Air-conditioned vapor-phase epitaxial reaction chamber, equipment and method for producing hydrides

Abstract

This invention discloses a time-controlled vapor-phase epitaxial reaction chamber, apparatus, and method for producing hydrides. The reaction chamber includes: a chamber with water-cooled sidewalls and a cavity defined by flanges, the cavity being divided into upper, middle, and lower sections; a metal source reaction boat assembly located in the upper half of the reaction chamber; a time-controlled reaction growth apparatus located in the middle of the reaction chamber; a heating device and a tail gas collection device located in the lower half of the reaction chamber; and a central gas path device located at the axial position of the reaction chamber, connecting the metal source reaction boat assembly in the upper half of the chamber and the time-controlled reaction growth apparatus in the middle of the chamber. This invention controls the growth time precisely by combining time modulation and spatial modulation, thereby increasing the flexibility of the growth program settings and enabling rapid epitaxial growth of ultra-thin and ultra-thick material stacked structures, meeting the low-cost epitaxial growth requirements of complex semiconductor devices.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of semiconductor, and particularly relates to a kind of space-time modulation hydride vapor phase epitaxy reaction chamber, hydride vapor phase epitaxy growth equipment and method. BACKGROUND

[0002] GaAs stacked solar cell is a typical representative of the third generation of new high-efficiency solar cells. III-V materials represented by GaAs have ideal direct band gap, very high light absorption coefficient and high stability, and the single-junction and multi-junction cell efficiencies are the highest among all kinds of solar cells. GaAs solar cell has high conversion efficiency, high reliability, high temperature resistance and strong anti-radiation ability, and has been widely used in remote sensing, meteorology and scientific experiment satellites, and has good on-orbit operation status, and is suitable for space orbit vehicles.

[0003] The biggest limitation of GaAs cell is the relatively high manufacturing cost, and at present it is only applied in a few fields such as space station. If the cost of III-V solar cell can be reduced by one order of magnitude, it can be applied to high-altitude long-endurance unmanned aerial vehicle system, commercial satellite and automobile industry; if the cost is reduced by more than two orders of magnitude, it can be applied to large-scale ground application. However, how to significantly reduce the cost without significantly sacrificing the efficiency is a very thorny problem. Many research institutions at home and abroad have carried out relevant research. It has been proved that the schemes such as epitaxial growth on silicon substrate and vapor phase growth on metal substrate are difficult to realize the dual goals of efficiency and cost. People must develop new theories to design the battery structure and preparation process, and solve the problem by adopting low-cost epitaxial growth technology, substrate reusable technology and new device structure.

[0004] In the low-cost epitaxy technology, a new technology of using a brand-new hydride vapor phase epitaxy (HVPE) to prepare a new type of high-efficiency III-V solar cell applicable to large-scale ground application can obtain a conversion efficiency comparable to that of a solar cell prepared by a metal organic chemical vapor deposition (MOCVD) technology. Further improvement of the technology can reduce the cost of the III-V solar cell to below 0.5 dollars per watt. Scientists of the NREL of the United States deeply analyze the film forming process of the HVPE epitaxy, and further innovatively propose a dynamic hydride vapor phase epitaxy (D-HVPE) technology, which controls the start and stop of the thin film epitaxial growth by rapid mechanical reciprocating transmission of a substrate, so as to realize high-speed growth of the thin film and fine control of a multi-layer structure. For this purpose, they design two relatively independent cavities, and divide the reaction gas into different material growth areas by a hydrogen gas curtain. In 2019, the growth rate of a GaAs epitaxial layer reached 300 μm / h, the efficiency of a single-junction GaAs cell was more than 25%, the efficiency of a single-junction GaInP cell reached 15.2%, and the efficiency of a double-junction GaInP / GaAs cell reached 24.9%. The AIST of Japan started to carry out research on the HVPE epitaxy technology of the III-V solar cell in 2016, they optimized the structure of the traditional HVPE equipment, and proposed a three-cavity design, which greatly improved the controllability of the HVPE process. In 2018, the efficiency of a GaAs solar cell prepared by the AIST reached 22.1%; in 2019, an Al source was added, and the efficiency of a double-junction solar cell prepared thereby reached 28.3%.

[0005] In addition, group III nitride semiconductors are increasingly important in the development and manufacture of visible and ultraviolet wavelength light emitting diodes (LEDs), laser diodes (LDs), and electronic devices including high power, high frequency, and high temperature transistors and integrated circuits. HVPE is also a commonly used method for depositing group III nitrides. As the demand for LEDs, LDs, transistors, and integrated circuits increases, the efficiency of depositing group III metal nitrides becomes more important. GaN-based devices, particularly LEDs and lasers, also face the problem of high growth costs. If HVPE technology can replace or be combined with existing MOCVD technology to grow devices including GaN-based thick film epitaxial layers and ultrathin quantum wells, superlattice structures, light emitting diodes, and laser diodes, the epitaxial cost can also be greatly reduced, and the performance of the devices can even be further improved. Therefore, an improved HVPE deposition method and HVPE equipment are also needed in this field for fast and low-cost deposition of these devices.

[0006] Therefore, in view of the above technical problems, it is necessary to provide a spatiotemporal modulation hydride vapor phase epitaxy reaction chamber, a hydride vapor phase epitaxy growth device, and a method.

[0007] The information disclosed in the background section is only for increasing the understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art. SUMMARY

[0008] The present application aims to provide a spatiotemporal modulation hydride vapor phase epitaxy reaction chamber, a hydride vapor phase epitaxy growth device and a method.

[0009] The present application can achieve a dynamic adjustment range of 0.01 nm / s-100 nm / s of super-large growth rate, precise control of the thickness of ultra-thin epitaxial films, super-fast growth of thick layer materials, and rapid and low-cost growth of GaAs-based multi-junction solar cells and GaN-based lasers.

[0010] To achieve the above-mentioned purpose, an embodiment of the present application provides a hydride vapor phase epitaxy (HVPE) reaction chamber. The reaction chamber is equipped with three or more metal sources, a continuously rotating gas path switching valve, and a growth zone composed of two or more independent sub-zones. When equipped with three metal sources, the reaction chamber can grow multiple layers of material thin layers containing different metals respectively, forming a stacked structure. For example, when the reaction chamber is equipped with three metal sources of gallium (Ga), aluminum (Al) and indium (In), it can epitaxially grow GaAs, InAs, AlAs, GaInAs, AlGaAs, GaN, AlN, InGaN, AlGaN, GaP, InP, AlGaInP and other material thin layers on the substrate in the same reaction chamber. On the one hand, the continuously rotating gas path switching valve can control the time when the three metal sources are introduced into the growth zone, and accurately control the thickness of each layer of material. On the other hand, the rotating or transmission mechanism is used to control the time when the substrate stays in each independent sub-growth zone, thereby accurately controlling the growth time of each layer of material and controlling the growth thickness.

[0011] The reaction chamber structure, in combination with gas path control and tail gas treatment systems, can form a new type of epitaxial growth equipment with low raw material cost, i.e., a time-space modulated hydride vapor phase epitaxy (TSM-HVPE) system. In combination with a corresponding growth process, the TSM-HVPE has the growth ability of precise control of ultra-thin material thickness and the characteristic of ultra-fast growth rate of thick layer material, and can be applied to the low-cost growth of semiconductor optoelectronic devices. The equipment in combination with a corresponding epitaxial method can realize a dynamic adjustment range of ultra-large growth rate of 0.01 nm / s to 100 nm / s, meet the rapid epitaxial growth of complex device structures based on GaAs or GaN semiconductor materials, such as multi-junction solar cells, light-emitting diodes, photodetectors, and lasers, and reduce the epitaxial cost of devices. In one possible embodiment, the TSM-HVPE reaction chamber is equipped with five metal sources. The five metal sources can respectively deliver gaseous compound precursors of gallium (Ga), indium (In), aluminum (Al), zinc (Zn), and (Mg) five metals into the reaction chamber. When these metal precursors are used to generate arsenide, an arsenic-containing gas such as AsH3 can be introduced. A continuously rotating gas path switching valve and a growth zone composed of two or more independent sub-zones can be used to accurately control the growth time of thin films containing different metals on the substrate, thereby achieving precise control of the thickness of epitaxial layers. The time modulation realized by the continuously rotating gas path switching valve can be combined with the spatial modulation realized by switching the substrate between different independent growth zones in different combinations to regulate the continuous growth of different epitaxial layers and form a stacked structure.

[0012] To achieve the above object, the technical scheme provided by a specific embodiment of the present application is as follows:

[0013] The time-space modulated hydride vapor phase epitaxy (TSM-HVPE) reaction chamber comprises:

[0014] A reaction chamber with a water-cooled side wall and a cavity defined by a flange, the cavity is divided into upper, middle and lower parts;

[0015] A metal source reaction boat assembly located in the upper half of the reaction chamber cavity, comprising a time sequence support device and a plurality of reaction boats, the time sequence support device comprises a plurality of first support bodies, any of the reaction boats is carried on any of the first support bodies, and the first outlet of the reaction boat is connected to the central gas path device;

[0016] A time-space modulated reaction growth device located in the middle part of the reaction chamber cavity;

[0017] A heating device and a tail gas collection device located in the lower half of the reaction chamber cavity;

[0018] A central gas passage device is located at the center of the chamber cavity, and connects the metal source reaction boat assembly in the upper half of the cavity and the time-space modulation reaction growth device in the middle of the cavity through the central gas passage.

[0019] In one or more embodiments of the present application, the metal source reaction boat assembly comprises:

[0020] A plurality of reaction boats, each of which has a first cavity and a second cavity formed outside the first cavity, the first cavity being connected with a first reaction gas supply pipeline for providing first reaction gas for reacting with first raw materials to generate metal compound precursors; and the second cavity being connected with a first carrier gas supply pipeline;

[0021] The first cavity is further provided with a first distributor matched with the first reaction gas supply pipeline, the first distributor comprising a first top plate and a plurality of first partitions closely arranged on the first top plate, a first reaction space being formed between adjacent first partitions and a gap being formed between the first partitions and the bottom of the first cavity, a first inlet being formed between the first top plate and the inner wall of the first cavity, and the first reaction gas flowing from the first inlet to the first reaction space to generate first metal compound precursors;

[0022] The bottom of the first cavity is further provided with a plurality of second partitions, each of which independently divides a first reaction space along the extension direction of the first partitions, and a gap being formed between the second partitions and the first top plate, and a first raw material supply area being formed between the first partitions and the second partitions;

[0023] The first cavity is further provided with a first outlet connected to a side of the first reaction space away from the first inlet, and the first outlet is provided with a first on-off valve;

[0024] The outer periphery of at least the second cavity is provided with a first heater.

[0025] In one or more embodiments of the present application, the time-space modulation reaction growth device comprises:

[0026] A load-bearing top plate and a heater of the load-bearing top plate. The load-bearing top plate separates the metal source reaction boat mounting area in the upper half of the chamber cavity and the time-space modulation reaction growth area in the middle.

[0027] A rotatable substrate tray and one or more substrate tray heaters;

[0028] A reaction zone ceiling with a space separation partition plate between the load-bearing top plate and the substrate tray, which divides the deposition growth reaction zone into two or more independent subspaces;

[0029] An evacuation channel located between the load-bearing top plate and the reaction zone ceiling;

[0030] a deposition growth reaction zone between the ceiling of the reaction zone and the substrate tray;

[0031] In one or more embodiments of the present application, the central gas path device comprises:

[0032] the central gas path, the central gas path heater, and the rotation mechanism of the gas path switching valve and the spherical valve core at the end of the central gas path device.

[0033] the evacuation channel and / or the deposition growth reaction zone are connected to the gas path switching valve to realize the selection of the flow path of the first reaction gas.

[0034] In one or more embodiments of the present application, the first support device is arranged on the periphery of the central gas path device.

[0035] In one or more embodiments of the present application, the timing support device further comprises:

[0036] the first support body, the first outlet of the reaction boat assembly is connected to the central gas path of the central gas path device of the time-space modulation reaction chamber device in a controllable manner through the first switching valve;

[0037] the first support device arranged on the periphery of the central gas path device of the time-space modulation reaction chamber device, the first support device comprises a plurality of first support bodies, and any reaction boat is carried on any first support body;

[0038] In one or more embodiments of the present application, the gas path switching valve at the end of the central gas path device comprises a switching valve base and a switching valve spherical valve core:

[0039] the switching valve base is provided with a plurality of upper layer gas paths and a plurality of lower layer gas paths;

[0040] the switching valve spherical valve core is provided with a plurality of first group channels and a plurality of second group channels;

[0041] the position of the switching valve spherical valve core, in the first state, the first group channels are connected to the upper layer gas paths; in the second state, the second group channels are connected to the lower layer gas paths.

[0042] In one or more embodiments of the present application, the timing support device further comprises:

[0043] the central gas path device and the metal source reaction boat assembly connected by the first support device, the first switching valve and the gas path switching valve cooperate to supply the gas including the first metal compound precursor to the target segmentation growth zone.

[0044] The device further comprises a plurality of first growth area interfaces matched with the lower gas path of the gas path switching valve base and a plurality of reaction areas, the reaction areas are separated by space isolation plates, a first growth area interface is matched with a reaction area, and the reaction area is defined by at least the lower surface of the reaction area ceiling, the upper surface of the substrate tray and the side surface of the space isolation plate.

[0045] The device further comprises an evacuation channel matched with the upper gas path of the gas path switching valve base, and the evacuation channel is defined by at least the upper surface of the reaction area ceiling and the lower surface of the load-bearing top plate.

[0046] In one or more embodiments of the present application, the device further comprises a second reaction gas device comprising a gas inlet pipeline for conveying the second reaction gas to the reaction area.

[0047] In one or more embodiments of the present application, the substrate tray is rotatably arranged around the gas inlet pipeline.

[0048] In one or more embodiments of the present application, the device further comprises a hollow water-cooled wall in the shape of a cylinder and cover flanges arranged at both ends of the water-cooled wall to limit the formation of a main reaction cavity; in the main reaction cavity: its upper part is limited by a reaction boat assembly, its middle part is limited by a vapor deposition device, and its lower part is limited by a heating sleeve and a substrate tray heater inside the sleeve; the heating sleeve is limited by a second reaction gas device.

[0049] In one or more embodiments of the present application, the upper surface of the load-bearing top plate and the lower surface of the substrate tray are further provided with heaters.

[0050] In one or more embodiments of the present application, a method for preparing a semiconductor device structure by using a spatiotemporal modulation hydride vapor phase epitaxy device.

[0051] In one or more embodiments of the present application, the metal source reaction boat for providing a metal compound precursor and the heater of the reaction boat are placed as independent components outside the cavity, connected to the central gas path in the cavity through a heating pipeline; and / or,

[0052] The metal source reaction boat for providing a metal compound precursor and the heater of the reaction boat are designed as a complete and independent metal source reactor, constituting a metal source reaction furnace, placed as a standard accessory outside the cavity, connected to the central gas path in the cavity through a heating pipeline.

[0053] In one or more embodiments of the present application, each metal source reaction boat of the metal source reaction boat assembly is an independent unit, and the heating and temperature can be independently and accurately controlled, and the type and flow rate of the gas can be independently and accurately controlled; a first switch valve that can continuously rotate is arranged between the reaction boat and the central gas path to control the entry or non-entry of the metal compound precursor into the central gas path.

[0054] In one or more embodiments of the present application, the metal source reaction boat assembly is provided with a first on-off valve between the metal source reaction boat and the central gas path, which can be continuously rotated to control the metal compound precursor to enter or not enter the central gas path; the on-off valve is designed and processed to be able to work stably for a long time under high temperature and strong corrosion conditions.

