CN112359417B - Method for maskless in-situ transverse epitaxy of alpha-phase gallium oxide film - Google Patents
Method for maskless in-situ transverse epitaxy of alpha-phase gallium oxide film Download PDFInfo
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- CN112359417B CN112359417B CN202011038141.4A CN202011038141A CN112359417B CN 112359417 B CN112359417 B CN 112359417B CN 202011038141 A CN202011038141 A CN 202011038141A CN 112359417 B CN112359417 B CN 112359417B
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- C30B25/02—Epitaxial-layer growth
- C30B25/18—Epitaxial-layer growth characterised by the substrate
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Abstract
The invention provides a maskless in-situ transverse epitaxial method for an alpha-phase gallium oxide film, which comprises the following steps of: (1) extending a gallium oxide buffer layer on a substrate; (2) Growing a layer of indium oxide quantum dots on the gallium oxide buffer layer in a very short time to obtain a patterned gallium oxide epitaxial substrate; (3) And continuously extending the alpha-phase gallium oxide film on the patterned gallium oxide epitaxial substrate until the upper parts of the indium oxide quantum dots are fully paved by the gallium oxide. The invention adopts the transverse epitaxial technology to ensure that the upper parts of the indium oxide quantum dots are fully paved by gallium oxide, the dislocation of the window area is cut off and disappears in the transverse growth area, and part of the dislocation bends to the transverse growth area by 90 degrees and cannot reach the surface of a film, so that the dislocation is greatly reduced.
Description
Technical Field
The invention relates to the technical field of semiconductors, in particular to a preparation method of an alpha-phase gallium oxide film, namely a maskless in-situ transverse epitaxial method of the alpha-phase gallium oxide film.
Background
Gallium oxide as a semiconductor material with ultra-wide bandgap has the advantages of high breakdown field strength, high electron saturation rate and the like, so that gallium oxide is another important preferred material in the application aspects of deep ultraviolet electronic devices and high-power electronic devices after III-nitride. Gallium oxide has five crystal forms of alpha, beta, gamma, kappa and delta, wherein the beta phase is the most stable, so that the gallium oxide can grow more easily, and the research on the epitaxy and the devices is the most extensive. The alpha-phase gallium oxide of the metastable phase of the corundum structure has larger forbidden bandwidth (Eg is approximately equal to 5.3 eV), and the alpha-In of the metastable phase of the corundum structure has the same structure as the alpha-In of the metastable phase of the corundum structure2O3(Eg ≈ 3.7 eV), sapphire (. Alpha. -Al)2O3Eg ≈ 9 eV), the range of adjustable band gap of the alloy is large, so that the research and development of the photoelectric device for expanding alpha-phase gallium oxide to UVC to UVA wave bands are attracted in recent years. The alpha-phase gallium oxide has better lattice match with the sapphire substrate with a corundum structure, so that higher quality can be obtained more easily. Further, sapphire (. Alpha. -Al)2O3) Substrate and beta-Ga2O3Substrate in processHas great advantages in low cost.
At present, the preparation method of gallium oxide mainly includes Metal Organic Chemical Vapor Deposition (MOCVD), molecular Beam Epitaxy (MBE), pulsed Laser Deposition (PLD), halide Vapor Phase Epitaxy (HVPE), ultrasonic-assisted Mist phase transport chemical vapor deposition (Mist-CVD), and the like. Due to the fact that the substrate and the epitaxial film have lattice mismatch, high-density edge dislocation caused by stress release can extend to the surface of the sample along with the progress of epitaxy, and crystal quality has a large promotion space.
