CN116334582A - Preparation system and method of multisource atomization vapor deposition gallium oxide film - Google Patents

Preparation system and method of multisource atomization vapor deposition gallium oxide film Download PDF

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CN116334582A
CN116334582A CN202310601968.9A CN202310601968A CN116334582A CN 116334582 A CN116334582 A CN 116334582A CN 202310601968 A CN202310601968 A CN 202310601968A CN 116334582 A CN116334582 A CN 116334582A
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oxide film
atomization
atomizing
raw material
solution tank
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刘洋
郭超
母凤文
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Jc Innovative Semiconductor Substrate Technology Co ltd
Beijing Qinghe Jingyuan Semiconductor Technology Co ltd
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Jc Innovative Semiconductor Substrate Technology Co ltd
Beijing Qinghe Jingyuan Semiconductor Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B17/00—Apparatus for spraying or atomising liquids or other fluent materials, not covered by the preceding groups
    • B05B17/04—Apparatus for spraying or atomising liquids or other fluent materials, not covered by the preceding groups operating with special methods
    • B05B17/06—Apparatus for spraying or atomising liquids or other fluent materials, not covered by the preceding groups operating with special methods using ultrasonic or other kinds of vibrations
    • B05B17/0607—Apparatus for spraying or atomising liquids or other fluent materials, not covered by the preceding groups operating with special methods using ultrasonic or other kinds of vibrations generated by electrical means, e.g. piezoelectric transducers
    • B05B17/0615—Apparatus for spraying or atomising liquids or other fluent materials, not covered by the preceding groups operating with special methods using ultrasonic or other kinds of vibrations generated by electrical means, e.g. piezoelectric transducers spray being produced at the free surface of the liquid or other fluent material in a container and subjected to the vibrations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
    • C23C16/4481—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by evaporation using carrier gas in contact with the source material
    • 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

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

The invention provides a preparation system and a preparation method of a multisource atomization vapor deposition gallium oxide film, wherein the preparation system of the multisource atomization vapor deposition gallium oxide film comprises an atomization unit and a reaction unit which are connected in sequence; the atomizing unit comprises at least one atomizing container, at least two atomizing modules are arranged in the atomizing container, the at least two atomizing modules respectively and independently comprise a solution tank and an ultrasonic wave generating mechanism, the solution tank is of an open structure, raw material solutions are contained in the solution tank, the ultrasonic wave generating mechanisms of the different atomizing modules are switched to atomize the raw material solutions in the solution tank to form mist, and the mist flows into the reaction unit to grow at least two oxide film layers which are sequentially laminated or grow alloy oxide films with at least two doping metals. The invention provides a plurality of atomization sources, which can control raw material solutions with different concentration ratios and different doping metals to atomize and obtain an oxide film or an alloy oxide film with a plurality of film layers.

Description

Preparation system and method of multisource atomization vapor deposition gallium oxide film
Technical Field
The invention belongs to the technical field of film preparation, relates to preparation of gallium oxide films, and particularly relates to a preparation system and a preparation method of a multisource atomization vapor deposition gallium oxide film.
Background
Mist-CVD (Mist Chemical Vapor Deposition, atomizing chemical vapor deposition) generally atomizes a raw material solution into micron-sized droplets by an ultrasonic atomizer, and then conveys the droplets to a reaction part by carrier gas to react at a certain temperature to form an oxide film. Mist-CVD works differently from molecular beam epitaxy (Molecular beam epitaxy, MBE) and Metal-organic chemical deposition (Metal-Organic Chemical Vapor Deposition, MOCVD) methods, can be performed at atmospheric pressure and relatively low temperature without the need for expensive vacuum systems and RF generators, and without the need for HCl, cl, as in the HVPE (Halide Vapor Phase Epitaxy ) method 2 The method has the advantages of equal intensity precursor, simple structure, simpler and cheaper installation and maintenance, higher efficiency, less energy consumption, less toxicity and danger, and is a safe, cheap and environment-friendly oxide semiconductor film growth method.
Ga 2 O 3 Is a transparent conductive oxide semiconductor, has a absorption edge of 240-280 nm, and has a larger forbidden bandwidth (4.9-5.3 eV) and breakdown field strength than SiC and GaN, so Ga 2 O 3 Can be widely applied to solar blind deep ultraviolet detectors and high-power devices. Ga 2 O 3 Has five isomers of alpha, beta, gamma, delta and epsilon, respectively. alpha-Ga 2 O 3 The crystals are metastable and the Mist-CVD process is typically used to produce a-Ga 2 O 3 A film. Mist-CVD is a promising growth for Ga due to its simplicity and low cost 2 O 3 A method of forming a film.