[0055] In one or more embodiments of the present application, the space-time modulation reaction growth device is configured with a central gas path device, and the end of the central gas path device is configured with a gas path switching valve and a rotating mechanism of the switching valve; the switching valve can be continuously rotated to control the reaction gas to enter the emptying channel or the reaction zone of the space-time modulation reaction growth device, and participate or not participate in the growth of the material.

[0056] In one or more embodiments of the present application, the space-time modulation reaction growth device has a central gas path device, and the end of the central gas path device is configured with a gas path switching valve and a rotating mechanism of a spherical valve core of the switching valve; the switching valve is designed and processed to be able to work stably for a long time under high temperature and strong corrosion conditions. The gas path switching valve is made of a material that can work stably for a long time under high temperature and strong corrosion conditions, and the material is selected from but not limited to quartz, boron nitride, aluminum oxide, aluminum nitride, silicon carbide, and hastelloy.

[0057] In one or more embodiments of the present application, the space-time modulation reaction growth device is configured with a load-bearing top plate for dividing the growth zone and the metal source reaction boat installation zone in the cavity, and a rotatable substrate tray; the load-bearing top plate and the substrate tray are respectively configured with independent heaters, and the temperatures can be independently controlled.

[0058] In one or more embodiments of the present application, the space-time modulation hydride vapor phase epitaxy (TSM-HVPE) reaction chamber is configured with metal compound precursors entering the reaction chamber from the top, and other reaction gases participating in the growth of the material entering the reaction chamber from the bottom; the metal compound precursors and the reaction gases participating in the growth of the material are isolated from each other before entering the growth zone of the reaction chamber, and the temperatures are independently controlled.

[0059] In one or more embodiments of the present application, the space-time modulation hydride vapor phase epitaxy growth equipment includes a space-time modulation device and a second reaction gas source and a first reaction gas source.

[0060] In one or more embodiments of the present application, a method for preparing a semiconductor device structure by using the space-time modulation hydride vapor phase epitaxy growth equipment.

[0061] In one or more embodiments of the present application, a time-space modulation hydride vapor phase epitaxy (TSM-HVPE) reaction chamber can be provided with a metal compound precursor reaction boat in the lower part of the reaction chamber, and the metal compound precursor enters the growth reaction zone from the bottom, while other reaction gases for material growth enter the reaction zone from the top.

[0062] Compared with the prior art, in the time-space modulation hydride vapor phase epitaxy reaction chamber, hydride vapor phase epitaxy growth device and method of the present application, the reaction chamber can be provided with three or more metal sources by independently arranging independent reaction boats, one continuous rotation gas path switching valve, and a growth zone composed of two or more independent sub-growth zones. When provided with multiple metal sources, the device can grow multiple layers of material thin layers containing different metals in sequence to form a stacked structure. For example, when the device is provided with gallium (Ga), aluminum (Al) and indium (In) metal sources, GaAs, InAs, AlAs, GaInAs, AlGaAs and other material thin layers can be epitaxially grown on a substrate in the same device. By using a continuously rotatable gas path switching valve, the time when the metal source is introduced into the growth zone can be controlled, and the thickness of each layer of material can be accurately controlled, which is the time modulation (TM) function. By using a rotating or transmission mechanism, the time when the substrate stays in each independent sub-growth zone can be controlled, thereby accurately controlling the growth time of each layer of material and controlling the growth thickness, which is the space modulation (SM) function. The device structure, combined with gas path control and tail gas treatment systems, can form a new type of epitaxial growth device with low raw material cost, i.e. a time-space modulation hydride vapor phase epitaxy growth system (TSM-HVPE). Combined with the corresponding growth process, TSM-HVPE has the ability to precisely control the thickness of ultra-thin materials and the ability to quickly grow ultra-thick materials, and can be applied to the low-cost growth of semiconductor optoelectronic devices. This device, combined with the corresponding epitaxial process, can achieve a dynamic adjustment range of ultra-large growth rate of 0.01 nm / s to 100 nm / s, meeting the rapid and low-cost epitaxial growth of complex device structures based on GaAs or GaN semiconductor materials, such as multi-junction solar cells, light-emitting diodes, photodetectors and lasers.

[0063] The present application aims to meet the urgent demand for low-cost and large-scale production of thin-film GaAs multi-junction solar cells and GaN-based lasers, and designs a HVPE device for HVPE epitaxial growth of GaAs-based multi-junction cells and GaN-based lasers, thereby significantly reducing the epitaxial cost of GaAs solar cells and GaN-based lasers. The present application combines the precise control of ultra-thin layer material epitaxial growth of MOCVD and the ultra-fast growth rate and low-cost raw material characteristics of HVPE. Attached Figure Description

[0064] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0065] Figure 1 This is a schematic diagram of the working state of a time-cooled hydrogen production vapor phase epitaxial growth apparatus according to an embodiment of the present invention.

[0066] Figure 2 This is a schematic diagram of the overall internal structure, key component connection method and functional area distribution of a time-cooled hydrogen production vapor phase epitaxial growth device according to an embodiment of the present invention, wherein (a) is a schematic diagram of the internal structure of the device; and (b) is a schematic isometric view of the internal structure of the device.

[0067] Figure 3 This is a schematic diagram of the reaction boat and the metal compound precursor delivery pipeline inside the time-cooled hydride vapor phase epitaxial growth apparatus according to an embodiment of the present invention.

[0068] Figure 4 This is a schematic diagram of the internal central gas path and its gas path switching valve of a time-cooled hydrogen production vapor phase epitaxial growth apparatus according to an embodiment of the present invention, wherein (a) is a schematic diagram of the connection state and (b) is a schematic diagram of the working principle.

[0069] Figure 5 This is a schematic diagram of a time-cooled vapor phase epitaxial growth apparatus for hydrogen production according to an embodiment of the present invention, wherein (a) is a schematic diagram of the internal growth zone structure and (b) is a schematic diagram of the growth zone partition structure.

[0070] Figure 6 This is a schematic diagram of the sub-division structure of the internal growth region of a time-cooled hydrogen production vapor phase epitaxial growth apparatus according to an embodiment of the present invention.

[0071] Figure 7 This is a schematic diagram of a time-controlled vapor phase epitaxial growth apparatus for hydrogen production according to an embodiment of the present invention, in which a gas path switching valve is used to select sub-regions of the growth zone in a time-division manner for time-modulated growth. (a) is a schematic diagram of the time-division selection of the AD reaction zone to become a growthable zone, (b) is a schematic diagram of the time-division selection of all reaction zones to become non-growable zones, and (c) is a schematic diagram of the time-division selection of the BE reaction zone to become a growthable zone.

[0072] Figure 8Fig. 1 is a schematic diagram of the internal structure of a time-space modulation hydride vapor phase epitaxy (HVPE) apparatus according to an embodiment of the present application, in which a substrate is rotated in and out of a growth zone by a substrate holder, and the growth is spatially modulated, wherein (a) is a schematic diagram of the time division selection of the AD reaction zone to become a growable zone, (b) is a schematic diagram of the time division selection of the CF reaction zone to become a growable zone, and (c) is a schematic diagram of the time division selection of the BE reaction zone to become a growable zone.

[0073] Figure 9 Fig. 2 is a schematic diagram of the internal structure of a time-space modulation hydride vapor phase epitaxy (HVPE) apparatus according to another embodiment of the present application, in which a gas path switching valve is used to control the time division of the entry of a metal compound precursor into a reaction zone and the evacuation of a channel, and the growth is temporally modulated, wherein (a) is a schematic diagram of the simultaneous connection of six symmetrically distributed branches, and (b) is a schematic diagram of the simultaneous disconnection of six symmetrically distributed branches.

[0074] Figure 10 Fig. 3 is a schematic diagram of a time-space modulation hydride vapor phase epitaxy (HVPE) apparatus according to another embodiment of the present application, in which an independent metal source reaction furnace is provided, wherein (a) is a schematic isometric view of the apparatus, and (b) is a schematic cross-sectional view of the apparatus.

[0075] Figure 11 Fig. 4 is a plot of the external quantum efficiency (EQE) curves of GaAs cells with different material window layers grown according to any one of the methods of embodiments 1-6 of the present application.

[0076] Figure 12 Fig. 5 is a plot of the IV curves of GaAs cells under illumination conditions according to any one of the methods of embodiments 1-6 of the present application.

[0077] Figure 13 Fig. 6 is a plot of the room temperature photoluminescence (PL) spectra of InGaAs / InP epitaxial layers grown according to any one of the methods of embodiments 1-6 of the present application.

[0078] Figure 14 Fig. 7 is a plot of the IV characteristic curves of InGaAs single-junction cells grown according to any one of the methods of embodiments 1-6 of the present application.

[0079] Figure 15 Fig. 8 is a plot of the EQE curves of InGaAs single-junction cells with different window layer thicknesses grown according to any one of the methods of embodiments 1-6 of the present application.

[0080] Figure 16 Fig. 9 is a plot of the EQE curves of GaInP / GaAs double-junction cells grown according to the methods of embodiments 1-6 of the present application.

[0081] Figure 17 Fig. 10 is a plot of the IV characteristic curves of GaInP / GaAs double-junction cells grown according to any one of the methods of embodiments 1-6 of the present application.

[0082] Figure 18 X-ray diffraction curve of AlGaN / GaN material grown according to the method of Example 7 of the present application.

[0083] Figure 19 Surface atomic force microscope image of AlGaN / GaN material grown according to the method of Example 7 of the present application.

[0084] Figure 20 X-ray diffraction curve of InGaN / GaN material grown according to the method of Example 7 of the present application.

[0085] Figure 21 Surface atomic force microscope image of InGaN / GaN material grown according to the method of Example 7 of the present application.

[0086] Figure 22 X-ray diffraction curve of p-type AlGaN / GaN material grown according to the method of Example 7 of the present application.

[0087] Figure 23 Surface atomic force microscope image of p-type AlGaN / GaN material grown according to the method of Example 7 of the present application.

[0088] Description Figures 11-17 The results of testing the same battery sample prepared using the methods of Examples 1-6 show that the methods of the present application have good stability and reproducibility.

[0089] For the purpose of promoting an understanding of the principles of the application, reference will now be made to the embodiment illustrated in the drawings and specific language will be used to describe the same. It will, nevertheless, be understood that no limitation of the scope of the application is thereby intended, such alterations and further modifications in the illustrated device, and such further applications of the principles of the application as illustrated therein being contemplated as would normally occur to one skilled in the art to which the application relates. DETAILED DESCRIPTION

[0090] In order to make the technical solutions in the present disclosure better understood, the technical solutions in the present disclosure will be described clearly and completely below in connection with the disclosed embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present disclosure, but not all the embodiments. Based on the embodiments in the present disclosure, all other embodiments obtained by those skilled in the art without creative efforts should fall within the protection scope of the present disclosure.

[0091] Unless otherwise defined, all terms used in disclosing the application, including technical terms, scientific terms, common terms and scientific terms, will be interpreted as terms commonly used by one of ordinary skill in the art to which the application belongs, and will not be interpreted as overly academic meanings or as overly limited meanings.

[0092] The purpose of the present application is to provide a time-space modulation hydride vapor phase epitaxy device, which can realize a super large growth rate dynamic adjustment range, a super thin layer epitaxial film thickness precise control, a thick layer material super fast growth, a rapid and low cost growth of GaAs-based multi-junction solar cells and GaN-based lasers.

[0093] To achieve the above-mentioned purpose, an embodiment of the present application provides a hydride vapor phase epitaxy (HVPE) device. The device can be equipped with three or more metal sources, a continuously rotating gas path switching valve, and a growth zone composed of two or more independent sub-zones. When equipped with multiple metal sources, the growth zone of the device can grow multiple layers of material thin layers containing different metals respectively, forming a stacked structure. For example, when the device is equipped with three metal sources of gallium (Ga), aluminum (Al) and indium (In), GaAs, InAs, AlAs, GaInAs, AlGaAs, GaN, AlN, InGaN, AlGaN, GaP, InP, AlGaInP and other material thin layers can be epitaxially grown on the substrate in sequence in the same device. By using the continuously rotating gas path switching valve, the time of the three metal sources entering the growth zone can be controlled, and the thickness of each layer of material can be accurately controlled.

[0094] In addition, the rotation axis can be used in combination with bearings and other rotating or transmission mechanisms to control the time of the substrate on the substrate tray staying in each independent sub-growth zone, thereby accurately controlling the growth time of each layer of material and controlling the growth thickness.

[0095] The device can be combined with a gas path control and tail gas treatment system to form a new type of epitaxial growth equipment with low raw material cost, namely a time-space modulation hydride vapor phase epitaxy growth system (TSM-HVPE). Combined with the corresponding growth process, TSM-HVPE has the growth ability of super thin material thickness precise control and the characteristics of super fast growth rate, and can be applied to the low cost growth of semiconductor optoelectronic devices. This equipment combined with the corresponding epitaxial method can realize a super large growth rate dynamic adjustment range of 0.01nm / s to 100nm / s, meet the rapid epitaxial growth of complex device structures based on GaAs or GaN semiconductor materials such as multi-junction solar cells, light emitting diodes, photodetectors and lasers, and reduce the epitaxial cost of devices.

[0096] In one possible embodiment, the device is equipped with five metal sources through the reaction boat. The five metal sources can respectively deliver gaseous compound precursors of five metals, gallium (Ga), indium (In), aluminum (Al), zinc (Zn), and magnesium (Mg) into the device. When these metal precursors are used to generate arsenides, an arsenic-containing gas, such as AsH3, can be introduced as a second reaction gas. A continuously rotating gas path switching valve and a growth zone composed of two or more independent sub-zones can be used to precisely control the time of growth of thin films containing different metals on the substrate, thereby achieving precise control of the thickness of the epitaxial layer. The time modulation achieved by the continuously rotating gas path switching valve can be combined with the spatial modulation achieved by switching the substrate between different independent growth zones in different combinations to complete the continuous growth of different epitaxial layers and form a stacked structure.

[0097] In one or more embodiments of the present application, the time and space modulation hydride vapor phase epitaxy (TSM-HVPE) device can place the metal compound precursor reaction boat in the lower part of the device, and the metal compound precursor enters the growth reaction zone from the bottom, and other reaction gases participating in the growth of the material enter the reaction zone from the top.

[0098] Compared with the existing HVPE equipment structure and technology, the time and space modulation hydride vapor phase epitaxy device according to the embodiments of the present application can achieve the HVPE growth of precise thickness, ultra-thin epitaxial layers, precise doping of epitaxial layers, and the HVPE growth of the overall epitaxial structure of semiconductor devices containing both ultra-thin epitaxial layers and ultra-thin epitaxial layers, through the design and configuration of the reaction boat and the switching valve in the cavity, the design and configuration of the gas path switching valve upstream of the growth reaction zone and adjacent to the growth reaction zone, and the design and configuration of the reaction zone ceiling with a spatial isolation plate that separates the growth reaction zone into independent sub-growth spaces.

[0099] The time and space modulation hydride vapor phase epitaxy (TSM-HVPE) device and its use method according to the embodiments of the present application can greatly reduce the epitaxial cost of GaAs and GaN-based devices by configuring metal sources and reaction gases.