Stress engineering and defect control of epitaxial films are commonly used as a common method to improve transport properties and breakdown field strength. The conventional lateral epitaxy technology is that masking materials are deposited on an epitaxial layer, a specific pattern window is etched, then epitaxial growth is carried out on the opened pattern window, and when the window is full, lateral spreading and extension are carried out until the whole epitaxial layer is connected into a whole. The transverse epitaxial technology can ensure that the dislocation of the window area is cut off and disappears in the transverse growth area, and part of the dislocation bends 90 degrees towards the transverse growth area and cannot reach the surface of the film, thereby greatly reducing the dislocation and improving the quality of the epitaxial layer. However, the conventional lateral epitaxy technique is complicated, a mask needs to be used, and etching may damage the surface of the thin film to a certain extent.
Disclosure of Invention
The invention aims to: the present invention is directed to overcoming the above-mentioned deficiencies in the prior art by providing a novel, simple, maskless, in-situ lateral epitaxy technique for epitaxially growing high quality gallium oxide films with low dislocation density.
The technical scheme is as follows: in order to achieve the purpose, the invention provides a maskless in-situ transverse epitaxy method for an alpha-phase gallium oxide film, which comprises the following steps:
(1) Extending a gallium oxide buffer layer on the substrate;
(2) Growing a layer of indium oxide quantum dots on the gallium oxide buffer layer in a very short time to obtain a patterned gallium oxide epitaxial substrate;
(3) And continuously extending the alpha-phase gallium oxide film on the patterned gallium oxide epitaxial substrate until the upper parts of the indium oxide quantum dots are fully paved by gallium oxide.
The invention adopts the transverse epitaxy technology, so that the upper parts of the indium oxide quantum dots are fully paved by gallium oxide, the dislocation of the window region is cut off and disappears in the transverse growth region, and part of the dislocation bends to the transverse growth region by 90 degrees and cannot reach the surface of a film, thereby greatly reducing the dislocation and improving the quality of an epitaxial layer, namely transverse epitaxy. The in-situ maskless lateral epitaxy technology greatly optimizes the process steps of the traditional lateral epitaxy and reduces the etching damage, thereby being a brand new method for laterally extending the high-quality gallium oxide film.
In the method, the size and the density of the quantum dots can be controlled by strictly controlling the growth conditions of the indium oxide quantum dots, namely the proportion of the area of the quantum dots can be controlled, and the area of the low dislocation density region can be controlled.
When the gallium oxide film grown by the method grows flat, an epitaxial substrate with high quality can be obtained, various oxides, doped gallium oxide and oxide alloy can be epitaxially grown on the epitaxial substrate, and various high-quality photoelectric detectors and thin film transistor structures can be prepared.
Several alternatives are provided below, but not as an additional limitation to the above general solution, but merely as a further addition or preference, each alternative may be combined individually for the above general solution or between several alternatives without technical or logical contradictions.
Optionally, the method for epitaxial growth of gallium oxide includes: metal organic vapor phase epitaxy, halide vapor phase epitaxy, and ultrasonic assisted mist transport chemical vapor deposition.
Optionally, the substrate is a sapphire substrate.
Optionally, the thickness of the gallium oxide buffer layer is 0.005-1 μm.
Optionally, the width of the indium oxide quantum dots is 0.004-0.2 μm, the height of the indium oxide quantum dots is 0.002-0.1 μm, and the distance between adjacent indium oxide quantum dots is 0.01-1 μm.
Has the advantages that: compared with the prior art, the invention has the following advantages:
1. the invention adopts a novel, simple and convenient maskless transverse epitaxy technology, and can obtain the gallium oxide single crystal film with high quality and low dislocation density;
2. in the process of transversely extending the gallium oxide, two wings of the extended gallium oxide can be polymerized on the upper parts of the indium oxide quantum dots to release stress, so that the quality of the film can be greatly improved;
3. the invention does not adopt optical etching and ion etching techniques which are necessary in the traditional transverse epitaxial growth technology, thereby greatly simplifying the transverse epitaxial growth technology.
Drawings
FIG. 1 is a schematic view of a gallium oxide thin film structure according to an embodiment;
FIG. 2 is a TEM cross-section of a gallium oxide thin film obtained by the method described in example;
FIG. 3 is a lateral bending model of dislocations according to an exemplary embodiment;
FIG. 4 is a schematic view of an exemplary embodiment of a vapor transport chemical vapor deposition system.