α-Ga 2 O 3 The forbidden band width is about 5.3eV, and has the same structure as sapphire, and the lattice mismatch between them in the a-axis and c-axis directions is about 4.81% and 3.54%. Similar crystal structure and smaller lattice mismatch, such that alpha-Ga 2 O 3 Can be grown on a sapphire substrate by a Mist-CVD method. However, the process is not limited to the above-mentioned process,the growth interface still has higher dislocation density and stress, how to grow higher-quality alpha-Ga 2 O 3 Films have been an important target of research.
Currently, lateral epitaxial overgrowth (Epitaxial Lateral Over-Growth, ELO) is commonly employed, or a buffer layer α - (Al) is added x Ga 1-x ) 2 O 3 Is such that alpha-Ga 2 O 3 Grown on sapphire. Compared with lateral epitaxial overgrowth, the method for adding the buffer layer is simpler and more efficient, does not need other equipment, and can be used for growth through Mist-CVD. However, the existing Mist-CVD apparatus is equipped with a single atomization source, requires replacement of raw material solutions when growing films of different materials and compositions, is cumbersome in steps, and is inefficient.
Thus, how to provide a plurality of different atomization sources to grow high quality alpha-Ga 2 O 3 The thin film, the multilayer metal oxide thin film, will become the key direction of research.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation system and a preparation method of a multisource atomization vapor deposition gallium oxide film, which can control raw material solutions with different concentration ratios or different doping metals to atomize and convey to a reaction unit for film preparation by switching on and off ultrasonic generating mechanisms of different atomization modules to obtain an oxide film with a multilayer film layer or an alpha-phase oxide alloy oxide film with different types.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a preparation system of a multisource atomization vapor deposition gallium oxide film, which comprises an atomization unit and a reaction unit which are sequentially connected;
the atomizing unit comprises at least one atomizing container, at least two atomizing modules are arranged in the atomizing container, the at least two atomizing modules respectively and independently comprise a solution tank and an ultrasonic generating mechanism, the solution tank is provided with an open structure, raw material solutions are contained in the solution tank, the ultrasonic generating mechanisms of different atomizing modules are switched to atomize the raw material solutions in the solution tank to form mist, and the mist flows into the reaction unit to grow at least two oxide film layers which are sequentially laminated or grow alloy oxide films with at least two doping metals.
The preparation system provided by the invention is provided with a plurality of independent atomization modules, each atomization module is provided with an independent ultrasonic atomization device, the plurality of atomization modules are arranged in the same atomization container, raw material solutions in different solution tanks corresponding to the atomization modules are atomized to form fog by switching on and off of ultrasonic generation mechanisms of the different atomization modules, and then enter a reaction unit to grow a film, and the problem that the traditional Mist-CVD can only grow a single-layer film is solved by providing a plurality of atomization sources, so that the preparation system is suitable for the growth of a plurality of buffer layers and the growth of various alloy oxide films, the raw material solutions do not need to be replaced in the growth process, and the doping components can be effectively controlled to obtain the high-quality multi-layer oxide film.
The raw material solutions in the different solution tanks are different from each other, and can be materials with different concentrations and proportions or materials with different doping metal elements. When different atomizing modules are switched, only one atomizing module can be started at a time, and at least two atomizing modules can be started at the same time. To help those skilled in the art better understand the overall technical solution and working procedure of the present invention, the present invention exemplarily provides the following different modes regarding the on and off of the atomizing module:
(1) First mode: the raw material solutions in different solution tanks are all materials with the same elements, but the element concentration and the proportion of each raw material solution are different;
when an ultrasonic generating mechanism of one atomizing module is started, raw material solution in a solution tank corresponding to the ultrasonic generating mechanism is atomized, mist is formed in an atomizing container, the other atomizing modules are kept closed, and the formed mist is sent into a reaction unit to grow a first film layer; after the growth is finished, closing the atomization module, starting another atomization module, forming mist with different material ratios in the atomization container, flowing into the reaction unit, and forming a second film layer on the surface of the first film layer; and the like, until the atomization of various raw material solutions in the atomization container is completed in turn, a plurality of oxide film layers can be formed in the reaction unit.