[0100] A reaction chamber is disclosed. The reaction chamber can have one or more precursor sources connected thereto. When two or more independent metal compound precursor sources are connected thereto, two or more independent material layers can be deposited. For example, in one embodiment, an independent gallium source, an independent aluminum source, and an independent In source can be connected to the reaction chamber, so that gallium arsenide, aluminum arsenide, and indium arsenide can be deposited on a substrate in the same reaction chamber. In one embodiment, five metal compound precursor sources can also be connected to the reaction chamber. For example, compound precursors such as gallium, indium, aluminum, magnesium, and zinc can be dispensed. When using the precursors as raw materials to form arsenic-containing compounds, an arsenic-containing gas such as AsH3 can be introduced into the reaction zone. AsH3 can be introduced into the reaction zone at a lower temperature and at a location separate from the metal compound precursors. When using the precursors to form phosphorus-containing compounds, a phosphorus-containing gas such as PH3 can be used. PH3 can be introduced into the reaction zone at a lower temperature and at a location separate from the metal compound precursors. When using the precursors to form nitrogen-containing compounds, a nitrogen-containing gas such as NH3 can be used. NH3 can be introduced into the reaction zone at a higher temperature and at a location separate from the metal compound precursors. The geometry of the reaction zone can be configured so that the precursors and the second reaction gas are introduced from two inlets above and below, respectively, to avoid high concentration mixing of the two reactants, the metal compound precursors and the reaction gas involved in material growth, and premature decomposition of AsH3 / PH3, and to promote premature decomposition of NH3 with higher temperature.

[0101] The design of the gas path switching valve is aimed at achieving rapid switching of the metal compound precursors into or out of the reaction growth zone of the reaction chamber. The reaction growth zone can be divided into several sub-zones (to selectively grow or not grow the corresponding films under the premise of rapid switching of the metal compound precursors) to achieve a spatiotemporal modulation of material growth, ensuring accurate control of the material growth thickness, achieving uniform growth of ultra-thin layers and rapid growth of ultra-thick layers.

[0102] In one embodiment, by rotating the gas path switching valve upstream of the reaction growth zone, the metal compound precursors can be switched between the evacuation channel and the reaction growth zone, and the thickness of the grown material is controlled by the time the metal compound precursors enter the reaction growth zone, achieving temporal modulation of material growth.

[0103] In another embodiment, the sub-growth zones divided by the gas path switching valve are configured as growable and non-growable regions, and by rotating the substrate tray, the substrate is switched between the growable and non-growable regions, and the thickness of the grown material is controlled by the time the substrate stays in the growable region, achieving spatial modulation of material growth, ensuring accurate control of the material thickness, achieving uniform growth of ultra-thin layers and rapid growth of ultra-thick layers.

[0104] In addition, in one embodiment, the reaction chamber is equipped with independent reaction zone ceiling heaters and substrate tray heaters to precisely control the temperature gradient from the reaction zone ceiling to the substrate.

[0105] In addition, in one embodiment, the chamber can also be equipped with a heated gas line connecting the reaction boat and the central gas line of the device, a driving device to drive the rotation of the substrate tray, such as a pulley structure connected to the bearing of the substrate tray, a heating sleeve at the tail gas end, and a low pressure evacuation system, etc.

[0106] In addition, in one embodiment, the device is configured to provide the reaction boat of the metal compound precursor and the heater of the reaction boat as an independent component outside the main reaction chamber, and the first reaction gas supply line is connected to the central gas line in the chamber through the on-off valve 108.

[0107] In addition, in one embodiment, the device is configured to provide the reaction boat of the metal compound precursor and the heater of the reaction boat as an independent component outside the main reaction chamber, and the first reaction gas supply line is connected to the central gas line in the chamber through the on-off valve 108.

[0108] In addition, in one embodiment, each reaction boat of the device is an independent unit, and each unit is heated and independently precisely controlled in temperature by the heater provided outside the second chamber, and the type and flow rate of the gas can be independently precisely controlled.

[0109] In addition, in one embodiment, an on-off valve can be provided between any reaction boat and the central gas line to control the entry or non-entry of the first metal compound precursor into the central gas line, and also to control the amount and speed of the entry of the first metal compound precursor. The on-off valve can work stably for a long time under high temperature and strong corrosion conditions.

[0110] In addition, in one embodiment, the device is configured with a central gas line, and the end of the central gas line is configured with a gas line switching valve and a rotating mechanism of the spherical valve core of the switching valve. The gas line switching valve can realize the control of the reaction gas entering the evacuation channel or entering any reaction zone in the reaction chamber by continuously rotating the valve core to participate or not participate in the growth of the material. The gas line switching valve can work stably for a long time under high temperature and strong corrosion conditions.

[0111] In addition, in one embodiment, the device is configured with a load-bearing top plate to divide the growth zone and the reaction boat mounting zone in the chamber, a rotatable substrate tray, and a reaction zone ceiling between the load-bearing top plate and the substrate tray; the space between the load-bearing top plate and the reaction zone ceiling constitutes the evacuation channel of the metal compound precursor.

[0112] In one embodiment, the device is configured with a rotatable substrate holder (rotating around the central gas channel), a reaction zone ceiling, and a space between the two, which forms a growth reaction zone. In the growth reaction zone, the metal compound precursor and other reaction gases for material growth react to form the compound needed for epitaxial material growth. The growth reaction zone is separated into two or more independent reaction zones by the space isolation plates on the reaction zone ceiling.

[0113] In one embodiment, the device is configured with the metal compound precursor entering from the top and the other reaction gases for material growth entering from the bottom. The metal compound precursor and the other reaction gases for material growth are isolated from each other before entering the growth zone of the device, and the temperatures are independently controlled.

[0114] In one embodiment, the device is configured with a load-bearing top plate separating the growth zone and the reaction boat installation zone in the cavity, and a rotatable substrate holder. The load-bearing top plate and the substrate holder are each configured with an independent heater, and the temperatures can be independently controlled.

[0115] In one embodiment, the device is further configured with:

[0116] The surface of the load-bearing top plate or the substrate holder or the reaction zone ceiling is provided with a coating containing quartz, graphite, special ceramic, and SiC, BN, TaC, etc.

[0117] Each reaction boat is connected to a first reaction gas supply pipeline for providing a first reaction gas capable of reacting with the metal, such as a pipeline for HCl and Cl2. The gas flows through the reaction boat containing the metal and reacts with the metal at a specified temperature to form a metal compound precursor. The first reaction gas supply pipeline can also be provided with a carrier gas delivery pipeline for delivering a carrier gas. The carrier gas delivery pipeline is connected to the central gas channel on one side and to a second carrier gas supply pipeline of the reaction boat on the other side. The carrier gas is mainly used to deliver the metal compound precursor, HCl, Cl2, AsH3, PH3, NH3, etc. The carrier gas can be H2, N2, Ar, He, etc.

[0118] In one embodiment, the device is further configured with an exhaust gas treatment system composed of a vacuum pump, a particle filter, a heating pipeline, a valve, etc., connected to the exhaust gas outlet of the device (such as the outlet of the evacuation structure), to treat the exhaust gas generated after the growth reaction and control the pressure inside the cavity.

[0119] The gas distribution system composed of a flow meter, a pressure gauge, a valve, a pipeline, etc., is connected to the gas inlet pipeline of the device to control the flow and pressure of the reaction gas and the carrier gas, and to distribute the metal compound precursor, the second reaction gas, and the carrier gas to the designated interfaces of the device.

[0120] In addition, in one embodiment, the functional components of the device are all placed inside the main reaction cavity, and the water-cooled wall of the cavity side wall is water-cooled; so that the device does not produce dust and / or volatile substances when working at high temperature, meeting the clean conditions for entering the super-clean room.

[0121] In addition, in one embodiment, the method for the space-time modulation growth of a semiconductor device structure comprises the following steps:

[0122] A time-space modulation hydride vapor phase epitaxy (TSM-HVPE) reaction system is used;

[0123] The two or more independent reaction growth subspaces are respectively set as a region (a growth zone) into which the metal compound precursor is introduced and a region (a non-growth zone) into which the metal compound precursor is not introduced by using the separation partition plate on the reaction zone ceiling itself, cooperating with the use of the rotation mechanism of the gas path switching valve and the switching valve spherical valve core, and the rotation mechanism of the substrate tray is used to control the time for which the substrate stays in the growth zone, so as to accurately control the growth time and growth thickness of the material, which is a space modulation growth method.

[0124] The specific steps include:

[0125] 1) The substrate is conveyed into the TSM-HVPE reaction chamber and placed on the substrate tray;

[0126] 2) The reaction zone ceiling above the substrate tray is provided with a space separation partition plate;

[0127] 3) Each substrate corresponds to a fan-shaped independent reaction growth subspace, and the fan-shaped independent reaction growth subspace is divided into two groups of growth zones and non-growth zones;

[0128] 4) The reaction boats containing metals are respectively heated to a set temperature;

[0129] 5) The load top plate is heated to a set temperature;

[0130] 6) HCl or Cl2 is introduced into the reaction boats containing metals to react with the metals to generate metal chloride precursors such as GaCl, AlCl3, InCl3, etc.;

[0131] 7) The switch valve between the first metal reaction boat and the center gas path of the reaction chamber is opened, and the first metal chloride precursor is introduced into the center gas path;

[0132] 8) The gas path switching valve is rotated to guide the carrier gas carrying the metal chloride precursor into the exhaust channel;

[0133] 9) The substrate tray is heated to a set temperature;

[0134] 10) Rotating the substrate tray to place the substrate in the non-growth zone;

[0135] 11) Rotating the gas path switching valve to allow the carrier gas carrying the metal chloride precursor to enter the designated growth zone, and setting the growth conditions;

[0136] 12) Opening the first kind of reaction gas participating in the growth of the material, and introducing it into the reaction zone;

[0137] 13) After the growth conditions are stable, rotating the substrate tray to allow the substrate to enter the growth zone, starting the growth, and calculating the residence time;

[0138] 14) After the growth time reaches the set value, rotating the substrate tray to allow the substrate to leave the growth zone by rotation and enter the non-growth zone, stopping the growth of the thin layer of the material containing the first kind of metal;

[0139] 15) Opening the on-off valve between the second kind of metal reaction boat and the center gas path of the reaction chamber, allowing the second kind of metal chloride precursor to enter the center gas path, and finally enter the designated growth zone through the gas path switching valve;

[0140] 16) Setting the growth conditions, and after the growth conditions are stable, rotating the substrate tray to allow the substrate to enter the growth zone, starting the growth, calculating the residence time, and completing the growth of the second kind of material;

[0141] 17) After the growth time reaches the set value, rotating the substrate tray to allow the substrate to leave the growth zone by rotation and enter the non-growth zone, stopping the growth of the thin layer of the material containing the second kind of metal;

[0142] 18) Opening the on-off valve between the third kind of metal reaction boat and the center gas path of the reaction chamber, allowing the third kind of metal chloride precursor to enter the center gas path, and finally enter the designated growth zone through the gas path switching valve;

[0143] 19) Setting the growth conditions, and after the growth conditions are stable, rotating the substrate tray to allow the substrate to enter the growth zone, starting the growth, calculating the residence time, and completing the growth of the third kind of material;

[0144] 20) After the growth time reaches the set value, rotating the substrate tray to allow the substrate to leave the growth zone by rotation and enter the non-growth zone, stopping the growth of the thin layer of the material containing the third kind of metal;

[0145] 21) Repeating the processes of 7) to 20) to complete the growth of the stacked structure of multiple materials.

[0146] In addition, in one embodiment, the method uses a temperature swing metallo-organometallic hydride vapor phase epitaxy (TSM-HVPE) device;

[0147] The reaction chamber center gas path end is equipped with a gas path switching valve and a rotating mechanism of the switching valve ball valve core. By rotating the ball valve core, the carrier gas carrying the metal compound precursor is sequentially switched between the reaction chamber growth area and the evacuation channel. The time and frequency of the metal compound precursor entering the growth area are accurately controlled, thereby accurately controlling the growth time and thickness of the material. This method is the first time modulation growth method.

[0148] The specific steps include:

[0149] 1) The substrate is transported into the TSM-HVPE reaction chamber and placed on the substrate tray.

[0150] 2) The reaction area ceiling above the substrate tray is provided with a spatial separation partition plate.

[0151] 3) Each substrate corresponds to a sector-shaped independent reaction and growth sub-space. The sector-shaped independent reaction and growth sub-space is divided into two groups of growable areas and non-growable areas.

[0152] 4) The metal-containing reaction boat is heated to a set temperature.

[0153] 5) The load-bearing top plate is heated to a set temperature.

[0154] 6) Open the HCl or Cl2 and introduce it into the metal-containing reaction boat to react with the metal to form metal chloride precursors such as GaCl, AlCl3, InCl3, etc.

[0155] 7) Open the switch valve between the first metal reaction boat and the reaction chamber center gas path to introduce the first metal chloride precursor into the center gas path.

[0156] 8) Rotate the gas path switching valve to introduce the carrier gas carrying the metal chloride precursor into the evacuation channel.

[0157] 9) Heat the substrate tray to a set temperature.

[0158] 10) Rotate the substrate tray to place the substrate in the growable area.

[0159] 11) Open the first reaction gas participating in material growth and introduce it into the growable area in the reaction area to set the growth conditions.

[0160] 12) Rotate the gas path switching valve to introduce the carrier gas carrying the metal chloride precursor into the growable area to start growth and calculate the growth time.

[0161] 13) After the growth time reaches the set value, rotate the gas path switching valve to introduce the carrier gas carrying the metal chloride precursor into the non-growable area to stop the growth of the first material and adjust the growth conditions.

[0162] 14) Open the switch valve between the second metal reaction boat and the center gas path of the reaction chamber, and pass the second metal chloride precursor into the center gas path, through the gas path switching valve into the non-growth area;

[0163] 15) Heat the substrate tray to the set temperature;

[0164] 16) Rotate the gas path switching valve to pass the carrier gas carrying the metal chloride precursor into the growth area, start the growth, and calculate the growth time;

[0165] 17) After the growth time reaches the set value, rotate the gas path switching valve to pass the carrier gas carrying the metal chloride precursor into the non-growth area, stop the growth of the second material, and adjust the growth conditions;

[0166] 18) Open the switch valve between the third metal reaction boat and the center gas path of the reaction chamber, and pass the third metal chloride precursor into the center gas path, through the gas path switching valve into the non-growth area;

[0167] 19) Heat the substrate tray to the set temperature;

[0168] 20) Rotate the gas path switching valve to pass the carrier gas carrying the metal chloride precursor into the growth area, start the growth, and calculate the growth time;

[0169] 21) After the growth time reaches the set value, rotate the gas path switching valve to pass the carrier gas carrying the metal chloride precursor into the non-growth area, stop the growth of the third material, and adjust the growth conditions;

[0170] 22) Repeat the processes of 14) to 21) to complete the growth of the stacked structure of multiple materials.

