CN112210828B - Gallium boat structure for reducing Si content in HVPE epitaxial film - Google Patents
Gallium boat structure for reducing Si content in HVPE epitaxial film Download PDFInfo
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- CN112210828B CN112210828B CN202011141095.0A CN202011141095A CN112210828B CN 112210828 B CN112210828 B CN 112210828B CN 202011141095 A CN202011141095 A CN 202011141095A CN 112210828 B CN112210828 B CN 112210828B
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- boron nitride
- pyrolytic boron
- tube
- epitaxial film
- gallium
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a gallium boat structure for reducing Si content in an HVPE epitaxial film. The structure is a multilayer structure, the outer layer is a quartz tube, and the left end is sealedOn a flange of HVPE, the support function is realized; the middle layer is provided with two pyrolytic boron nitride tubes, namely a first pyrolytic boron nitride tube and a second pyrolytic boron nitride tube, so as to prevent corrosive gas Cl 2 The inner layer is a pyrolytic boron nitride crucible used for containing liquid metal gallium; the first pyrolytic boron nitride tube is sleeved in the quartz tube; the second pyrolytic boron nitride tube is sleeved in the first pyrolytic boron nitride tube; the pyrolytic boron nitride crucible is placed inside a second pyrolytic boron nitride tube. After the invention is adopted, the corrosive gas Cl can be effectively prevented 2 Contact with the quartz tube to prevent the quartz tube from being corroded and avoid beta-Ga 2 O 3 Si impurities are doped into the epitaxial film, so that the carrier concentration of the epitaxial film is reduced, and the purity of the epitaxial film is improved.
Description
Technical Field
The invention relates to a growth technology of single crystal materials, in particular to a gallium boat structure for reducing Si content in an HVPE epitaxial film, which is a novel gallium boat structure used for a horizontal structure Halide Vapor Phase Epitaxy (HVPE) furnace.
Background
Gallium oxide (Ga) 2 O 3 ) Is a fourth generation oxide semiconductor material following a third generation semiconductor such as GaN, siC, etc., and has a crystal structure of 5 (alpha, beta, gamma, delta, epsilon), wherein beta-Ga 2 O 3 Is the one with the most stable structure. beta-Ga compared with semiconductors such as Si, gaN, siC, etc 2 O 3 The band gap is large, the theoretical breakdown field strength can reach 8MV/cm, the on-resistance is small, the Baridge optimum value is high, and the method can be used for manufacturing high-performance power electronic devices and has wide application prospect.
At present beta-Ga 2 O 3 The most promising application is a Schottky switch device, and the preparation of a vertical SBD device with ultrahigh breakdown voltage requires a thick epitaxial film, the thickness of the epitaxial film needs to be more than 7 mu m, and the carrier concentration needs to be controlled at 10 16 cm 3 Orders of magnitude and below. Under the condition of the epitaxial film with the same thickness, the lower the carrier concentration is, the higher the reverse breakdown voltage of the prepared SBD device is. Among various epitaxial methods, the HVPE method is the only method with high growth speed and can convert beta-Ga into beta-Ga 2 O 3 A growth method for increasing the thickness of an epitaxial film to 7 μm or more, and a method for producing beta-Ga 2 O 3 Optimal selection of SBD devices.
Because the gallium boat of HVPE adopts a quartz structure, corrosive gas Cl is generated under the condition of high temperature 2 The gallium boat flowing through the quartz structure can generate certain corrosion effect on quartz, namely, the gallium boat flows through the quartz structure in beta-Ga 2 O 3 Si element is doped into beta-Ga in the growth process 2 O 3 In (1). Si in beta-Ga 2 O 3 Is a shallow donor which can lead to beta-Ga 2 O 3 The epitaxial film is n-type, and the carrier concentration can reach 10 17 cm -3 High carrier concentrations will result in the production of beta-Ga 2 O 3 The reverse breakdown voltage of the device is low, thereby degrading the performance of the device.