(2) Second mode: the raw material solutions in the different solution tanks are respectively materials with different elements;
scheme one: simultaneously starting an ultrasonic generating mechanism of the two atomizing modules to atomize the raw material solution in the solution tank corresponding to the ultrasonic generating mechanism, forming mixed mist with two different elements in the atomizing container, keeping the other atomizing modules closed, sending the formed mixed mist into a reaction unit to grow a film layer, and closing the two atomizing modules after the growth is finished to obtain a required single-layer film with different types of alpha-phase oxides; the other two atomization modules of other combinations can be directly started after the raw material solution is not needed to be replaced and one type of film layer is taken out, and can comprise any one of the two modules, mist with different elements is formed in the atomization container and flows into the reaction unit to form two types of film layers, and after the growth is finished, the other two atomization modules are closed, so that the required other single-layer film with different types of alpha-phase oxides is obtained.
Scheme II: simultaneously, the ultrasonic generating mechanisms of the three atomizing modules are started to atomize the raw material solution in the solution tank corresponding to the ultrasonic generating mechanisms, mixed mist with three different elements is formed in the atomizing container, the other atomizing modules are kept closed, the formed mixed mist is sent into the reaction unit to generate alloy oxide films containing three metal elements, and the like, the ultrasonic generating mechanisms of the atomizing modules can be started at will to form corresponding multiple metal alloy oxide films.
In the present invention, when one solution tank is atomized, the remaining solution tanks can be taken out to replenish the raw material solution.
As a preferable technical scheme of the invention, the atomization unit further comprises an air inlet pipeline, an air outlet pipeline and a mixing pipeline.
The air inlet pipeline is connected with the atomization container and is used for providing carrier gas.
The mixing pipeline is internally circulated with dilution gas.
One end of the air outlet pipeline is connected with the atomizing container, and the other end of the air outlet pipeline is communicated with the mixing pipeline and is used for discharging fog in the atomizing container into the mixing pipeline and mixing the fog with diluent gas to obtain mixed gas.
The mixing pipeline is connected with the reaction unit and is used for sending mixed gas into the reaction unit.
In the invention, carrier gas is introduced into an atomization container by utilizing an air inlet pipeline, and mist formed by atomizing a raw material solution in a solution tank is carried out by an air outlet pipeline, enters a mixing pipeline, and is mixed with diluent gas and then is fed into a growing film in a reaction unit.
As a preferable technical scheme of the invention, the ultrasonic wave generating mechanism comprises a base, wherein the base is arranged at the bottom of the solution tank, and at least one ultrasonic wave generating component is arranged in the base.
The base is close to one side surface of solution jar has seted up the holding tank, hold the medium liquid in the holding tank, ultrasonic wave that the ultrasonic wave subassembly produced passes through the medium liquid passes through the solution jar.
The media liquid comprises deionized water.
As a preferable mode of the invention, the top surface of the atomizing container is provided with a first vent hole, and the first vent hole is used for discharging mist.
The side wall of the atomization container is provided with a second vent hole, and the second vent hole is used for circulating carrier gas.
The bottom surface of the solution tank is provided with a membrane, which contacts the medium liquid.
The separator comprises polyethylene, polytetrafluoroethylene or polyvinylidene fluoride.
The top of the solution tank is of an open structure, namely, a non-cover design is adopted, a diaphragm is arranged at the bottom of the solution tank, ultrasonic waves generated by the ultrasonic wave generating assembly are transmitted to the diaphragm through medium liquid, atomization of raw material solution in the solution tank is achieved, the raw material solution directly enters the atomization container, and the raw material solution is discharged out of the atomization container along with carrier gas.
As a preferable technical scheme of the invention, the reaction unit comprises a reaction chamber, and a rectification chamber, a reaction chamber and a buffer chamber are sequentially arranged in the reaction chamber along the flow direction of mist.
A substrate is arranged in the reaction chamber and used for growing the oxide film layer.
The substrate includes c-plane sapphire.
The top and the bottom of the peripheral wall of the reaction chamber are respectively provided with a first heating component and a second heating component.
And the outlet end of the buffer chamber is also provided with a vacuumizing assembly.
The invention adopts the vacuumizing assembly to vacuumize, drives the mixed gas to flow in the reaction chamber, and the mixed gas enters the reaction chamber after being rectified in the rectification chamber, forms an oxide film layer on the surface of the substrate by growth, and is discharged out of the reaction chamber under the action of the vacuumizing assembly after entering the buffer chamber again after the reaction.