Detailed Description
The invention will be further described with reference to the following figures and specific examples. It is to be understood that the present invention may be embodied in various forms, some of which are illustrated in the accompanying drawings and described below as illustrative and non-limiting embodiments, and are not intended to limit the invention to the specific embodiments described.
It is to be understood that the features listed above for different embodiments may be combined with each other, where technically feasible, to form further embodiments within the scope of the present invention. Furthermore, the particular examples and embodiments of the invention described are non-limiting, and modifications may be made in the structure, steps, sequence of steps, or illustrated above without departing from the scope of the invention.
The embodiment is as follows:
this example provides a maskless in-situ lateral epitaxy method of an alpha-phase gallium oxide film, which selects a sapphire substrate and applies a Mist-CVD-based method to the sapphire substrateAnd an alpha-phase gallium oxide film is extended on the substrate. In this embodiment, a mist phase transport chemical vapor deposition system proposed in patent 201811030854 is adopted, which is shown in fig. 4 and comprises: an ultrasonic atomization source, a reaction chamber and a heating system. The reaction chamber is internally provided with an airflow bundling device which is of a horizontal structure as a whole, the height of a reaction type in a growth area is 1-3mm, the width of the reaction type in the growth area is 2.5-3.5cm, a reaction source is aqueous solution, the aqueous solution is atomized into micron-sized liquid drops by an ultrasonic atomizer and then is transported into the reaction chamber by transport gas, meanwhile, diluent gas and the transport gas enter the reaction chamber from the same gas port, waste gas is discharged out of the reaction chamber from the other side and enters a tail gas treatment device, the pressure of the reaction chamber is maintained to be slightly higher than one atmosphere, doping and alloy can be provided by a plurality of atomization sources, or mixed solution which is prepared in proportion can be added into one source. The transport gas is selected to be N2 to avoid premature oxidation of the reactants, and the diluent gas is selected to be N2 or O2Or N2And O2The flow of the mixed gas is controlled by a digital gas mass flow meter. The airflow converging structure is made of quartz, the sample water is placed on the quartz support at the bottom, and the height of the reaction chamber is determined by the thickness of the quartz support.
Based on the mist phase transport chemical vapor deposition system, the specific steps of the embodiment are as follows:
1. placing a substrate on a proper position of a quartz support, placing the quartz support into an airflow bundling device, and placing the airflow bundling device into a growth cavity to enable the substrate to be located at a position close to the front end of the growth cavity; adjusting conditions such as deposition temperature, gas flow, atomizer power and the like, opening a gas inlet switch of a gallium source, ultrasonically atomizing water-soluble gallium salt into micron-sized liquid drops by an ultrasonic atomizer, conveying the liquid drops into a reaction chamber by transport gas and dilution gas, and extending a first uniform gallium oxide buffer layer on a sapphire substrate; the thickness of the gallium oxide buffer layer is 0.005-1 μm;
2. closing an air inlet switch of a gallium source, opening an air inlet switch of an indium source, adjusting the deposition temperature and the deposition time, ultrasonically atomizing water-soluble indium salt into micron-sized liquid drops by an ultrasonic atomizer in a very short time, conveying the liquid drops into a reaction chamber by transport gas and dilution gas, and carrying out in-situ epitaxy on a layer of uniform indium oxide quantum dots on a gallium oxide buffer layer to obtain a patterned surface; the width of the indium oxide quantum dots is 0.004-0.2 mu m, the height of the indium oxide quantum dots is 0.002-0.1 mu m, and the distance between the adjacent indium oxide quantum dots is 0.01-1 mu m;
3. and finally, closing an air inlet switch of the indium source, opening the air inlet switch of the gallium source, ultrasonically atomizing water-soluble gallium salt into micron-sized liquid drops by an ultrasonic atomizer, conveying the micron-sized liquid drops into a reaction chamber by conveying gas and diluting gas, and transversely extending a second layer of gallium oxide film on the indium oxide quantum dots to grow flat gallium oxide to obtain the gallium oxide film.