[0171] In addition, in one embodiment, the method uses a time and space modulated hydride vapor phase epitaxy (TSM-HVPE) device;

[0172] Using the gas path switching valve and the rotating mechanism of the switching valve ball valve core configured at the end of the center gas path of the reaction chamber, by rotating the ball valve core, the carrier gas carrying the metal compound precursor is sequentially switched between the growth area and the evacuation channel of the reaction chamber, the time and frequency of the compound precursor participating in the material growth reaction passing into the growth area are accurately controlled, and thus the growth time and growth thickness of the material are accurately controlled. This method is the second time modulation growth method;

[0173] 1) The substrate is transported into the TSM-HVPE reaction chamber and placed on the substrate tray;

[0174] 2) The substrate tray is above the reaction area ceiling with a separation partition;

[0175] 3) All the reaction zones are set to be growth zones;

[0176] 4) Each of the metal containing reaction boats is heated to a set temperature;

[0177] 5) The weight top plate is heated to a set temperature;

[0178] 6) Open the HCl or Cl2 and introduce it into the metal containing reaction boat to react with the metal to form metal chloride precursors such as GaCl, AlCl3, InCl3, etc;

[0179] 7) Open the switch valve between the first metal reaction boat and the center gas line of the reactor chamber to introduce the first metal chloride precursor into the center gas line;

[0180] 8) Rotate the gas line switch valve to introduce the carrier gas with the metal chloride precursor into the evacuation channel and set the growth conditions;

[0181] 9) Heat the substrate holder to a set temperature and rotate the substrate holder at a set speed;

[0182] 10) Open the first material growth reaction gas and introduce it into the reaction zone and set the growth conditions;

[0183] 11) Rotate the gas line switch valve to introduce the carrier gas with the metal chloride precursor into the reaction zone to start the growth and count the growth time;

[0184] 12) After the growth time reaches a set value, rotate the gas line switch valve to introduce the carrier gas with the metal chloride precursor into the evacuation channel to stop the growth of the first material and adjust the growth conditions;

[0185] 13) Open the switch valve between the second metal reaction boat and the center gas line of the reactor chamber to introduce the second metal chloride precursor into the center gas line;

[0186] 14) Heat the substrate holder to a set temperature;

[0187] 15) Rotate the gas line switch valve to introduce the carrier gas with the metal chloride precursor into the reaction zone to start the growth and count the growth time;

[0188] 16) After the growth time reaches a set value, rotate the gas line switch valve to introduce the carrier gas with the metal chloride precursor into the evacuation channel to stop the growth of the second material and adjust the growth conditions;

[0189] 17) Open the switch valve between the third metal reaction boat and the center gas line of the reactor chamber to introduce the third metal chloride precursor into the center gas line;

[0190] 18) Rotate the gas path switching valve to allow the carrier gas with metal chloride precursor to flow into the reaction zone to start the growth, and calculate the growth time;

[0191] 19) After the growth time reaches the set value, rotate the gas path switching valve to allow the carrier gas with metal chloride precursor to flow into the evacuation channel to stop the growth of the third material, and adjust the growth conditions;

[0192] 20) Repeat the above processes 13) - 19) to complete the growth of the stacked structure of multiple materials.

[0193] Figure 1 is a schematic diagram of a TSM-HVPE apparatus 100 according to one embodiment. The apparatus includes a main reaction chamber 130 enclosed by lid flanges 122a and 122b, and water-cooled walls 102 and 120. The main reaction chamber 130 is mainly divided into an upper reaction boat installation area and a lower material growth area. Between the reaction boat installation area and the material growth area, a load-bearing ceiling 112 and its heater 110 are arranged. The temperature of the load-bearing ceiling 112 can be independently and accurately controlled to meet the technical requirements of material growth. In the material growth area, a substrate tray 114 is provided with a heater 118. Thus, the temperature of the substrate tray 114 can be independently and accurately controlled to meet the technical requirements of material growth. The substrate tray 114 is connected to the gas inlet pipe 126. In another embodiment, the gas inlet pipe 126 can also be the rotation axis of the substrate tray 114.

[0194] In one embodiment, the substrate tray 114 is provided with a substrate groove 116 for placing a substrate for material growth.

[0195] In one embodiment, a temperature-controllable heating sleeve 124 is further arranged between the growth area of the main reaction chamber 130 and the evacuation outlet, for protecting the gas inlet pipe 126, the substrate tray 114 and the heater 118 from being eroded by corrosive gas; at the same time, the heating sleeve 124 can also be used to prevent excessive deposition of reaction tail gas near the gas outlet, affecting the gas flow rate and flow field configuration of the chamber.

[0196] In one embodiment, the first reactant gas, such as HCl or Cl2, which reacts with the metal source to form the metal compound precursor, and the carrier gas, such as H2 or N2, can be introduced into the reaction boat 106 and the central gas path 104, respectively, through the gas inlet lines in the upper portion of the main reaction chamber 130. The second reactant gas, such as AsH3 and / or PH3, or NH3, which participates in the material growth, can be introduced into the growth reaction zone 216 through the gas inlet line 126 in the lower portion of the main reaction chamber 130. The temperature of the gas inlet line 126 can be precisely controlled to be low to inhibit the pre-decomposition of AsH3 or PH3, or to be high to promote the sufficient decomposition of NH3 and increase its utilization rate. In one embodiment, the second reactant gas which participates in the material growth can be AsH3 or PH3. In another embodiment, the second reactant gas which participates in the material growth can be O2 or NH3.

[0197] In one embodiment, the reaction boat 106 is configured with an independent heating unit, and the temperature can be precisely controlled according to the different types of metals. Between the reaction boat 106 and the central gas path 104, a switching valve 108 is configured to control the metal compound precursor from the reaction boat 106 to enter or not to enter the central gas path 104.

[0198] To react with the second reactant gas from the gas inlet line 126, the metal compound precursor can be delivered from two or more reaction boats 106 into the central gas path 104 of the main reaction chamber 130, respectively. The two or more reaction boats 106 can contain one or more of Ga, Al, and In, respectively, i.e., each reaction boat can provide one type of metal compound precursor required for film deposition. It should be understood that more or less reaction boats can also be included, as described above. In one embodiment, the metal source can include Ga in liquid form in the reaction boat 106, and Al in solid form in the reaction boat 106. In one embodiment, the metal source further includes In in solid form in the reaction boat 106. In one embodiment, the metal source Al and / or In is in the form of solid powder in the reaction boat 106. In one embodiment, the metal source Al and / or In can be in the form of solid particles.

[0199] In one embodiment, the first reaction gas HCl or Cl2, etc. can be made to flow through the surface and / or interior of the metal in the reaction boat 106, to react to form a metal compound precursor, which is then carried by the carrier gas into the central gas path 104 in the main reaction chamber 130, and finally reaches the material growth reaction zone 216 or the evacuation channel 218. In one embodiment, the two or more metal sources can include eutectic materials and alloys thereof. In another embodiment, the TSM-HVPE apparatus 100 can be configured to access a dopant source and one or more intrinsic metal sources for growing thin film materials with controllable doping concentrations.

[0200] In one embodiment, the central gas path 104 can also be configured with an independent heating unit to precisely control its temperature to meet the technical requirements of the delivery of the metal compound precursor. At the end of the central gas path 104, where it communicates with the material growth reaction zone 216, a gas path switching valve 128 is configured to control whether the metal compound precursor and its carrier gas can enter the material growth reaction zone 216 to participate in material growth. When the switching valve 128 gas path is connected to the evacuation channel 218, the metal compound precursor does not participate in the material growth reaction and is directly evacuated from the exhaust outlet on the side wall of the chamber assembly 120; when the switching valve 128 gas path is connected to the growth zone, the metal compound precursor flows over the substrate holder 114 to participate in the material growth reaction on the corresponding substrate, and then is evacuated from the exhaust outlet on the side wall of the chamber assembly 120.

[0201] Figure 2 is Figure 1 FIG. 1 is a schematic diagram of a reaction apparatus of a time-space modulation hydride vapor phase epitaxy growth apparatus 100 according to one embodiment. In Figure 2In a front view of one embodiment, more than two reaction boats 106 are connected to the central gas path 104 through the first outlet on the support body 206, which also serves as a gas passage. The reaction boat 106 is seated on the upper surface of the support body 206, and the two are in gas passage communication through the on-off valve 108. The on-off valve 108 for the metal compound precursor is located on the lower portion of the support body 206. Around the on-off valve 108, the lower portion of the support body 206 is also provided with a separate heater 208 for each reaction boat 106, to ensure that the temperature of the support body 206 itself can be maintained at a set value required for the delivery of the metal compound precursor. Each reaction boat 106 is provided with an independent heater 204, to increase the degree of reaction between the metal source and the reaction gas, and to increase the utilization rate of the reaction gas. The reaction boat 106 can be heated by the combined use of the heater 204 and the lower portion heater 208 of the support body 206, to control the reaction temperature. For example, in one embodiment, the reaction boat 106 containing metallic gallium (Ga) can be heated to a temperature of about 750°C to about 850°C, and then Ga reacts with HCl or Cl2 introduced into the reaction boat 106 to form a metal chloride, GaCl3 or GaCl. GaCl3 or GaCl is carried by H2 or N2, and / or a mixed gas of the two, or even an argon carrier gas, through the outlet in the middle of the bottom of the reaction boat 106 into the support body 206, and then, after passing through the on-off valve 108, is delivered to the central gas path 104, and is further mixed with H2 or N2, and / or a mixed gas of the two, in the central gas path 104, and is finally delivered to the material growth reaction zone 216 or into the evacuation channel 218. The central gas path 104 can also be provided with an independent heater to ensure that its temperature meets the technical requirements for the delivery of the metal compound precursor.

[0202] After entering the central gas path 104, the metal compound precursor is carried by a carrier gas such as H2 or N2, and / or a mixed gas of the two, into the switching valve seat 128a of the gas path switching valve. The components connected to the switching valve seat 128a include the load-bearing top plate 112, and the ceiling 214 of the growth reaction zone 216. The space between the lower surface of the load-bearing top plate 112 and the upper surface of the ceiling 214 of the growth reaction zone 216 is the evacuation channel 218. The space between the lower surface of the ceiling 214 of the reaction zone and the upper surface of the substrate tray 114 is the material growth reaction zone 216. The reaction zone 216 is divided into two or more independent sub-growth zones 522 by the space isolation plate 214a provided on the lower surface of the ceiling 214 of the reaction zone. The first group of channels 128b U and the second group of channels 128b D in the spherical gas path switching valve core 128b are respectively connected to the upper gas path 128a U and the lower gas path 128a DWith this arrangement, switching of the metal compound precursor between the evacuation channel 218 and the growth reaction zone 216 can be achieved, enabling start-stop control of material growth.

[0203] Figure 2 Figure 6B is a schematic isometric view of a metal source mounting region of one embodiment. This embodiment is configured with gallium, aluminum, and indium, three metal sources, in reaction boats 106. The weight plate 112 is heated by a heater 110 above it, which can be set to a temperature of about 600 °C to about 1600 °C. The substrate tray 114 is heated by a heater 118 below it, which can be set to a temperature of about 400 °C to about 1400 °C. During material growth, the temperature of the weight plate 112 is usually set to be higher than the temperature of the substrate tray 114.

[0204] Figure 3 Figure 7 is a cross-sectional view of the connection of the reaction boat 106 to the metal compound precursor delivery line, including the reaction boat support 206 and the central gas line 104, according to one embodiment of the present application;

[0205] In one embodiment, the reaction boat 106 can be a cylindrical vessel made of high purity quartz material, which includes a top cover 302 and a cylinder 306. The cylinder 306 is surrounded by a heater 204, and the interior of the cylinder can be heated by the heater 204 to a temperature required for the reaction of the metal source and the first reaction gas. The interior of the cylinder 306 is divided into a peripheral carrier gas passage and an interior metal compound precursor generation region 308 by an inner top cover 316 and an inner sidewall 318. The center of the metal compound precursor generation region 308 is a metal compound precursor outlet 320. The bottom periphery of the interior metal compound precursor generation region 308 corresponding to the outlet 320 is provided with a plurality of concentric circular partitions (second partitions) and a first partition 322 that is movable up and down in cooperation with the first top cover, which divides the interior metal compound precursor generation region 308 into a plurality of small spaces as the placement region of the metal source. The first reaction gas, such as HCl or Cl2, enters from the center of the inner top cover 316 of the metal compound precursor generation region, and is dispersed in all directions under the drive of the first top cover, and then flows into the metal source placement region defined by the first partition 322 through the gap between the sidewalls. The first reaction gas converges on the outlet 320 of the precursor from the periphery of the generation region 308 through a tortuous path, and in this process, the first reaction gas reacts with the metal to generate the metal compound precursor. The metal compound precursor enters from the top of the outlet 320 of the precursor, and enters the reaction boat support 206 through the spherical sealing connection port 310 between the bottom center of the reaction boat 106 and the reaction boat support 206, and then flows to the central gas line 104 in a controlled manner.

[0206] In one embodiment, the spherical sealing connection port 310 includes two parts. The upper half is a spherical recess 310a, located in the center of the bottom of the reaction boat 106; the lower half is a spherical protrusion 310b, located on the upper surface of the support body 206. The spherical recess 310a and the spherical protrusion 310b are matched with each other, and both have gas through holes inside that are in communication with each other. The support body 206 is divided into two channels inside. One is a carrier gas channel 206a, which is directly connected to the central gas path 104; the other is a metal compound precursor channel 206b, which is controlled by the precursor on-off valve 108 to control whether the precursor enters the central gas path 104.

[0207] Figure 4 FIG. 4 is a schematic diagram of the connection structure 400 of the internal central gas path 104 of the reaction device and the gas path switching valve base 128a of the spatiotemporal modulation hydride vapor phase epitaxy growth equipment 100 according to one embodiment of the present application. The central gas path 104 includes two passages, one of which is a carrier gas passage 402, which can be located in the center of the central gas path 104 and directly connected to the material growth reaction zone 416; the other is a metal compound precursor passage 404, which can be located around the carrier gas passage 402 and connected to a plurality of on-off valves 108.

[0208] As an embodiment, the gas path switching valve 128 can include two parts, one of which is the switching valve base 128a, and the other is the switching valve spherical valve core 128b. Connected to the switching valve base 128a are the load-bearing top plate 112 and the reaction zone ceiling 214. The area between the lower surface of the load-bearing top plate 112 and the upper surface of the reaction zone ceiling 214 is the evacuation channel 218; the area between the lower surface of the reaction zone ceiling 214 and the upper surface of the substrate tray 114 is the material growth reaction zone 216. There are upper gas paths 128a U and lower gas paths 128a D in the switching valve base 128a. The upper gas paths 128a U are connected to the evacuation channel 218, and the lower gas paths 128a D are connected to the reaction zone 216. There are also two sets of gas channels in the switching valve spherical valve core 128b, and the two sets of channels are different in distance from the center of the sphere in the horizontal direction. The first set of channels 128b U is far from the center of the sphere by a distance d1, and the opening position left on the surface of the spherical valve core in the vertical direction is high, which can communicate with the upper gas paths 128a U of the switching valve base 128a; the second set of channels 128b D is close to the center of the sphere by a distance d2, and the opening position left on the surface of the spherical valve core in the vertical direction is low, which can communicate with the lower gas paths 128a Dconnected. The ball valve core 128b of the switching valve can rotate continuously in a plane around the vertical central axis of the carrier gas passage 402 as the rotation axis. When the ball valve core 128b is rotated to position (a), its first group of passages 128b U connected, the metal compound precursor is introduced into the evacuation passage 218, and material growth cannot be performed; when the ball valve core 128b is rotated to position (b), its second group of passages 128b U connected, the metal compound precursor is introduced into the material growth reaction zone 216, and material growth can be performed. D connected, the metal compound precursor is introduced into the material growth reaction zone 216, and material growth can be performed. D connected, the metal compound precursor is introduced into the material growth reaction zone 216, and material growth can be performed.

[0209] Figure 5 is a schematic diagram of the internal growth zone structure 500 of the reaction device of the time-space modulation hydride vapor phase epitaxy growth equipment 100 according to an embodiment of the present application, and is a schematic diagram of the sub-zone structure of the growth zone. Figure 5 The space isolation plate 214a arranged on the lower surface of the reaction zone ceiling 214 in (a) divides the reaction zone into six fan-shaped sub-growth zones 522. The lower gas passage 128a D of the switching valve base 128a has an outlet 506 through which the metal compound precursor enters the reaction zone 216. The outlet 508 is the opening of the carrier gas passage 402 of the central gas passage 104 in the reaction zone, through which the carrier gas enters the reaction zone 216. Figure 5 (b) is a top view cross-sectional view of the lower gas passage 128a D of the switching valve base 128a when it is in the central position. As can be seen from it, the space isolation plate 214a of the reaction zone ceiling 214 divides the reaction zone 216 into six equal parts, and the lower gas passage of the switching valve base 128a is symmetrically distributed and respectively passes into each sub-growth zone 522.