In a second aspect, the present invention provides a method for preparing a multisource atomized vapor deposition gallium oxide film, where the preparation method adopts the preparation system of the multisource atomized vapor deposition gallium oxide film in the first aspect, and the preparation method includes:
providing at least two atomizing modules containing different raw material solutions, and placing the atomizing modules in the same atomizing container;
(II) switching different atomizing modules to independently perform ultrasonic atomization treatment to form mist;
(iii) feeding the mist into a reaction unit to grow at least two oxide film layers stacked in sequence, or to grow an alloy oxide film having at least two doping metals.
According to the invention, different raw material solutions are switched for atomization, so that mist with different material concentrations and proportions or different elements is formed, multiple atomization sources are provided, and a plurality of sequentially laminated oxide film layers are formed in the reaction chamber, so that components and concentrations thereof in the raw material solutions can be controlled, and a high-quality gallium oxide film is formed.
As a preferable technical scheme of the invention, different raw material solutions of the at least two atomizing modules all contain the same gallium source and doped metal source, and the molar ratio of gallium to doped metal in the raw material solutions is different.
The molar ratio of gallium/doped metal in the raw material solution is 1 (0.2-2.5), for example, it may be 1:0.2, 1:0.5, 1:0.8, 1:1.0, 1:1.2, 1:1.5, 1:1.8, 1:2.0, 1:2.2 or 1:2.5, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
The doping metal element of the doping metal source comprises at least one of Fe, al, in and Sn.
The raw material solution is also added with a solvent.
The solvent comprises deionized water. HCl with the mass fraction of 1% can be added into the solvent, so that the growth quality of the film can be improved. In addition, according to the practical situation, the person skilled in the art can selectively add H with the mass fraction of 1.5% into the solvent 2 O 2 . As a preferred technical scheme of the invention, the different raw material solutions of the at least two atomizing modules are respectively at least one gallium source and at least one doped metal source. The doping metal element of the doping metal source comprises at least one of Fe, al, in and Sn.
The raw material solution is also added with a solvent.
The solvent comprises deionized water. HCl with the mass fraction of 1% can be added into the solvent, so that the growth quality of the film can be improved. In addition, according to the practical situation, the person skilled in the art can selectively add H with the mass fraction of 1.5% into the solvent 2 O 2 。
The gallium source in the present invention may be a gallium-containing compound including, but not limited toGa(acac) 3 Or GaCl 3 The method comprises the steps of carrying out a first treatment on the surface of the The doped metal source refers to a metal element-containing compound including, but not limited to, fe (acac) 3 、Al(acac) 3 、In(acac) 3 、FeCl 3 、AlCl 3 、InCl 3 、SnCl 4 。
As a preferable technical scheme of the invention, the preparation method further comprises the following steps:
and independently introducing carrier gas and diluent gas into the atomization unit, carrying out mist by the carrier gas, mixing the mist with the diluent gas to obtain mixed gas, and sending the mixed gas into the reaction unit to grow an oxide film layer.
The flow rate of the carrier gas is 2 to 8L/min, for example, 2L/min, 3L/min, 4L/min, 5L/min, 6L/min, 7L/min or 8L/min, but the carrier gas is not limited to the recited values, and other values not recited in the range of the values are applicable.
The carrier gas comprises nitrogen, argon, air or oxygen.
The flow rate of the dilution gas is 0.3 to 2L/min, for example, 0.3L/min, 0.5L/min, 1.0L/min, 1.2L/min, 1.5L/min, 1.8L/min or 2.0L/min, but the flow rate is not limited to the recited values, and other values not recited in the range are applicable.
The diluent gas comprises air, oxygen or nitrogen.
In a preferred embodiment of the present invention, the temperature for growing the oxide film layer is 400 to 600 ℃, for example, 400 ℃, 420 ℃, 450 ℃, 480 ℃, 500 ℃, 530 ℃, 550 ℃, 580 ℃, or 600 ℃, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value range are equally applicable.
The time for growing the oxide film layer is 20 to 60min, for example, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 60min, but the time is not limited to the listed values, and other values not listed in the range of the values are applicable.
The thickness of the oxide film layer is 200 to 500nm, and may be 200nm, 220nm, 250nm, 280nm, 300nm, 320nm, 350nm, 380nm, 400nm, 430nm, 450nm, 480nm or 500nm, for example, but is not limited to the values listed, and other values not listed in the range are applicable.