Thus, the preparation of the alpha-phase gallium oxide film is finished. If necessary, the epitaxial growth of alpha-In can be continued on the flat gallium oxide2O3、α-Al2O3And alloys thereof; if an optoelectronic device is required to be manufactured, various layers of structures required by the device can be continuously grown on the optoelectronic device.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention, and such modifications and adaptations are intended to be within the scope of the invention.
Claims (2)
1. A maskless in-situ lateral epitaxy method for an alpha-phase gallium oxide film is characterized by comprising the following steps: (1) extending a gallium oxide buffer layer on a substrate; (2) Growing a layer of indium oxide quantum dots on the gallium oxide buffer layer in a very short time to obtain a patterned gallium oxide epitaxial substrate; (3) Continuously extending an alpha-phase gallium oxide film on the patterned gallium oxide epitaxial substrate until the upper parts of the indium oxide quantum dots are fully paved by gallium oxide;
the method for extending the alpha-phase gallium oxide film specifically comprises the following steps: an ultrasonic-assisted mist phase transport chemical vapor deposition method; ultrasonically atomizing water-soluble gallium salt into micron-level liquid drops by an ultrasonic atomizer, conveying the liquid drops into a reaction chamber by conveying gas and diluent gas, and generating a first gallium oxide buffer layer on a substrate, wherein the thickness of the gallium oxide buffer layer is 0.005-1 mu m;
then closing an air inlet switch of the gallium salt, opening an air inlet switch of the indium source, ultrasonically atomizing the water-soluble indium salt into micron-level liquid drops by an ultrasonic atomizer, conveying the liquid drops into a reaction chamber by transport gas and diluent gas, and carrying out in-situ epitaxy on a layer of uniform indium oxide quantum dots on a gallium oxide buffer layer to obtain a patterned surface: the width of the indium oxide quantum dots is 0.004-0.2 mu m, the height is 0.002-0.1 mu m, and the interval between adjacent indium oxide quantum dots is 0.01-1 mu m;
and then closing an air inlet switch of the indium salt, opening an air inlet switch of a gallium source, carrying the water-soluble gallium salt into micron-level liquid drops through the ultrasonic atomizer, then carrying the liquid drops to a reaction chamber through transport gas and diluent gas, and epitaxially growing a second gallium oxide film on the indium oxide quantum dots.
2. The method of maskless in situ, lateral epitaxy of an alpha phase gallium oxide film according to claim 1, wherein said substrate is a sapphire substrate.
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| US7554109B2 (en) * | 2003-09-05 | 2009-06-30 | Dot Metrics Technology, Inc. | Quantum dot optoelectronic devices with nanoscale epitaxial lateral overgrowth and methods of manufacture |
| CN1300387C (en) * | 2004-11-12 | 2007-02-14 | 南京大学 | Process for non-mask transverse epitaxial growth of high quality gallium nitride |
| CN104988579A (en) * | 2015-07-08 | 2015-10-21 | 西安电子科技大学 | Gallium oxide film based on sapphire substrate and growing method of gallium oxide film |
| CN107587190A (en) * | 2017-08-14 | 2018-01-16 | 南京大学 | A kind of method for preparing GaN substrate material |
| CN109423694B (en) * | 2017-08-21 | 2022-09-09 | 株式会社Flosfia | Crystalline film, semiconductor device including the same, and method of manufacturing the same |
| CN110504343B (en) * | 2018-05-18 | 2021-02-23 | 中国科学院苏州纳米技术与纳米仿生研究所 | Gallium oxide film based on sapphire substrate and growth method and application thereof |
| CN109056066A (en) * | 2018-09-05 | 2018-12-21 | 南京大学 | A kind of system of ultrasonic wave added mist phase transport chemical vapor deposition growing gallium oxide |
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