[0210] Figure 6 is a schematic diagram of the sub-zone structure of the growth zone 600 of the reaction device of the time-space modulation hydride vapor phase epitaxy growth equipment 100 according to an embodiment of the present application, and is a further detailed description of Figure 5 . The reaction zone 216 is divided into six sub-growth zones 522 by the space isolation plate 214a of the ceiling 214, and are respectively marked as A, B, C, D, E, and F. These six sub-growth zones can be divided into three pairs according to the diagonal positions, namely AD, BE, and CF, and each group is connected to one pair of passages of the lower gas passage 128a D of the switching valve base 128a. By rotating the ball valve core 128b of the gas passage switching valve 128, the reaction zone into which the metal compound precursor enters can be selected among AD, BE, and CF, so as to become a growable area.

[0211] Figure 7 This is a schematic diagram of the time-modulated growth 700 of a vapor-phase epitaxial growth apparatus 100 for hydrogen production according to an embodiment of the present invention, which utilizes a gas path switching valve to time-division select sub-regions of the growth zone for time-modulated growth 700. Figure 6 Further explanation: The ball valve core 128b of the air circuit switching valve 128 has two symmetrical second sets of channels 128b. D It can connect with the lower air passage 128a of the switching valve base 128a. D A pair of pathways in it are connected, and it can only be connected to 128a. D A pair of passages are connected. When valve core 128b is in Figure 7 When in position (a), it is in the second group of channels 128b. D The outlet is connected to the lower air passage 128a of the switching valve base 128a. D A pair of pathways in the middle are connected to the reaction zone pair AD, making the AD reaction zone pair a growth-promotable region. When the valve core 128b is in Figure 7 When in position (b), the second group of channels 128b D The air outlet and the lower air passage 128a of the switching valve base 128a D All channels are disconnected, and all reaction zones become non-growth zones. When valve core 128b is in Figure 7 When in position (c), it is in the second group of channels 128b. D The outlet is connected to the lower air passage 128a of the switching valve base 128a. D A pair of pathways in the system are connected to the BE reaction zone, making the BE reaction zone a growth zone. Therefore, it can be understood that by rotating the spherical valve core 128b of the gas path switching valve 128, the second set of channels 128b of the valve core 128b can be selected. D The air outlet can connect with the lower air passage 128a of the switching valve base 128a. D The interconnected pathways alter the position of the growable region within reaction zone 216. By controlling the duration of this interconnection, the thickness of the growth material can be controlled, thus achieving a time-modulated growth mode.

[0212] Figure 8 This is a schematic diagram of the interior of the reaction apparatus of a time-controlled hydrogen production vapor phase epitaxial growth device 100 according to an embodiment of the present invention, in which a substrate tray drives the substrate to rotate and enter and exit the growth zone for spatial modulation growth 800. The diagram shows two symmetrical second sets of channels 128b of the gas path switching valve 128 and the ball valve core 128b. D The lower air passage 128a of the switching valve base 128a DA fixed pair of passages are connected and remain stationary during material growth. Assume the initial relative positions of the ball valve core 128b and the switching valve base 128a of the initial gas path switching valve 128 are as follows: Figure 8 As shown in (a). At this point, the metal compound precursor passes through the second set of channels 128b. D and lower air passage 128a D Entering reaction region 216, the reaction region pair AD is designated as a growable region. In this configuration, material growth can occur on the substrate within the AD reaction region. After growth, the substrate tray 114 is rotated, causing the reaction region pair CF to move to its original position as the AD reaction region pair, thus transforming the CF reaction region pair into a growable region, as shown below. Figure 8 As shown in (b), material growth can be performed on the substrate in the CF region. After growth is complete, the substrate tray 114 is rotated further, causing the reaction region pair BE to move to the original position of the CF reaction region pair, thus turning the BE reaction region pair into a growable region, as shown in Figure (b). Figure 8 As shown in (c), material growth can be performed on the substrate in the BE region. By repeating this process, the thickness of the material growth can be controlled by adjusting the time the substrate spends in the growth region, ultimately achieving a spatial modulation growth method for the material.

[0213] Figure 9 This is a schematic diagram of the reaction apparatus 100 of a time-controlled hydride vapor phase epitaxial growth device according to another embodiment of the present invention, in which a gas path switching valve controls the time-division entry of a metal compound precursor into the reaction zone and the venting channel for time-modulated growth 900. In this embodiment, the spherical valve core 128b of the gas path switching valve 128 is provided with six symmetrically distributed second sets of channels 128b. D Second group of channels 128b D It can be connected to the lower air passage 128a of the switching valve base 128a. D The six symmetrically distributed branches are simultaneously connected, such as Figure 9 As shown in (a); or disconnected simultaneously, as shown in (a). Figure 9 As shown in (b). When the gas path switching valve 128 is in Figure 9 In state (a), the metal compound precursor cannot enter reaction zone 216, and all sub-growth zones 522 will become non-growth zones, thus stopping material growth. At this time, if the spherical valve core 128b is rotated, causing the gas path switching valve 128 to be in position... Figure 9 In state (b), the metal compound precursor enters reaction zone 216, and all sub-growth zones 522 become growable zones, allowing material growth. This cycle, with the gas path switching valve continuously switching between the two states, controls the material growth time, thereby controlling the material growth thickness and achieving another method of time-based material growth control.

[0214] Figure 10 Figure 12 (a) is a schematic isometric view of a reaction apparatus of a time and space modulated hydride vapor phase epitaxy growth apparatus 1000 according to another embodiment of the present application, which is equipped with independent metal source reaction furnaces 1010. The reaction vessel 106 of the reaction apparatus is designed and manufactured as an independent metal source reaction furnace 1010, which has an independent sealed water-cooled shell 1012, and has the same or similar internal structure as the reaction vessel 106. The reaction apparatus of the apparatus 1000 is equipped with six independent metal source reaction furnaces 1010, each of which can precisely control the temperature of the reaction vessel.

[0215] Figure 10 Figure 12 (b) is a schematic cross-sectional view of the reaction apparatus of the time and space modulated hydride vapor phase epitaxy growth apparatus 1000 according to another embodiment of the present application, which is equipped with independent metal source reaction furnaces 1010. The cavity of the reaction apparatus is composed of the water-cooled wall 1004 of the main cavity, the water-cooled flange 1002, and the water-cooled shells 1012 of the six independent metal source reaction furnaces 1010. Inside the cavity, the reaction vessel is connected to the support body 1016 through the hemispherical interface 1014, and is connected to the central gas path 104 through the support body 1016, and is finally connected to the gas path switching valve 128. The metal source reaction furnace 1010 is equipped with a side wall heater 1006 and a bottom heater 1008 to control the temperature in the reaction vessel, to ensure that the metal and the reaction gas are fully reacted to generate a metal compound precursor.

[0216] Compared with the prior art, the growth of HVPE based on the time and space modulation according to the embodiments of the present application precisely controls the thickness of the thin layer of material through the control of the growth time, increases the flexibility of the growth program setting, and can realize the epitaxial growth of the stacked structure of ultra-thin layer materials, and meets the epitaxial growth requirements of complex semiconductor devices.

[0217] As an embodiment, when the growth of HVPE based on the time and space modulation is performed, the rotation of the substrate tray 114 around the axis can be continuous or repeated, to realize the position switching of the target substrate between the growable area and the non-growable area or different growth areas, to control the time of the substrate staying in the growable area, i.e. the growth time of the material, and to further control the thickness of the grown material layer. The embodiments of the present application can improve the efficiency of material growth.

[0218] Embodiment 1:

[0219] This embodiment describes a time-controlled and space-modulated growth method for semiconductor device structures using a time-controlled hydride vapor phase epitaxy (TSM-HVPE) reaction chamber. The TSM-HVPE reaction chamber in this embodiment is equipped with three metal sources: gallium (Ga), aluminum (Al), and indium (In); a doping gas, hydrogen selenide (H2Se), as an n-type dopant; a doping metal-organic source, diethylzinc (DEZn), as a p-type dopant; and reaction gases HCl, AsH3, and PH3. Furthermore, the gas path switching valve 128 is made of alumina. In this embodiment, the spherical valve core 128b of the gas path switching valve 128 within the main reaction chamber 130 is configured with only two symmetrical second sets of channels 128b. D ,like Figure 6 As shown, it can only simultaneously connect with the lower air passage 128a of the switching valve base 128a. D Two symmetrical pathways among the six branch pathways are connected respectively. This configuration of the gas path switching valve 128 can only simultaneously set two diagonally arranged sub-growth regions 522 of the material growth reaction zone 216 as growable regions, while the other four sub-growth regions are simultaneously set as non-growable regions. Specific steps include:

[0220] 1) H2 or N2 is introduced into all gas passages of the central gas passage 104, the metal source reaction boat 106, and the inlet pipe 126.

[0221] 2) The temperature of the reaction vessel 106 containing metallic gallium (Ga) and metallic indium (In) is increased and stabilized to 800°C.

[0222] 3) Increase the temperature of the aluminum (Al) reaction vessel 106 to 400℃ and stabilize it.

[0223] 4) Increase and stabilize the temperature of the support body 206, central gas passage 104, and load-bearing top plate 112 of the metal source reaction boat 106 at 800℃.

[0224] 5) HCl is introduced into the reaction gas pipeline 324 of the Ga reaction boat 106, causing HCl to react with Ga to generate GaCl; the switch valve 108 of the Ga reaction boat 106 is opened, allowing the precursor GaCl to be carried by the carrier gas through the reaction boat support 206 into the central gas path 104, and then through the gas path switching valve 128 into the exhaust channel 218. The gas flow rate is adjusted to the set value required for GaAs material growth.

[0225] 6) GaAs substrates are transferred into the TSM-HVPE main reaction chamber 130 and placed in the substrate grooves 116 on the substrate tray 114; only two diagonal grooves of the six substrate grooves 116 are placed with the formal GaAs substrates, and the other four grooves are placed with the dummy pieces. The two formal GaAs substrates are placed in the C and F sub-growth zones 522 of the growth reaction zone 216, respectively.

[0226] 7) The substrate tray is heated to 650°C.

[0227] 8) The first reaction gas AsH3 is opened and introduced into the A and D sub-growth zones 522 of the growth reaction zone 216.

[0228] 9) The gas path switching valve 128 is rotated so that the carrier gas carrying the metal chloride precursor is introduced into the designated A and D sub-reaction zones, which become the growable zones.

[0229] 10) After the growth conditions are stable, the substrate tray 114 is rotated so that the GaAs substrates enter the growable zones A and D, and the growth of the GaAs buffer layer on the GaAs substrates is started. The growth rate is controlled to be about 60 μm / h, and the growth time is calculated so that the thickness of the GaAs buffer layer is 1 μm.

[0230] 11) After the growth is completed, the gas path switching valve 128 is rotated so that the gas carrying the precursor GaCl enters the evacuation channel 218, and the growth is stopped.

[0231] 12) At the same time, HCl is introduced into the reaction gas pipeline 324 of the metal In reaction boat 106 so that the In reacts with the HCl to form InCl; the switch valve 108 of the In reaction boat 106 is opened so that the precursor InCl is carried by the carrier gas into the central gas path 104 through the reaction boat support 206, and then enters the evacuation channel 218 through the gas path switching valve 128. The gas flow is adjusted to the set value required for the growth of GaInP material.

[0232] 13) The first reaction gas AsH3 is closed, and the second reaction gas PH3 and the n-type doping gas H2Se are opened and introduced into the B and E sub-growth zones 522 of the growth reaction zone 216.

[0233] 14) The gas path switching valve 128 is rotated so that the carrier gas carrying the metal chloride precursor is introduced into the designated B and E sub-reaction zones, which become the growable zones.

[0234] 15) After the growth conditions are stable, the substrate tray 114 is rotated so that the GaAs substrates enter the growable zones B and E, and the growth of the n + -GaInP etching stop layer on the GaAs buffer layer is started. The growth rate is controlled to be about 2 μm / h, and the growth time is calculated so that the thickness of the n +- GaInP etch stop layer thickness is 0.3 microns.

[0235] 16) After growth is completed, rotate gas path switching valve 128 to allow gas carrying precursors GaCl and InCl to enter evacuation channel 218 and growth is stopped.

[0236] 17) Turn off n-type dopant gas H2Se, turn on p-type dopant source DEZn, adjust gas flow, and introduce carrier gas carrying PH3 and DEZn into C, F sub-growth zones.

[0237] 18) Rotate gas path switching valve 128 to allow carrier gas carrying metal chloride precursors to enter designated C, F sub-reaction zones to make them into growable zones.

[0238] 19) After growth conditions are stabilized, rotate substrate holder 114 to bring GaAs substrate into growable zones C, F, and start growing p-GaInP emitter region on n-GaInP etch stop layer. Control growth rate at about 2 μm / h, and calculate growth time to make p-GaInP emitter region thickness 0.15 microns. + -GaInP etch stop layer thickness is 0.3 microns. + -GaInP emitter region. Control growth rate at about 2 μm / h, and calculate growth time to make p-GaInP emitter region thickness 0.15 microns. + -GaInP emitter region thickness is 0.15 microns.

[0239] 20) After growth is completed, rotate gas path switching valve 128 to allow gas carrying precursors GaCl and InCl to enter evacuation channel 218 and growth is stopped.

[0240] 21) Turn off p-type dopant source DEZn and second reaction gas PH3, turn on first reaction gas AsH3 and n-type dopant gas H2Se, adjust gas flow, and introduce carrier gas carrying AsH3 and H2Se into A, D sub-growth zones.

[0241] 22) Rotate gas path switching valve 128 to allow carrier gas carrying metal chloride precursors to enter designated A, D sub-reaction zones to make them into growable zones.

[0242] 23) After growth conditions are stabilized, rotate substrate holder 114 to bring GaAs substrate into growable zones A, D, and start growing n-GaAs base region on p-GaInP emitter region. Control growth rate at about 60 μm / h, and calculate growth time to make n-GaAs base region thickness 1.5 microns. + -GaInP emitter region. Control growth rate at about 2 μm / h, and calculate growth time to make p-GaInP emitter region thickness 0.15 microns.

[0243] 24) After growth is completed, rotate gas path switching valve 128 to allow gas carrying precursors GaCl to enter evacuation channel 218 and growth is stopped.

[0244] 25) Repeat the above steps 8) - 24) to sequentially complete n-GaAs base region with thickness 0.03 microns, p-GaInP emitter region with thickness 0.15 microns, and p-GaInP etch stop layer with thickness 0.3 microns.+ - GaInP window layer, n + - GaAs layer, p + - GaInP back surface field layer, p-GaInP base region, n + - GaInP emitter region growth.

[0245] 26) At the same time, HCl is introduced into the reaction gas line 324 of the metal Al reaction boat 106 to react with Al to form AlCl3; the switch valve 108 of the Al reaction boat 106 is opened to allow the precursor AlCl3 to enter the central gas path 104 through the reaction boat support 206 under the carrying of the carrier gas, and then enter the evacuation channel 218 through the gas path switching valve 128. The gas flow is adjusted to the set value required for growing AlInP material.

[0246] 27) n + After the growth of the GaInP emitter region is completed, the gas path switching valve 128 is rotated to allow the carrier gas carrying the precursor GaCl to enter the evacuation channel 218, and the growth is stopped.

[0247] 28) The precursor GaCl source is closed, and the carrier gas carrying PH3 and H2Se is introduced into the preceding n + The pair of sub-growth region sub-reaction regions behind the sub-reaction region of the GaInP emitter region growth, such as A and D.

[0248] 29) The gas path switching valve 128 is rotated to allow the carrier gas carrying the metal chloride precursors AlCl3 and InCl to enter the designated A and D sub-reaction regions, so that they become growable regions.

[0249] 30) After the growth conditions are stable, the substrate tray 114 is rotated to allow the GaAs substrate to enter the growable regions A and D, and the growth of the n + - GaInP emitter region. + - AlInP window layer. The growth rate is controlled at about 2 μm / h, and the growth time is calculated to make the n + The thickness of the AlInP window layer is 0.025 μm.

