside the first vent pipe, and the second protective sub-tube being sleeved outside the second vent pipe; the method specifically includes: A protective gas is introduced into the first protective sub-tube to suppress the pre-reaction between the nitrogen-containing precursor gas and the metal-containing precursor gas diffusing from the side wall of the first outlet tube. A protective gas is introduced into the second protective sub-tube to suppress the pre-reaction between the metal-containing precursor gas and the nitrogen-containing precursor gas diffusing from the side wall of the second outlet tube.

6. The growth method according to claim 5, characterized in that, The HVPE equipment further includes an air inlet chamber, which is disposed above and communicates with the growth chamber. The air inlet chamber includes a first cavity and a second cavity, which are separated. The first cavity includes a first precursor air cavity and a first protective air cavity, which are separated. The second cavity includes a second precursor air cavity and a second protective air cavity, which are separated. Multiple first air outlet pipes are provided, and at least part of the first air outlet pipes are disposed in the second cavity. The air inlet ends of all the first air outlet pipes are communicated with the first precursor air cavity. Multiple second air outlet pipes are provided, and the air inlet ends of all the second air outlet pipes are communicated with the second precursor air cavity. The protective pipe includes multiple first protective sub-pipes and multiple second protective sub-pipes. The air inlet ends of all the first protective sub-pipes are communicated with the first protective air cavity, and the air inlet ends of all the second protective sub-pipes are communicated with the second protective air cavity. Before supplying the metal-containing precursor gas and the nitrogen-containing precursor gas to the top of the seed crystal through the first gas outlet pipe and the second gas outlet pipe respectively, the method further includes: The metal-containing precursor gas is introduced into all the first outlet pipes through the first precursor gas chamber; The nitrogen-containing precursor gas is introduced into all the second outlet pipes through the second precursor gas chamber; Before introducing the protective gas into the protective tube, the procedure also includes: The protective gas is introduced into all the first protective sub-tubes through the first protective gas chamber; The protective gas is introduced into all the second protective sub-tubes through the second protective gas chamber.

7. The growth method according to claim 6, characterized in that, The HVPE device further includes a first gas source cavity, which is disposed on one side of the air inlet cavity; the first gas source cavity includes a separated first gas source sub-cavity and a second gas source sub-cavity, and a gallium boat is disposed in the first gas source sub-cavity. Before introducing the metal-containing precursor gas into the first precursor gas chamber, the method further includes: The reaction gas is introduced into the first gas source sub-cavity, and the reaction gas reacts with the liquid gallium metal in the gallium boat to generate the metal-containing precursor gas, and the metal-containing precursor gas in the first gas source sub-cavity is introduced into the first precursor gas cavity. And / or, before introducing the protective gas into the first protective gas chamber, the method further includes: The protective gas is introduced into the first protective gas chamber through the second gas source sub-chamber.

8. The growth method according to claim 6, characterized in that, The HVPE equipment further includes a second air source chamber, which is disposed on one side of the air inlet chamber; the second air source chamber includes a separated third air source sub-chamber and a fourth air source sub-chamber; Before introducing the nitrogen-containing precursor gas into the second precursor gas chamber, the process also includes: The nitrogen-containing precursor gas is introduced into the second precursor gas chamber through the third gas source sub-chamber; And / or, before introducing the protective gas into the second protective gas chamber, the method further includes: The protective gas is introduced into the second protective gas chamber through the fourth gas source sub-chamber.

9. A semiconductor substrate, characterized in that, The semiconductor substrate is prepared using the semiconductor substrate growth method based on HVPE equipment as described in any one of claims 1-8.

10. An HVPE device, characterized in that, For growing a semiconductor substrate, the semiconductor substrate comprising a seed crystal and a nitrogen-containing metal layer stacked together, the HVPE apparatus comprising: The growth chamber contains the seed crystal. The first gas outlet pipe is used to provide a metal-containing precursor gas to the top of the seed crystal; The second vent pipe, arranged parallel to the first vent pipe, is used to provide a nitrogen-containing precursor gas to the top of the seed crystal; wherein the metal-containing precursor gas and the nitrogen-containing precursor gas react to generate the nitrogen-containing metal layer. A protective tube is disposed around the first and second vent pipes; the lengths of the first and second vent pipes within the growth chamber are both less than or equal to the length of the protective tube within the growth chamber, and the protective tube is sealed relative to the area where the seed crystal is located; the protective tube is used to introduce protective gas to suppress the pre-reaction of the metal-containing precursor gas diffusing from the side wall of the first vent pipe and the nitrogen-containing precursor gas diffusing from the side wall of the second vent pipe to generate pre-reaction products; The controller is connected to the first outlet pipe, the second outlet pipe, and the protective pipe respectively; the controller is used to control the flow rates of the metal-containing precursor gas, the nitrogen-containing precursor gas, and the protective gas respectively.

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