The mixed gas of mist, carrier gas and diluent gas formed by the atomization unit enters the reaction chamber, and is not evaporated immediately after contacting the high-temperature substrate due to the Leton frost effect, but a steam layer is formed between the surface of the substrate and the liquid drops, so that the mixed gas is evaporated slowly and becomes small in the process of passing through the surface of the whole substrate, required raw materials are continuously provided for film growth, and the film grows uniformly on the surface of the whole substrate.
The numerical ranges recited herein include not only the above-listed point values, but also any point values between the above-listed numerical ranges that are not listed, and are limited in space and for the sake of brevity, the present invention is not intended to be exhaustive of the specific point values that the stated ranges include.
The system refers to an equipment system, a device system or a production device.
Compared with the prior art, the invention has the beneficial effects that:
the preparation system and the preparation method of the multisource atomization vapor deposition gallium oxide film are provided with a plurality of independent atomization modules, the atomization modules are arranged in the same atomization container, raw material solutions in different solution tanks corresponding to the atomization modules are atomized to form Mist by switching on and off of ultrasonic wave generating mechanisms of the different atomization modules, and then enter a reaction unit to grow films, so that a plurality of atomization sources are provided, the problem that the traditional Mist-CVD can only grow single-layer films is solved, the preparation system and the preparation method are suitable for growth of multi-layer buffer layers and growth of various alloy oxide films, raw material solutions do not need to be replaced in the growth process, doping components can be effectively controlled, and the high-quality multi-layer oxide film is obtained.
Drawings
Fig. 1 is a schematic structural view of an atomizing container according to embodiment 1 of the present invention;
fig. 2 is a schematic structural diagram of an atomization module provided in embodiment 1 of the present invention;
fig. 3 is a schematic structural diagram of a reaction chamber according to embodiment 1 of the present invention.
Wherein, 001-carrier gas; 002-diluent gas; 003-a first flow regulating assembly; 004-a second flow rate adjustment assembly; 005-atomizing vessel; 006-a first vent; 007-a second vent; 008-an air intake duct; 009-an outlet pipe; 010-mixing pipes;
A100-a first atomization module; b100-a second atomizing module; c100-a third atomization module; d100—a fourth atomization module; 101-a solution tank; 102-a raw material solution; 103-a base; 104-a first ultrasonic generator; 105-a second ultrasonic generator; 106-a medium liquid; 107-a membrane;
19-a reaction chamber; 20-rectifying chamber; 21-a reaction chamber; 22-a substrate; 23-a first heating assembly; 24-a second heating assembly; 25-a buffer chamber; 26-vacuumizing assembly; 27-an air outlet; 28-air inlet.
Detailed Description
It should be understood that in the description of the present invention, the terms "center," "upper," "lower," "front," "rear," "left," "right," "top," "bottom," "inner," "outer," and the like indicate or are based on the orientation or positional relationship shown in the drawings, merely to facilitate description of the present invention and to simplify the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first", "a second", etc. may explicitly or implicitly include one or more such feature. In the description of the present invention, unless otherwise indicated, the meaning of "a plurality" is two or more.
It should be noted that, in the description of the present invention, unless explicitly specified and limited otherwise, the terms "disposed," "connected," and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art in a specific case.
The technical scheme of the invention is further described below by the specific embodiments with reference to the accompanying drawings.
In one specific embodiment, the invention provides a preparation system of a multisource atomization vapor deposition gallium oxide film, which comprises an atomization unit and a reaction unit which are connected in sequence; the atomizing unit comprises at least one atomizing container 005, at least two atomizing modules are arranged in the atomizing container 005, the at least two atomizing modules respectively and independently comprise a solution tank 101 and an ultrasonic wave generating mechanism, the solution tank 101 is provided with an open structure, a raw material solution 102 is contained in the solution tank 101, the ultrasonic wave generating mechanism for switching different atomizing modules atomizes the raw material solution 102 in the solution tank 101 to form mist, and the mist flows into the reaction unit to grow at least two oxide film layers which are sequentially laminated or grow an alloy oxide film with at least two doping metals.