[0250] 31) The first reaction gas of the metal source is closed, and the temperature of all the heaters in the entire main reaction chamber 130 is lowered.

[0251] 32) After the temperature is lowered to below 100 degrees, the second reaction gas is closed.

[0252] 33) The chamber is opened, and the epitaxial wafer is taken out, and the growth of the double-junction GaAs-based solar cell is completed.

[0253] Example 2:

[0254] As in Example 1, specifically characterized in that only the Time Modulation function as shown in Figure 7 is used to complete the epitaxial growth of the semiconductor device in Example 1.

[0255] The specific steps include:

[0256] 1) H2 or N2 is introduced into all gas passages of the central gas path 104, the metal source reaction boat 106, and the gas inlet pipe 126.

[0257] 2) The temperature of the reaction boat 106 of the metal gallium (Ga) and the metal indium (In) is raised and stabilized to 800°C.

[0258] 3) The temperature of the reaction boat 106 of the metal aluminum (Al) is raised and stabilized to 400°C.

[0259] 4) The temperature of the support body 206 of the metal source reaction boat 106, the central gas path 104, and the load-bearing top plate 112 is raised and stabilized at 800°C.

[0260] 5) HCl is introduced into the reaction gas pipe 324 of the Ga reaction boat 106 to react with Ga to form GaCl; the switch valve 108 of the Ga reaction boat 106 is opened to allow the precursor GaCl to enter the central gas path 104 through the reaction boat support body 206 under the carrying of the carrier gas, and then enter the evacuation passage 218 through the gas path switching valve 128 (the gas path switching valve 128 is made of silicon nitride). Adjust the gas flow to the set value required for growing GaAs material.

[0261] 6) The GaAs substrate is conveyed into the TSM-HVPE main reaction cavity 130 and placed in the substrate groove 116 on the substrate tray 114; of the six substrate grooves 116, only two diagonal grooves are placed with formal GaAs substrates, and the other four grooves are placed with accompanying pieces. Two formal GaAs substrates are placed in the C and F sub-growth zones 522 of the growth reaction zone 216.

[0262] 7) The substrate tray is heated to 650°C.

[0263] 8) The first reaction gas AsH3 is introduced into all sub-growth zones 522 of the growth reaction zone 216.

[0264] 9) The gas path switching valve 128 is rotated to allow the carrier gas carrying the metal chloride precursor to enter the designated A and D sub-reaction zones, so that they become growable zones.

[0265] 10) After the growth conditions are stable, rotate the substrate tray 114 to make the GaAs substrate enter the growth zone A, D, and start growing the GaAs buffer layer on the GaAs substrate. Control the growth rate at about 60 μm / h, and calculate the growth time to make the GaAs buffer layer 1 μm thick.

[0266] 11) After the growth is completed, rotate the gas path switching valve 128 to make the gas carrying the precursor GaCl enter the evacuation channel 218, and stop the growth.

[0267] 12) At the same time, introduce HCl into the reaction gas pipeline 324 of the metal In reaction boat 106 to make the HCl react with In to form InCl; open the switch valve 108 of the In reaction boat 106 to make the precursor InCl carried by the carrier gas enter the central gas path 104 through the reaction boat support 206, and then enter the evacuation channel 218 through the gas path switching valve 128. Adjust the gas flow to the set value required for growing the GaInP material.

[0268] 13) Close the first reaction gas AsH3, and open the second reaction gas PH3 and the n-type doping gas H2Se, and introduce them into all the sub-growth zones 522 in the growth reaction zone 216 A-F.

[0269] 14) Rotate the gas path switching valve 128 to make the carrier gas carrying the metal chloride precursor pass through the second group of channels 128b D through B-E, C-F sub-reaction zones, and enter the evacuation channel close to the A-D sub-reaction zones.

[0270] 15) After the growth conditions are stable, rotate the gas path switching valve 128 to make the carrier gas carrying the metal chloride precursor enter the designated A, D sub-reaction zones to make them become the growth zones.

[0271] 16) Start growing the n + -GaInP etching stop layer on the GaAs buffer layer. Control the growth rate at about 2 μm / h, and calculate the growth time to make the n + -GaInP etching stop layer 0.3 μm thick.

[0272] 17) After the growth is completed, rotate the gas path switching valve 128 to make the gas carrying the precursors GaCl and InCl enter the evacuation channel 218, and stop the growth.

[0273] 18) Close the n-type doping gas H2Se, open the p-type doping source DEZn, adjust the gas flow, and introduce the carrier gas carrying PH3 and DEZn into all the sub-growth zones A-F.

[0274] 19) Rotate the gas path switching valve 128 to make the carrier gas carrying the metal chloride precursor pass through the second group of channels 128bD Pass through B-E, C-F sub-reaction zones, into the evacuation channel next to A-D sub-reaction zones.

[0275] 20) Rotate gas path switching valve 128 to let the carrier gas with metal chloride precursors into the designated A, D sub-reaction zones, making them into growable zones.

[0276] 21) Start to grow p-GaInP window layer on the p-GaInP etch stop layer. Control the growth rate at about 2 μm / h, calculate the growth time so that the p-GaInP window layer is 0.045 μm thick. + -GaInP etch stop layer. Control the growth rate at about 2 μm / h, calculate the growth time so that the p-GaInP etch stop layer is 0.15 μm thick. + -GaInP etch stop layer. Control the growth rate at about 2 μm / h, calculate the growth time so that the p-GaInP etch stop layer is 0.15 μm thick. + -GaInP etch stop layer. Control the growth rate at about 2 μm / h, calculate the growth time so that the p-GaInP etch stop layer is 0.15 μm thick.

[0277] 22) After the growth is completed, rotate gas path switching valve 128 to let the gas with precursors GaCl and InCl into evacuation channel 218, and stop the growth.

[0278] 23) Turn off p-type dopant source DEZn and the second reaction gas PH3, turn on the first reaction gas AsH3 and n-type dopant gas H2Se, adjust the gas flow, and let the carrier gas with AsH3 and H2Se into all sub-growth zones A-F.

[0279] 24) Rotate gas path switching valve 128 to let the carrier gas with metal chloride precursors pass through the second group of channels 128b D Pass through B-E, C-F sub-reaction zones, into the evacuation channel next to A-D sub-reaction zones.

[0280] 25) After the growth conditions are stable, rotate gas path switching valve 128 to let the carrier gas with metal chloride precursors into the designated A, D sub-reaction zones, making them into growable zones.

[0281] 26) Start to grow n-GaAs base region on the p-GaInP emitter region. Control the growth rate at about 60 μm / h, calculate the growth time so that the n-GaAs base region is 1.5 μm thick. + -GaInP etch stop layer. Control the growth rate at about 2 μm / h, calculate the growth time so that the p-GaInP etch stop layer is 0.15 μm thick.

[0282] 27) After the growth is completed, rotate gas path switching valve 128 to let the gas with precursor GaCl into evacuation channel 218, and stop the growth.

[0283] 28) Repeat the above steps 8) - 27) to sequentially complete the growth of n + -GaInP window layer, n + -GaAs layer, p +- GaInP back surface field layer, p-GaInP base region with a thickness of 0.9 microns, n + Growth of GaInP emitter region.

[0284] 29) At the same time, HCl is introduced into the reaction gas pipeline 324 of the metal Al reaction boat 106 to react with Al to form AlCl3; the switch valve 108 of the Al reaction boat 106 is opened to allow the precursor AlCl3 carried by the carrier gas to enter the central gas pipeline 104 through the reaction boat support 206, and then enter the evacuation channel 218 through the gas pipeline switching valve 128. The gas flow is adjusted to the set value required for growing AlInP material.

[0285] 30) n + After the growth of the GaInP emitter region is completed, the gas pipeline switching valve 128 is rotated to allow the carrier gas carrying the precursor GaCl to enter the evacuation channel 218, and the growth is stopped.

[0286] 31) The precursor GaCl source is closed, and the carrier gas carrying PH3 and H2Se is introduced into all the A-F sub-growth regions 522 in the growth reaction region 216.

[0287] 32) After the growth conditions are stable, the gas pipeline switching valve 128 is rotated to allow the carrier gas carrying the metal chloride precursors AlCl3 and InCl to enter the designated A and D sub-reaction regions, so that they become growable regions.

[0288] 33) Start growing n + n + -AlInP window layer on the GaInP emitter region. The growth rate is controlled at about 2 μm / h, and the growth time is calculated to make the n + -AlInP window layer with a thickness of 0.025 microns.

[0289] 34) Close the first reaction gas of the metal source, and reduce the temperature of all the heaters in the entire main reaction chamber 130.

[0290] 35) After the temperature drops below 100 degrees, the second reaction gas is closed.

[0291] 36) Open the chamber, take out the epitaxial wafer, and complete the growth of the double-junction GaAs-based solar cell.

[0292] Example 3:

[0293] As in Example 2, the specific feature is that only the Time Modulation function is used to complete the epitaxial growth of the semiconductor device in Example 1.

[0294] The specific steps include:

[0295] 1) H2 or N2 is introduced into all gas passages of the central gas path 104, the metal source reaction boat 106, and the gas inlet pipe 126.

[0296] 2) The temperature of the reaction boat 106 of the metal gallium (Ga) and the metal indium (In) is raised and stabilized to 800°C.

[0297] 3) The temperature of the reaction boat 106 of the metal aluminum (Al) is raised and stabilized to 400°C.

[0298] 4) The temperature of the support body 206 of the metal source reaction boat 106, the central gas path 104, and the load-bearing top plate 112 is raised and stabilized to 800°C.

[0299] 5) HCl is introduced into the reaction gas pipe 324 of the reaction boat 106 of the metal Ga, so that GaCl is generated by the reaction of HCl and Ga; the switch valve 108 of the Ga reaction boat 106 is opened, so that the precursor GaCl carried by the carrier gas enters the central gas path 104 through the reaction boat support body 206, and then enters the evacuation passage 218 through the gas path switching valve 128 (the gas path switching valve 128 is made of high-purity quartz). The gas flow is adjusted to the set value required for growing GaAs material.

[0300] 6) The GaAs substrate is conveyed into the TSM-HVPE main reaction cavity 130 and placed in the substrate groove 116 on the substrate tray 114; of the six substrate grooves 116, only two diagonal grooves are used to place the formal GaAs substrates, and the other four grooves are used to place the accompanying pieces. The two formal GaAs substrates are placed at the positions of the C and F sub-growth zones 522 of the growth reaction zone 216.

[0301] 7) The substrate tray is heated to 650°C.

[0302] 8) The first reaction gas AsH3 is introduced into all the sub-growth zones 522 of the growth reaction zone 216.

[0303] 9) The gas path switching valve 128 is rotated, so that the carrier gas carrying the metal chloride precursor is introduced into the designated A and D sub-reaction zones, so that they become the growable zones.

[0304] 10) After the growth conditions are stabilized, the substrate tray 114 is rotated, so that the GaAs substrate enters the growable zones A and D, and the growth of the GaAs buffer layer on the GaAs substrate is started. The growth rate is controlled to be about 60 μm / h, the growth time is calculated, and the thickness of the GaAs buffer layer is 1 micron.

[0305] 11) After the growth is completed, the gas path switching valve 128 is rotated, so that the gas carrying the precursor GaCl enters the evacuation passage 218, and the growth is stopped.

[0306] 12) At the same time, HCl is introduced into the reaction gas line 324 of the metal In reaction boat 106 to react with In to form InCl; the switch valve 108 of the In reaction boat 106 is opened to allow the precursor InCl to enter the central gas line 104 through the reaction boat support 206 under the carrier gas, and then enter the evacuation channel 218 through the gas line switching valve 128. The gas flow is adjusted to the set value required for growing GaInP material.

[0307] 13) The first reaction gas AsH3 is closed, and the second reaction gas PH3 and the n-type doping gas H2Se are opened and introduced into all the A-F sub-growth zones 522 in the growth reaction zone 216.

[0308] 14) After the growth conditions are stable, the gas line switching valve 128 is reversed to allow the carrier gas carrying the metal chloride precursor to enter the designated A and D sub-reaction zones again to become the available growth zones.

[0309] 15) The growth of the n + -GaInP etching stop layer is started on the GaAs buffer layer. The growth rate is controlled at about 2 μm / h, and the growth time is calculated to make the n + -GaInP etching stop layer has a thickness of 0.3 μm.

[0310] 16) After the growth is completed, the gas line switching valve 128 is rotated to allow the carrier gas carrying the precursors GaCl and InCl to enter the evacuation channel 218, and the growth is stopped.

[0311] 17) The n-type doping gas H2Se is closed, and the p-type doping source DEZn is opened, and the gas flow is adjusted to allow the carrier gas carrying PH3 and DEZn to enter all the A-F sub-growth zones.

[0312] 18) After the growth conditions are stable, the gas line switching valve 128 is reversed to allow the carrier gas carrying the metal chloride precursor to enter the designated A and D sub-reaction zones again to become the available growth zones.

[0313] 19) The growth of the p + -GaInP etching stop layer is started on the GaAs buffer layer. The growth rate is controlled at about 2 μm / h, and the growth time is calculated to make the n + -GaInP etching stop layer has a thickness of 0.3 μm. + -GaInP etching stop layer has a thickness of 0.3 μm.

[0314] 20) After the growth is completed, the gas line switching valve 128 is rotated to allow the carrier gas carrying the precursors GaCl and InCl to enter the evacuation channel 218, and the growth is stopped.

[0315] 21) Turn off the p-type doping source DEZn and the second reaction gas PH3, turn on the first reaction gas AsH3 and the n-type doping gas H2Se, adjust the gas flow rate, and introduce the carrier gas carrying AsH3 and H2Se into all sub-growth regions of AF.

[0316] 22) After the growth conditions stabilize, reverse the rotation of the gas path switching valve 128 to allow the carrier gas carrying the metal chloride precursor to re-enter the designated A and D sub-reaction zones, making them growable zones.

[0317] 23) Start at p + An n-GaAs base region was grown on the GaInP emitter region. The growth rate was controlled at approximately 60 μm / h, and the growth time was calculated to achieve a n-GaAs base region thickness of 1.5 μm.

[0318] 24) After growth is complete, rotate the gas path switching valve 128 to allow the gas carrying the precursor GaCl to enter the venting channel 218, and the growth stops.

[0319] 25) Repeat steps 8)-27) above to sequentially complete the process for n with a thickness of 0.03 micrometers. + -GaInP window layer, with a thickness of 0.045 micrometers and n + -GaAs layer, p-type with a thickness of 0.15 micrometers + -GaInP back surface field layer, p-GaInP base region with a thickness of 0.9 μm, n-GaInP with a thickness of 0.03 μm + -Growth of GaInP emitter regions.

[0320] 26) Simultaneously, HCl is introduced into the reaction gas pipeline 324 of the Al reaction boat 106, causing HCl to react with Al to generate AlCl3; the switch valve 108 of the Al reaction boat 106 is opened, allowing the precursor AlCl3 to be carried by the carrier gas through the reaction boat support 206 into the central gas path 104, and then through the gas path switching valve 128 into the exhaust channel 218. The gas flow rate is adjusted to the set value required for the growth of AlInP material.

[0321] 27) n with a thickness of 0.03 micrometers + -After the GaInP emitter region is grown, rotate the gas path switching valve 128 to allow the gas carrying the precursor GaCl to enter the venting channel 218, and the growth stops.

[0322] 28) Turn off the precursor GaCl source and introduce carrier gas carrying PH3 and H2Se into all AF sub-growth zones 522 of the growth reaction zone 216.

[0323] 29) After the growth conditions are stable, reverse rotate the gas path switching valve 128, so that the carrier gas with metal chloride precursors AlCl3 and InCl is introduced into the designated A, D sub-reaction zones, so that they become available growth zones.