Disclosure of Invention
The invention aims to solve the problem of growing beta-Ga by an HVPE method 2 O 3 The problem of high Si concentration in the gallium oxide epitaxial film in the process provides a novel gallium boat structure, which is a gallium boat structure for reducing the Si content in the HVPE epitaxial film. The gallium boat is suitable for an HVPE furnace with a horizontal structure, and by utilizing the structure, the concentration of Si atoms in HVPE gallium oxide crystals can be greatly reduced, and the purity of a gallium oxide epitaxial film is improved, so that the preparation of an SBD device with high breakdown voltage is facilitated, and the performance of the device is improved.
The technical scheme adopted by the invention is as follows: a gallium boat structure for reducing Si content in an HVPE epitaxial film is characterized in that the gallium boat structure is of a multi-layer structure, the outer layer of the gallium boat structure is a quartz tube, and the left end of the gallium boat structure is sealed on a flange of HVPE to play a role in supporting; the middle layer is two pyrolytic boron nitride tubes, namely a first pyrolytic boron nitride tube and a second pyrolytic boron nitride tube, so as to prevent corrosive gas Cl 2 The inner layer is a pyrolytic boron nitride crucible used for containing liquid metal gallium; the first pyrolytic boron nitride tube is sleeved in the quartz tube; second heatThe first pyrolytic boron nitride tube is sleeved with the boron nitride removing tube; the pyrolytic boron nitride crucible is placed inside a second pyrolytic boron nitride tube.
The beneficial effects produced by the invention are as follows: after the invention is adopted, the corrosive gas Cl can be effectively prevented 2 Contact with the quartz tube to prevent the quartz tube from being corroded and avoid beta-Ga 2 O 3 Si impurities are doped into the epitaxial film, so that the carrier concentration of the epitaxial film is reduced, and the purity of the epitaxial film is improved.
Drawings
FIG. 1 is a schematic view of an HVPE chamber configuration of the invention;
FIG. 2 is an exploded view of the gallium boat 102 parts of FIG. 1;
FIG. 3 is an enlarged assembly view of the gallium boat 102 of FIG. 1.
Detailed Description
The invention is further described below with reference to the accompanying drawings.
As shown in fig. 2 and 3, a gallium boat 102 for reducing the Si content in the HVPE epitaxial film has a multi-layer structure, an outer layer is a quartz tube 102a, and the left end is sealed on a flange of HVPE to play a role of support; the middle layer is two pyrolytic boron nitride tubes, namely a first pyrolytic boron nitride tube 102b and a second pyrolytic boron nitride tube 102c, which prevent corrosive gas Cl 2 The inner layer is a pyrolytic boron nitride crucible 102d which is contacted with the quartz tube 102a and is used for containing liquid metal gallium; the first pyrolytic boron nitride tube 102b is sleeved in the quartz tube 102a (its outer diameter is slightly smaller than the inner diameter of the quartz tube 102 a); the second pyrolytic boron nitride tube 102c is nested within the first pyrolytic boron nitride tube 102b (with an outer diameter slightly smaller than the inner diameter of the first pyrolytic boron nitride tube 102 b); the pyrolytic boron nitride crucible 102d is placed within the second pyrolytic boron nitride tube 102 c. The assembled gallium boat 102 is schematically shown in FIG. 3.