The preparation system provided by the invention is provided with a plurality of independent atomization modules, the plurality of atomization modules are arranged in the same atomization container 005, the raw material solution 102 in the corresponding different solution tanks 101 is atomized to form Mist by switching on and off of the ultrasonic wave generating mechanisms of the different atomization modules, and then enters the reaction unit to grow a film, so that a plurality of atomization sources are provided, the problem that the traditional Mist-CVD can only grow a single-layer film is solved, the preparation system is suitable for the growth of a plurality of buffer layers and the growth of various alloy oxide films, the raw material solution 102 is not required to be replaced in the growth process, the doping components can be effectively controlled, and the high-quality multi-layer oxide film is obtained.
The raw material solutions 102 in different solution tanks 101 are different from each other, and the materials with different raw material concentrations and proportions can also be materials with different doping metal elements. When different atomizing modules are switched, only one atomizing module can be started at a time, and at least two atomizing modules can be started at the same time. To help those skilled in the art better understand the overall technical solution and working procedure of the present invention, the present invention exemplarily provides the following different modes regarding the on and off of the atomizing module:
(1) First mode: the raw material solutions 102 in different solution tanks 101 are all materials with the same elements, but the element concentration and the proportion of each raw material solution 102 are different;
when the ultrasonic wave generating mechanism of one atomizing module is started, the raw material solution 102 in the solution tank 101 is atomized correspondingly, mist is formed in the atomizing container 005, other atomizing modules are kept closed, the formed mist is sent into the reaction unit to grow into a first layer of film layer, after the growth is finished, the atomizing module is closed, the other atomizing module is started, mist with different material proportions is formed in the atomizing container 005 and flows into the reaction unit, a second layer of film layer is formed on the surface of the first layer of film layer, and the like until the atomization of various raw material solutions 102 in the atomizing container 005 is sequentially completed, and a plurality of layers of oxide film layers can be formed in the reaction unit.
(2) Second mode: the raw material solutions 102 in the different solution tanks 101 are respectively materials with different elements;
scheme one: simultaneously starting ultrasonic wave generating mechanisms of the two atomizing modules to atomize the raw material solution 102 in the solution tank 101 corresponding to the ultrasonic wave generating mechanisms, forming mixed mist with two different elements in an atomizing container 005, keeping the other atomizing modules closed, sending the formed mixed mist into a reaction unit to grow a film layer, and closing the two atomizing modules after the growth is finished to obtain a required single-layer film with different types of alpha-phase oxides; the other two atomization modules of other combinations can be directly started after the raw material solution 102 is not needed to be replaced and one type of film layer is taken out, and can comprise any one of the two modules, mist with different elements is formed in the atomization container 005 and flows into the reaction unit to form two types of film layers, and after the growth is finished, the other two atomization modules are closed, so that the required other single-layer film with different types of alpha-phase oxides is obtained.
Scheme II: simultaneously, the ultrasonic wave generating mechanisms of the three atomizing modules are started to atomize the raw material solution 102 in the solution tank 101 corresponding to the ultrasonic wave generating mechanisms, mixed mist with three different elements is formed in the atomizing container 005, the other atomizing modules are kept closed, the formed mixed mist is sent into the reaction unit to grow alloy oxide films containing three metal elements, and the like, so that the ultrasonic wave generating mechanisms of the atomizing modules can be started at will to form corresponding multiple metal alloy oxide films.
In some embodiments, the atomizing unit further comprises an inlet conduit 008, an outlet conduit 009, and a mixing conduit 010. The gas inlet line 008 is connected to the atomizing container 005 for supplying carrier gas 001. The diluent gas 002 flows through the mixing pipe 010. One end of the air outlet pipeline 009 is connected with the atomizing container 005, and the other end of the air outlet pipeline is communicated with the mixing pipeline 010, and is used for discharging fog in the atomizing container 005 into the mixing pipeline 010 and mixing the fog with the diluent gas 002 to obtain mixed gas. The mixing pipe 010 is connected to the reaction unit for feeding a mixed gas into the reaction unit. The top surface of the atomizing container 005 is provided with a first vent 006 for connecting with an air outlet pipe 009 to discharge mist. A second ventilation hole 007 is formed in the side wall of the atomizing container 005 and is used for communicating with the air inlet pipeline 008 so as to circulate carrier gas 001. In the invention, carrier gas 001 is introduced into an atomization container 005 through an air inlet pipeline 008, mist formed by atomizing a raw material solution 102 in a solution tank 101 is carried out through an air outlet pipeline 009, enters a mixing pipeline 010, and is mixed with diluent gas 002 and then is fed into a reaction unit together to grow a film. And the air inlet pipeline 008 and the mixing pipeline 010 of the invention are respectively provided with a first flow regulating component 003 and a second flow regulating component 004 so as to independently control the flow rate of the carrier gas 001 or the diluent gas 002.