[0324] 30) Start growing n + -GaInP emission region on the n + -AlInP window layer. Control the growth rate at about 2 μm / h, calculate the growth time so that the n + -AlInP window layer is 0.025 microns thick.

[0325] 31) Turn off the first reaction gas of the metal source, and reduce the temperature of all heaters in the entire main reaction chamber 130.

[0326] 32) After the temperature drops below 100 degrees, turn off the second reaction gas.

[0327] 37) Open the chamber, take out the epitaxial wafer, and complete the growth of the double-junction GaAs-based solar cell.

[0328] Example 4:

[0329] As in Example 1, the specific feature is that only the Space Modulation function is used to complete the epitaxial growth of the semiconductor device in Example 1.

[0330] The specific steps include:

[0331] 1) H2 or N2 is introduced into all gas passages of the central gas path 104, the metal source reaction boat 106, and the gas inlet pipeline 126.

[0332] 2) The temperature of the reaction boat 106 of the metal gallium (Ga) and the metal indium (In) is raised and stabilized to 800°C.

[0333] 3) The temperature of the reaction boat 106 of the metal aluminum (Al) is raised and stabilized to 400°C.

[0334] 4) The temperature of the support body 206 of the metal source reaction boat 106, the central gas path 104, and the load-bearing top plate 112 is raised and stabilized at 800°C.

[0335] 5) HCl is introduced into the reaction gas pipeline 324 of the metal Ga reaction boat 106, so that HCl reacts with Ga to form GaCl; the switch valve 108 of the Ga reaction boat 106 is opened, so that the precursor GaCl is carried by the carrier gas into the central gas path 104 through the reaction boat support body 206, and then into the evacuation passage 218 through the gas path switching valve 128 (the gas path switching valve 128 is made of silicon nitride). Adjust the gas flow to the set value required for growing GaAs material.

[0336] 6) GaAs substrates are transferred into the TSM-HVPE main reaction chamber 130 and placed in the substrate grooves 116 on the substrate tray 114; only two diagonal grooves of the six substrate grooves 116 are placed with the formal GaAs substrates, and the other four grooves are placed with the dummy pieces. The two formal GaAs substrates are placed in the C and F sub-growth zones 522 of the growth reaction zone 216, respectively.

[0337] 7) The substrate tray is heated to 650°C.

[0338] 8) The first reaction gas AsH3 is opened and introduced into all the A-F sub-growth zones 522 of the growth reaction zone 216.

[0339] 9) The gas path switching valve 128 is rotated to make the carrier gas carrying the metal chloride precursor pass into the designated A and D sub-reaction zones, so that they become the growable zones.

[0340] 10) After the growth conditions are stable, the substrate tray 114 is rotated to make the GaAs substrates enter the growable zones A and D, and the growth of the GaAs buffer layer on the GaAs substrates is started. The growth rate is controlled at about 60 μm / h, and the growth time is calculated so that the thickness of the GaAs buffer layer is 1 micron.

[0341] 11) After the growth is completed, the substrate tray 114 is rotated to make the GaAs substrates enter the non-growth zones B and E, and the growth is stopped.

[0342] 12) At the same time, HCl is introduced into the reaction gas pipeline 324 of the metal In reaction boat 106 to make the In react with HCl to generate InCl; the switch valve 108 of the In reaction boat 106 is opened to make the precursor InCl carried by the carrier gas enter the central gas path 104 through the reaction boat support 206, and then enter the designated A and D sub-reaction zones through the gas path switching valve 128. The gas flow is adjusted to the set value required for growing the GaInP material.

[0343] 13) The first reaction gas AsH3 is closed, and the second reaction gas PH3 and the n-type doping gas H2Se are opened and introduced into the A-F sub-growth zones 522 of the growth reaction zone 216.

[0344] 14) The substrate tray 114 is rotated to make the GaAs substrates enter the non-growth zones C and F.

[0345] 15) After the growth conditions are stable, the substrate tray 114 is rotated to make the GaAs substrates enter the growable zones A and D, and the growth of the n + -GaInP etching stop layer on the GaAs buffer layer is started. The growth rate is controlled at about 2 μm / h, and the growth time is calculated so that the thickness of the n +- The GaInP etch stop layer thickness is 0.3 microns.

[0346] 16) After growth is completed, rotate the substrate tray 114 to bring the GaAs substrate into the non-growth zones B, E, and growth is stopped.

[0347] 17) Turn off the n-type dopant gas H2Se, turn on the p-type dopant source DEZn, adjust the gas flow, and introduce the carrier gas carrying PH3 and DEZn into all of the sub-growth zones 522 in A-F.

[0348] 18) Rotate the substrate tray 114 to bring the GaAs substrate into the non-growth zones C, F.

[0349] 19) After the growth conditions are stable, rotate the substrate tray 114 to bring the GaAs substrate into the growth zones A, D, and start growing the p-GaInP window layer on the n-GaAs base region. + - The p-GaInP window layer is grown on the n-GaAs base region. + - The GaInP emitter region. Control the growth rate at about 2 μm / h, and calculate the growth time so that the p-GaInP emitter region thickness is 0.15 microns. + - The GaInP emitter region thickness is 0.15 microns.

[0350] 20) After growth is completed, rotate the substrate tray 114 to bring the GaAs substrate into the non-growth zones B, E, and growth is stopped.

[0351] 21) Turn off the p-type dopant source DEZn and the second reaction gas PH3, turn on the first reaction gas AsH3 and the n-type dopant gas H2Se, adjust the gas flow, and introduce the carrier gas carrying AsH3 and H2Se into all of the sub-growth zones 522 in A-F.

[0352] 22) Rotate the substrate tray 114 to bring the GaAs substrate into the non-growth zones C, F.

[0353] 23) After the growth conditions are stable, rotate the substrate tray 114 to bring the GaAs substrate into the growth zones A, D, and start growing the n-GaAs base region on the p-GaInP emitter region. + - The n-GaAs base region is grown on the p-GaInP emitter region. Control the growth rate at about 60 μm / h, and calculate the growth time so that the n-GaAs base region thickness is 1.5 microns.

[0354] 24) After growth is completed, rotate the substrate tray 114 to bring the GaAs substrate into the non-growth zones B, E, and growth is stopped.

[0355] 25) Repeat or cycle the above steps 8) - 24) to sequentially complete the n-GaInP window layer with a thickness of 0.03 microns, the n-GaInP etch stop layer with a thickness of 0.3 microns, the p-GaInP emitter region with a thickness of 0.15 microns, and the n-GaAs base region with a thickness of 1.5 microns. + - The GaInP window layer with a thickness of 0.045 microns, the GaInP etch stop layer with a thickness of 0.3 microns, the p-GaInP emitter region with a thickness of 0.15 microns, and the n-GaAs base region with a thickness of 1.5 microns. +- GaAs layer, p + - GaInP back surface field layer, p-GaInP base region of 0.9 microns in thickness, n + - Growth of GaInP emitter region.

[0356] 26) At the same time, HCl is introduced into the reaction gas line 324 of the metal Al reaction boat 106, so that the HCl reacts with the Al to form AlCl3; the switch valve 108 of the Al reaction boat 106 is opened, so that the precursor AlCl3 carried by the carrier gas enters the central gas path 104 through the reaction boat support 206, and then enters the designated A, D sub-reaction zones through the gas path switching valve 128. The gas flow is adjusted to the set value required for growing the AlInP material.

[0357] 27) n + After the growth of the GaInP emitter region is completed, the substrate tray 114 is rotated so that the GaAs substrate enters the non-growth zones B and E, and the growth is stopped.

[0358] 28) The precursor GaCl source is closed, and the carrier gas carrying PH3 and H2Se is introduced into all the A-F sub-growth zones 522.

[0359] 29) The substrate tray 114 is rotated so that the GaAs substrate enters the non-growth zones C and F.

[0360] 30) After the growth conditions are stable, the substrate tray 114 is rotated so that the GaAs substrate enters the growth zones A and D, and the growth of n + - GaInP emitter region is started. + - AlInP window layer. The growth rate is controlled at about 2 μm / h, and the growth time is calculated so that the n + The thickness of the AlInP window layer is 0.025 microns.

[0361] 31) The first reaction gas of the metal source is closed, and the temperature of all the heaters in the entire main reaction chamber 130 is lowered.

[0362] 38) After the temperature is lowered to below 100 degrees, the second reaction gas is closed.

[0363] 39) The chamber is opened, and the epitaxial wafer is taken out, and the growth of the double-junction GaAs-based solar cell is completed.

[0364] Example 5:

[0365] As in Example 4, the specific feature is that only the Space Modulation function is used to complete the epitaxial growth of the semiconductor device in Example 1.

[0366] The specific steps include:

[0367] 1) H2or N2is introduced into all gas passages of the central gas path 104, the metal source reaction boat 106, and the gas inlet pipe 126.

[0368] 2) The temperature of the reaction boat 106 of the metal gallium (Ga) and the metal indium (In) is raised and stabilized to 800°C.

[0369] 3) The temperature of the reaction boat 106 of the metal aluminum (Al) is raised and stabilized to 400°C.

[0370] 4) The temperature of the support body 206 of the metal source reaction boat 106, the central gas path 104, and the load-bearing top plate 112 is raised and stabilized at 800°C.

[0371] 5) HCl is introduced into the reaction gas pipe 324 of the reaction boat 106 of the metal Ga, so that the HCl reacts with the Ga to generate GaCl; the switch valve 108 of the Ga reaction boat 106 is opened, so that the precursor GaCl carried by the carrier gas enters the central gas path 104 through the reaction boat support body 206, and then enters the evacuation passage 218 through the gas path switching valve 128. The gas flow is adjusted to the set value required for growing GaAs material.

[0372] 6) The GaAs substrate is conveyed into the TSM-HVPE main reaction cavity 130 and placed in the substrate groove 116 on the substrate tray 114; of the six substrate grooves 116, only the grooves at the diagonal positions of two formal GaAs substrates are placed, and the other four grooves are placed with accompanying pieces. The two formal GaAs substrates are respectively placed at the positions of the C and F sub-growth zones 522 of the growth reaction zone 216.

[0373] 7) The substrate tray is heated to 650°C.

[0374] 8) The first reaction gas AsH3is opened and introduced into all the sub-growth zones 522 of the growth reaction zone 216.

[0375] 9) The gas path switching valve 128 is rotated, so that the carrier gas carrying the metal chloride precursor is introduced into the designated A and D sub-reaction zones, so that they become growable zones.

[0376] 10) After the growth conditions are stabilized, the substrate tray 114 is rotated, so that the GaAs substrate enters the growable zones A and D, and the growth of the GaAs buffer layer on the GaAs substrate is started. The growth rate is controlled at about 60 μm / h, the growth time is calculated, and the thickness of the GaAs buffer layer is 1 micron.

[0377] 11) After the growth is completed, the substrate tray 114 is rotated, so that the GaAs substrate enters the non-growth zones B and E, and the growth is stopped.

[0378] 12) At the same time, HCl is introduced into the reaction gas line 324 of the In reaction boat 106 to react with In to form InCl; the switch valve 108 of the In reaction boat 106 is opened to allow the precursor InCl to enter the central gas line 104 through the reaction boat support 206 under the carrier gas, and then enter the designated A, D sub-growth zones through the gas line switching valve 128. The gas flow is adjusted to the required set value for growing GaInP material.

[0379] 13) The first reaction gas AsH3 is closed, and the second reaction gas PH3 and the n-type doping gas H2Se are opened and introduced into the A-F sub-growth zones 522 of the growth reaction zone 216.

[0380] 14) After the growth conditions are stable, the substrate tray 114 is reversed to allow the GaAs substrate to enter the growth zones A, D again, and the growth of n + -GaInP etching stop layer. The growth rate is controlled at about 2 μm / h, and the growth time is calculated to make the n + The thickness of the GaInP etching stop layer is 0.3 μm.

[0381] 15) After the growth is completed, the substrate tray 114 is rotated to allow the GaAs substrate to enter the non-growth zones C, F, and the growth is stopped.

[0382] 16) The n-type doping gas H2Se is closed, and the p-type doping source DEZn is opened and adjusted to the gas flow, and the carrier gas carrying PH3 and DEZn is introduced into all the A-F sub-growth zones 522.

[0383] 17) After the growth conditions are stable, the substrate tray 114 is reversed to allow the GaAs substrate to enter the growth zones A, D again, and the growth of p + -GaInP etching stop layer. The growth rate is controlled at about 2 μm / h, and the growth time is calculated to make the n + -GaInP etching stop layer. The growth rate is controlled at about 2 μm / h, and the growth time is calculated to make the n + The thickness of the GaInP etching stop layer is 0.3 μm.

[0384] 18) After the growth is completed, the substrate tray 114 is rotated to allow the GaAs substrate to enter the non-growth zones C, F, and the growth is stopped.

[0385] 19) The p-type doping source DEZn and the second reaction gas PH3 are closed, and the first reaction gas AsH3 and the n-type doping gas H2Se are opened and adjusted to the gas flow, and the carrier gas carrying AsH3 and H2Se is introduced into all the A-F sub-growth zones 522.

[0386] 20) After the growth conditions are stable, rotate the substrate tray 114 in the reverse direction to make the GaAs substrate enter the growable zones A and D again, and start growing the p + -GaInP emitter region. Control the growth rate at about 60 μm / h, and calculate the growth time so that the n-GaAs base region is 1.5 μm thick.

[0387] 21) After the growth is completed, rotate the substrate tray 114 to make the GaAs substrate enter the non-growth zones C and F, and stop growing.

[0388] 22) Repeat the steps of 8) - 24) above to sequentially complete the growth of the n + -GaInP window layer, n + -GaAs layer, p + -GaInP back surface field layer, p-GaInP base region, n + -GaInP emitter region.

[0389] 23) At the same time, introduce HCl into the reaction gas line 324 of the metal Al reaction boat 106 to make the HCl react with the Al to form AlCl3; open the switch valve 108 of the Al reaction boat 106 to make the precursor AlCl3 carried by the carrier gas enter the central gas path 104 through the reaction boat support 206, and then enter the designated A and D sub-reaction zones through the gas path switching valve 128. Adjust the gas flow to the set value required for growing the AlInP material.

[0390] 24) After the growth of the n + -GaInP emitter region is completed, rotate the substrate tray 114 to make the GaAs substrate enter the non-growth zones B and E, and stop growing.

[0391] 25) Close the precursor GaCl source, and introduce the carrier gas carrying PH3 and H2Se into all the sub-growth zones 522 of A-F.

[0392] 26) After the growth conditions are stable, rotate the substrate tray 114 in the reverse direction to make the GaAs substrate enter the growable zones A and D, and start growing the n + -GaInP emitter region. Control the growth rate at about 60 μm / h, and calculate the growth time so that the n-GaAs base region is 1.5 μm thick. + -AlInP window layer. Control the growth rate at about 2 μm / h, and calculate the growth time so that the n + -AlInP window layer is 0.025 μm thick.

[0393] 27) Close the first reaction gas of the metal source, and reduce the temperature of all the heaters in the entire main reaction chamber 130.

[0394] 28) After the temperature drops to 100 degrees, the second reaction gas is turned off.

[0395] 29) The chamber is opened, and the epitaxial wafer is removed, completing the growth of the double-junction GaAs-based solar cell.