The design and working principle of the invention are as follows: the HVPE apparatus furnace body structure is shown in FIG. 1, a quartz tube cavity 101 is placed in a multi-temperature-zone resistance furnace, two ends of the quartz tube cavity are sealed by flanges, and carrier gas nitrogen and source gas O are filled from the left end 2 And tail gas at the right end is discharged. The pyrolytic boron nitride crucible 102d in the gallium boat 102 holds gallium metal, the left end of the gallium boat 102 is sealed on a flange, cl 2 Flowing through the gallium boat and reacting with the galliumGaCl is generated and carried to the base 104 through the nitrogen carrier gas, on the surface of the substrate 103 and O 2 Reacting the gallium oxide. The substrate 103 is placed on a susceptor 104. The gallium boat 102 is mainly used for containing raw material metal gallium and isolating oxygen to prevent GaCl and O 2 Early mixing to form beta-Ga 2 O 3 And (4) polycrystallization. Typically, the gallium boat 102 is made of quartz, and the corrosive gas Cl is present at high temperature 2 Can cause corrosion to quartz, and leads to the unintended doping of beta-Ga in Si element 2 O 3 In the epitaxial film, the carrier concentration of the epitaxial film is caused to be high. In order to reduce the carrier concentration, it is necessary to prevent corrosive gas Cl 2 The invention adopts a multilayer structure to prevent the corrosion of the quartz by corrosive gas. The outer layer is a quartz tube structure, one end of the outer layer can be connected with the flange, and the outer layer plays a role in fixing and supporting the inner layer pyrolytic boron nitride piece. The middle and inner layers are pyrolytic boron nitride tube structures mainly used for preventing Cl 2 In contact with the quartz. The pyrolytic boron nitride crucible is placed inside the second pyrolytic boron nitride tube at the inner layer, and liquid metal gallium is placed inside the crucible. The right nozzle of the second pyrolytic boron nitride in the inner layer is opposite to the base 104, so that GaCl can reach the surface of the substrate at a certain flow rate, and the GaCl is mixed with oxygen to generate gallium oxide to be deposited on the surface of the substrate.
The invention may also be used for internal gallium/aluminum boat structures of HVPE grown GaN, alN, etc.
Claims (1)
1. The gallium boat structure for reducing the Si content in the HVPE epitaxial film is characterized in that the gallium boat structure is of a multi-layer structure, the outer layer of the gallium boat structure is a quartz tube (102 a), and the left end of the gallium boat structure is sealed on a flange of HVPE to play a supporting role; the middle layer is two pyrolytic boron nitride tubes, namely a first pyrolytic boron nitride tube (102 b) and a second pyrolytic boron nitride tube (102 c), and corrosive gas Cl is prevented 2 The quartz tube (102 a) is contacted, and a right nozzle of the second pyrolytic boron nitride is opposite to the base (104), so that GaCl is ensured to reach the surface of the substrate at a certain flow rate; the inner layer is a pyrolytic boron nitride crucible (102 d) used for containing liquid metal gallium; the first pyrolytic boron nitride tube (102 b) is sleeved in the quartz tube (102 a) and has the outer diameter ratio of the quartz tube (102 b)a) The inner diameter is slightly smaller; a second pyrolytic boron nitride tube (102 c) is sleeved in the first pyrolytic boron nitride tube (102 b); the pyrolytic boron nitride crucible (102 d) is placed inside the second pyrolytic boron nitride tube (102 c) with an outside diameter slightly smaller than the inside diameter of the first pyrolytic boron nitride tube (102 b).
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| CN202011141095.0A CN112210828B (en) | 2020-10-22 | 2020-10-22 | Gallium boat structure for reducing Si content in HVPE epitaxial film |
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| CN202011141095.0A CN112210828B (en) | 2020-10-22 | 2020-10-22 | Gallium boat structure for reducing Si content in HVPE epitaxial film |
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| CN112210828B true CN112210828B (en) | 2023-03-28 |
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| US4592307A (en) * | 1985-02-28 | 1986-06-03 | Rca Corporation | Vapor phase deposition apparatus |
| JP2007197302A (en) * | 2005-12-28 | 2007-08-09 | Sumitomo Electric Ind Ltd | Fabrication method and fabrication apparatus of group iii nitride crystal |
| CN111041559B (en) * | 2019-12-13 | 2021-07-20 | 四川大学 | Synthetic container and synthetic method of quaternary sulfur lithium compound polycrystal |
| CN211689296U (en) * | 2019-12-26 | 2020-10-16 | 北京国晶辉红外光学科技有限公司 | Reaction tube device for synthesizing semiconductor polycrystalline material |
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