In some embodiments, the ultrasonic wave generating mechanism comprises a base 103, the base 103 is disposed at the bottom of the solution tank 101, and at least one ultrasonic wave generating assembly is disposed in the base 103. The base 103 is provided with a containing groove near one side surface of the solution tank 101, medium liquid 106 is contained in the containing groove, and ultrasonic waves generated by the ultrasonic wave generating assembly are transmitted to the solution tank 101 through the medium liquid 106. The media liquid 106 comprises deionized water.
In some embodiments, the atomizing unit in the invention can also realize remote control through software and hardware and electromechanical control technology. According to the preparation system, the control unit is arranged as a terminal for operation and monitoring by operation staff, so that the on and off of the ultrasonic wave generating mechanisms of different atomization modules can be switched remotely independently, when the ultrasonic wave generating assembly of one atomization module is started, the ultrasonic wave generating assemblies of other atomization modules are controlled to be closed, so that raw material solutions 102 in different corresponding solution tanks 101 are atomized to form mist, and then enter the reaction unit to generate films, and various atomization sources are provided.
In some embodiments, a bottom surface of the solution tank 101 is provided with a membrane 107, the membrane 107 contacting the media liquid 106. The diaphragm 107 comprises polyethylene, polytetrafluoroethylene or polyvinylidene fluoride. The top of the solution tank 101 is of an open structure, namely, a non-cover design is adopted, a diaphragm 107 is arranged at the bottom of the solution tank, ultrasonic waves generated by the ultrasonic wave generating component are transmitted to the diaphragm 107 through a medium liquid 106, atomization of the raw material solution 102 in the solution tank 101 is achieved, the raw material solution directly enters an atomization container 005, and the raw material solution is discharged out of the atomization container 005 along with carrier gas 001.
In some embodiments, the reaction unit includes a reaction chamber 19, and a rectification chamber 20, a reaction chamber 21, and a buffer chamber 25 are sequentially disposed in the reaction chamber 19 along the mist flow direction. A substrate 22 is disposed in the reaction chamber 21, and the substrate 22 is used for growing the oxide film layer. The substrate 22 comprises c-plane sapphire. The top and bottom of the outer peripheral wall of the reaction chamber 21 are respectively provided with a first heating element 23 and a second heating element 24. The first heating element 23 and the second heating element 24 independently comprise a resistance heater, an infrared radiation heater or an induction heater, and the heater may be made of ceramics, ceramic fiber, quartz or halogen tube. The outlet end of the buffer chamber 25 is also provided with a vacuum pumping assembly 26. The vacuumizing assembly 26 can be a pneumatic vacuumizing device or an electric vacuumizing device, the vacuumizing assembly 26 is adopted to vacuumize, mixed gas is driven to flow in the reaction chamber 19, the mixed gas flows in the rectification chamber 20 and enters the reaction chamber 21 after being rectified in the rectification chamber 20, an oxide film layer grows on the surface of the substrate 22, and the reacted mixed gas is discharged out of the reaction chamber 19 under the action of the vacuumizing assembly 26 after entering the buffer chamber 25 again.
In another embodiment, the invention provides a preparation method of a multisource atomized vapor deposition gallium oxide film, wherein the preparation method adopts the preparation system of the multisource atomized vapor deposition gallium oxide film, and the preparation method comprises the following steps:
(1) Providing at least two different feed solutions 102 to be placed in an atomization unit;
(2) Switching different raw material solutions 102 to independently perform ultrasonic atomization treatment to form mist;
(3) And sequentially feeding the mist into a reaction unit to grow at least two oxide film layers which are sequentially stacked, or to grow an alloy oxide film with at least two doping metals.