[0396] Example 6:

[0397] This embodiment is a growth method using a time and space modulation hydride vapor phase epitaxy (TSM-HVPE) reaction chamber for semiconductor device structures. The TSM-HVPE reaction chamber in this embodiment is equipped with three metal sources of gallium (Ga), aluminum (Al), and indium (In), a doped gas of hydrogen selenide (H2Se) as an n-type dopant, a doped metal organic source of diethyl zinc (DEZn) as a p-type dopant, a reaction gas of HCl, a reaction gas of AsH3, and another reaction gas of PH3. In addition, the ball valve core 128b of the gas path switching valve 128 in the main reaction chamber 130 in this embodiment is configured with six symmetric second group channels 128b D As shown in Figure 9 , it can simultaneously communicate with the six passages of the lower gas path 128a D of the switching valve base 128a, and can simultaneously set all six sub-growth zones 522 of the material growth reaction zone 416 as growable zones or non-growable zones at one time. The specific steps include:

[0398] 1) H2 or N2 is introduced into all gas passages of the central gas path 104, the metal source reaction boat 106, and the gas inlet pipeline 126.

[0399] 2) The temperature of the reaction boat 106 of the metal gallium (Ga) and the metal indium (In) is raised and stabilized to 800°C.

[0400] 3) The temperature of the reaction boat 106 of the metal aluminum (Al) is raised and stabilized to 400°C.

[0401] 4) The temperature of the support body 206 of the metal source reaction boat 106, the central gas path 104, and the load-bearing top plate 112 is raised and stabilized at 800°C.

[0402] 5) HCl is introduced into the reaction gas pipeline 324 of the Ga reaction boat 106, so that HCl reacts with Ga to form GaCl; the switch valve 108 of the Ga reaction boat 106 is opened, so that the precursor GaCl carried by the carrier gas enters the central gas path 104 through the reaction boat support body 206, and then enters the exhaust passage 218 through the gas path switching valve 128. Adjust the gas flow to the set value required for growing GaAs material.

[0403] 6) GaAs substrates are transferred into the TSM-HVPE main reaction chamber 130 and placed in the substrate grooves 116 on the substrate tray 114; six GaAs substrates are placed in the six substrate grooves 116.

[0404] 7) The substrate tray is heated to 650°C.

[0405] 8) The first reaction gas AsH3 is opened and introduced into all of the sub-growth zones 522 of the growth reaction zone 216.

[0406] 9) After the growth conditions are stable, the gas path switching valve 128 is rotated so that the carrier gas carrying the metal chloride precursor is introduced into the designated reaction zone 216, which becomes a growth zone.

[0407] 10) A GaAs buffer layer is grown on the GaAs substrate. The growth rate is controlled to be about 60 μm / h, and the growth time is calculated so that the GaAs buffer layer is 1 μm thick.

[0408] 11) After the growth is completed, the gas path switching valve 128 is rotated so that the gas carrying the precursor GaCl is introduced into the evacuation channel 218, and the growth is stopped.

[0409] 12) At the same time, HCl is introduced into the reaction gas channel 324 of the metal In reaction boat 106 so that the HCl reacts with the In to form InCl; the switching valve 108 of the In reaction boat 106 is opened so that the precursor InCl is carried by the carrier gas into the central gas channel 104 through the reaction boat support 206 and then into the evacuation channel 218 through the gas path switching valve 128. The gas flow is adjusted to the set value required for growing the GaInP material.

[0410] 13) The first reaction gas AsH3 is closed, and the second reaction gas PH3 and the n-type doping gas H2Se are opened and introduced into the growth reaction zone 216.

[0411] 14) After the growth conditions are stable, the gas path switching valve 128 is rotated so that the carrier gas carrying the metal chloride precursor is introduced into the reaction zone 216, which becomes a growth zone.

[0412] 15) An n + -GaInP etching stop layer is grown on the GaAs buffer layer. The growth rate is controlled to be about 2 μm / h, and the growth time is calculated so that the n + -GaInP etching stop layer is 0.3 μm thick.

[0413] 16) After the growth is completed, the gas path switching valve 128 is rotated so that the gas carrying the precursors GaCl and InCl is introduced into the evacuation channel 218, and the growth is stopped.

[0414] 17) Turn off n-type dopant gas H2Se, turn on p-type dopant source DEZn, adjust gas flow, introduce carrier gas carrying PH3 and DEZn into the growth zone.

[0415] 18) After the growth conditions are stable, rotate the gas path switching valve 128 to make the carrier gas carrying the metal chloride precursor pass into the designated reaction zone 216 to become a growth zone.

[0416] 19) In the p + -GaInP window layer, grow a p + -GaInP emitter region. Control the growth rate at about 2 μm / h, calculate the growth time so that the p + -GaInP emitter region is 0.15 μm thick.

[0417] 20) After the growth is complete, rotate the gas path switching valve 128 to make the gas carrying the precursors GaCl and InCl pass into the evacuation channel 218, and the growth stops.

[0418] 21) Turn off the p-type dopant source DEZn and the second reaction gas PH3, turn on the first reaction gas AsH3 and the n-type dopant gas H2Se, adjust the gas flow, and introduce the carrier gas carrying AsH3 and H2Se into the reaction zone 216.

[0419] 22) After the growth conditions are stable, rotate the gas path switching valve 128 to make the carrier gas carrying the metal chloride precursor pass into the reaction zone 216 to become a growth zone.

[0420] 23) In the n + -GaInP emitter region, grow a n-GaAs base region. Control the growth rate at about 60 μm / h, calculate the growth time so that the n-GaAs base region is 1.5 μm thick.

[0421] 24) After the growth is complete, rotate the gas path switching valve 128 to make the gas carrying the precursor GaCl pass into the evacuation channel 218, and the growth stops.

[0422] 25) Repeat the above steps 8) - 24) in sequence to complete the growth of an n + -GaInP window layer that is 0.045 μm thick, an n + -GaAs layer that is 0.15 μm thick, a p + -GaInP back surface field layer that is 0.9 μm thick, a p-GaInP base region that is 0.03 μm thick, and an n + -GaInP emitter region.

[0423] 26) An n +After the growth of the GaInP emitter region is completed, the gas path switching valve 128 is rotated to allow the gas carrying the precursor GaCl to enter the evacuation channel 218, and the growth is stopped.

[0424] 27) At the same time, the reaction gas line 324 of the reaction boat 106 of the metal Al is connected to the HCl, so that the HCl reacts with the Al to form AlCl3; the switch valve 108 of the Al reaction boat 106 is opened, so that the precursor AlCl3 carried by the carrier gas enters the central gas path 104 through the reaction boat support 206, and then enters the evacuation channel 218 through the gas path switching valve 128. The gas flow is adjusted to the set value required for the growth of the AlInP material.

[0425] 28) The precursor GaCl source is closed, and the carrier gas carrying PH3 and H2Se is introduced into the reaction zone 216.

[0426] 29) After the growth conditions are stable, the gas path switching valve 128 is rotated to allow the carrier gas carrying the metal chloride precursors AlCl3 and InCl to enter the reaction zone 216, so that it becomes a growth zone.

[0427] 30) The n + The n + The AlInP window layer. The growth rate is controlled at about 2 μm / h, and the growth time is calculated so that the n + The thickness of the AlInP window layer is 0.025 microns.

[0428] 31) The first reaction gas of the metal source is closed, and the temperature of all the heaters in the entire main reaction chamber 130 is lowered.

[0429] 32) After the temperature is lowered to below 100 degrees, the second reaction gas is closed.

[0430] 33) The chamber is opened, and the epitaxial wafer is taken out, completing the growth of the double-junction GaAs-based solar cell.

[0431] Example 7:

[0432] This example is a growth method using a time and space modulation hydride vapor phase epitaxy (TSM-HVPE) reaction chamber for the time and space modulation of semiconductor device structures. The TSM-HVPE reaction chamber in this example is equipped with six metal sources of gallium (Ga), aluminum (Al), indium (In), magnesium (Mg), scandium (Sc), and yttrium (Y), one doped gas silane (SiH4) as an n-type dopant, one reaction gas HCl or Cl2, and one reaction gas NH3, as shown in Figure 10 In the configuration of the metal sources and reaction gases in this example, the specific steps in Examples 1-6 are referred to, and Figure 7 and Figure 8The time modulation growth and the space modulation growth mode shown can respectively complete the growth of n-type and / or p-type materials GaN, AlGaN, InGaN, AlScN, AlYN, and AlInGaN at different growth rates of 1-100 μm / h, and constitute the structure of GaN laser, light emitting diode, and high mobility field effect transistor.

[0433] It is apparent to those skilled in the art that the present disclosure is not limited to the details of the foregoing exemplary embodiments, and thus can be implemented in other particular forms without departing from the spirit or essential characteristics of the present disclosure. The foregoing embodiments are thus to be considered in all respects as illustrative and not restrictive, the scope of the present disclosure being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. No feature of the claims is to be construed as limiting the claims to the exact nature of the features described therein.

[0434] Furthermore, it should be understood that although the present specification describes particular embodiments, each of which contains only a single independent technical solution, the specification is merely a description of a number of embodiments of the present disclosure and thus does not describe every conceivable embodiment of the present disclosure. The description herein of one embodiment does not exclude other embodiments from the scope of the present disclosure. The technical solutions in each embodiment can be combined with the technical solutions in other embodiments to form other embodiments of the present disclosure.

Claims

1. A time-controlled vapor-phase epitaxial reaction chamber for producing hydrides, characterized in that, The application relates to a reaction chamber for depositing and growing thin films, comprising: a reaction chamber with water-cooled side walls and a cavity defined by flanges, the cavity being divided into upper, middle and lower parts; a metal source reaction boat assembly located in the upper half of the cavity of the reaction chamber, comprising time sequence supporting devices and a plurality of reaction boats, wherein the time sequence supporting devices comprise a plurality of first supporting bodies, any of the reaction boats is carried on any of the first supporting bodies, and the first outlet of the reaction boat is connected to the central gas path device; a time-space modulation reaction growth device located in the middle part of the cavity of the reaction chamber, wherein the time-space modulation reaction growth device comprises a load-bearing top plate, a heater on the load-bearing top plate, the load-bearing top plate separates the upper half of the reaction chamber into a metal source reaction boat assembly installation area and a time-space modulation reaction growth area adjacent to the lower part of the load-bearing top plate, a rotatable substrate tray and a heater of the substrate tray, a reaction area ceiling with space separation plates arranged between the load-bearing top plate and the substrate tray, the space separation plates divide the deposition and growth reaction area into two or more independent subspaces, an evacuation channel located between the load-bearing top plate and the reaction area ceiling, and a deposition and growth reaction area located between the reaction area ceiling and the substrate tray; a heating device and a tail gas collecting device located in the lower half of the cavity of the reaction chamber; a central gas path device located at the central position of the cavity of the reaction chamber, which connects the metal source reaction boat assembly in the upper half of the cavity and the time-space modulation reaction growth device in the middle part of the cavity through the central gas path.

2. The spatiomodulated hydride vapor phase epitaxy reaction chamber of claim 1, wherein, The metal source reaction boat assembly comprises a plurality of reaction boats, any of the reaction boats has a first cavity and a second cavity formed outside the first cavity, the first cavity is connected with a first reaction gas supply pipeline for providing first reaction gas for generating metal compound precursors through first raw materials reaction, and the second cavity is connected with a first carrier gas supply pipeline; a first distributor matched with the first reaction gas supply pipeline is further arranged in the first cavity, the first distributor comprises a first top plate and a plurality of first separation plates closely arranged on the first top plate, a first reaction space is formed between adjacent first separation plates, a gap is formed between the first separation plates and the bottom of the first cavity, a first inlet is formed between the first top plate and the inner wall of the first cavity, and the first reaction gas flows from the first inlet to the first reaction space to generate first metal compound precursors; a plurality of second separation plates are further arranged on the bottom of the first cavity, one first reaction space is independently divided by one second separation plate along the extension direction of the first separation plates, a gap is formed between the second separation plates and the first top plate, and a first raw material supply area is formed between the first separation plates and the second separation plates; the first cavity is further provided with a first outlet connected to one side of the first reaction space away from the first inlet, and the first outlet is provided with a first on-off valve; at least a first heater is arranged outside the periphery of the second cavity.

3. The spatiomodulated hydride vapor phase epitaxy reaction chamber of claim 1, wherein, The central gas path device comprises a central gas path, a central gas path heater arranged on the central gas path, and a gas path switching valve and a rotating mechanism of a spherical valve core of the switching valve arranged at the end of the central gas path.

4. The spatiomodulated hydride vapor phase epitaxy reaction chamber of claim 2, wherein, The first outlet of the reaction boat is controlled by a first switch valve to controllably connect to the central gas path of the central gas path device through the first support body.

5. The spatiomodulated hydride vapor phase epitaxy reaction chamber of claim 3, wherein, The gas path switch valve of the central gas path device includes a switch valve base and a switch valve spherical valve core: The switch valve base is provided with a plurality of upper layer gas paths and a plurality of lower layer gas paths; The switch valve spherical valve core is provided with a plurality of first group channels and a plurality of second group channels; The switch valve spherical valve core satisfies: in the first state, the first group channels are connected to the upper layer gas paths; In the second state, the second group channels are connected to the lower layer gas paths.

6. The spatiomodulated hydride vapor phase epitaxy reaction chamber of claim 1, wherein, The space-time modulation reaction growth device is matched with the first switch valve and the gas path switch valve to supply the gas including the first metal compound precursor to the target reaction area; A plurality of first growth area interfaces matched with the lower layer gas paths of the base of the gas path switch valve and a plurality of independent subspaces are included, one of the first growth area interfaces is matched with one of the independent subspaces, and one of the independent subspaces is at least defined by the lower surface of the reaction area ceiling, the upper surface of the substrate tray and the side surface of the space isolation plate.

7. The time and space modulated hydride vapor phase epitaxy chamber of claim 1, wherein, The evacuation channel is at least defined by the upper surface of the reaction area ceiling and the lower surface of the load-bearing top plate, and the evacuation channel is matched with the upper layer gas paths of the base of the gas path switch valve.

8. The spatially modulated hydride vapor phase epitaxy chamber of claim 1, wherein, The space-time modulation reaction growth device further includes a second reaction gas device including a second reaction gas inlet pipeline for conveying the second reaction gas to the reaction area.

9. The spatially modulated hydride vapor phase epitaxy chamber of claim 1, wherein, The substrate tray of the space-time modulation reaction growth device is rotatably arranged with the inlet pipeline as the axis.

10. The spatiotemporal modulation hydride vapor phase epitaxy chamber of claim 1, wherein, The reaction chamber includes a hollow water-cooled wall in a cylindrical shape and cover flanges arranged at both ends of the water-cooled wall to limit the formation of a main reaction cavity; In the main reaction cavity, the load-bearing top plate is used as the main isolation structure: the upper part is limited by the reaction boat assembly, the middle part is limited by the vapor deposition device, and the lower part is limited by the heating sleeve and the substrate tray heater inside the sleeve; the second reaction gas device is limited in the heating sleeve.

11. The spatiomodulated hydride vapor phase epitaxy reaction chamber of claim 1, wherein, The central gas path of the central gas path device is provided with a gas path switch valve and a rotating mechanism for rotating the spherical valve core of the switch valve; through the continuous rotation of the spherical valve core, the switch valve can control the reaction gas to enter the evacuation channel or the deposition growth reaction area of the space-time modulation reaction growth device.

12. The spatiomodulated hydride vapor phase epitaxy reaction chamber of claim 11, wherein, The gas path switch valve is made of a material that can work stably for a long time under high temperature and strong corrosion conditions, and the material is selected from, but not limited to, quartz, boron nitride, aluminum oxide, aluminum nitride, silicon carbide and hastelloy.

13. A space-time modulation hydride vapor phase epitaxy growth device, comprising the space-time modulation hydride vapor phase epitaxy reaction chamber according to any one of claims 1-12, a second reaction gas source connected to the second reaction gas inlet pipeline and a first reaction gas source connected to the first reaction gas supply pipeline.

14. A method for preparing a semiconductor device structure by using the space-time modulation hydride vapor phase epitaxy growth device according to claim 13.

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