In some embodiments, the different raw material solutions 102 of the at least two atomizing modules each contain the same gallium source and doped metal source, the molar ratio of gallium/doped metal In the raw material solutions 102 is different, the molar ratio of gallium/doped metal In the raw material solutions 102 is 1 (0.2-2.5), and the doped metal element of the doped metal source includes at least one of Fe, al, in and Sn. The doping metal element of the doping metal source comprises at least one of Fe, al, in and Sn. The gallium source in the present invention may be a gallium-containing compound including, but not limited to, ga (acac) 3 Or GaCl 3 The method comprises the steps of carrying out a first treatment on the surface of the The doped metal source refers to a metal element-containing compound including, but not limited to, fe (acac) 3 、Al(acac) 3 、In(acac) 3 、FeCl 3 、AlCl 3 、InCl 3 、SnCl 4 。
The raw material solution102 is also added with a solvent. The solvent comprises deionized water. HCl with the mass fraction of 1% can be added into the solvent, so that the growth quality of the film can be improved. In addition, according to the practical situation, the person skilled in the art can selectively add H with the mass fraction of 1.5% into the solvent 2 O 2 . Wherein typical but non-limiting combinations are: a combination of HCl and deionized water, a combination of hydrogen peroxide and deionized water, or a combination of HCl, deionized water and hydrogen peroxide.
In some embodiments, the different feedstock solutions 102 of the at least two atomizing modules are at least one gallium source and at least one dopant metal source, respectively. The doping metal element of the doping metal source comprises at least one of Fe, al, in and Sn. The gallium source in the present invention may be a gallium-containing compound including, but not limited to, ga (acac) 3 Or GaCl 3 The method comprises the steps of carrying out a first treatment on the surface of the The doped metal source refers to a metal element-containing compound including, but not limited to, fe (acac) 3 、Al(acac) 3 、In(acac) 3 、FeCl 3 、AlCl 3 、InCl 3 、SnCl 4 。
The raw material solution 102 is further added with a solvent. The solvent comprises deionized water. HCl with the mass fraction of 1% can be added into the solvent, so that the growth quality of the film can be improved. In addition, according to the practical situation, the person skilled in the art can selectively add H with the mass fraction of 1.5% into the solvent 2 O 2 . Wherein typical but non-limiting combinations are: combinations of HCl and deionized water, combinations of hydrogen peroxide and deionized water, and combinations of HCl, deionized water and hydrogen peroxide.
In some embodiments, the method of making further comprises:
and independently introducing carrier gas 001 and diluent gas 002 into the atomization unit, wherein the carrier gas 001 brings mist out, and is mixed with the diluent gas 002 to obtain mixed gas, and the mixed gas is sent into the reaction unit to grow an oxide film layer. The flow rate of the carrier gas 001 is 2-8L/min, and the carrier gas 001 comprises nitrogen, argon, air or oxygen. The flow rate of the diluent gas 002 is 0.3-2L/min, and the diluent gas 002 comprises air, oxygen or nitrogen.
In some embodiments, the temperature of the growth of the oxide film layer is 400-600 ℃, the time of the growth of the oxide film layer is 20-60 min, and the thickness of the oxide film layer is 200-500 nm.
Example 1
The embodiment provides a preparation system of a multisource atomization vapor deposition gallium oxide film, which comprises an atomization unit and a reaction unit which are connected in sequence.
As shown in fig. 1 and 2, the atomizing unit includes an atomizing container 005, an outlet pipe 009, an inlet pipe 008, and a mixing pipe 010. Four atomizing modules are arranged in the atomizing container 005 and respectively recorded as a first atomizing module A100, a second atomizing module B100, a third atomizing module C100 and a fourth atomizing module D100, and the four atomizing modules respectively and independently comprise a solution tank 101 and an ultrasonic generating mechanism. The four solution tanks 101 are respectively referred to as a first solution tank, a second solution tank, a third solution tank, and a fourth solution tank. The first solution tank, the second solution tank, the third solution tank and the fourth solution tank are internally provided with raw material solutions 102 with different concentrations and proportions. The ultrasonic wave generating mechanism comprises a base 103, the base 103 is arranged at the bottom of the solution tank 101, and two ultrasonic wave generating components, namely a first ultrasonic wave generator 104 and a second ultrasonic wave generator 105, are arranged in the base 103. The surface of one side of the base 103, which is close to the solution tank 101, is provided with a containing groove, medium liquid 106 is contained in the containing groove, and the medium liquid 106 is deionized water. The solution tank 101 has an open structure, a diaphragm 107 is arranged on the bottom surface of the solution tank 101, and ultrasonic waves generated by the first ultrasonic generator 104 and the second ultrasonic generator 105 are transmitted to the diaphragm 107 through a medium liquid 106 to realize atomization of the raw material solution 102.
Offer the second vent 007 on the lateral wall of atomizing container 005, second vent 007 intercommunication admission line 008 for let in carrier gas 001, first air vent 006 has been seted up to atomizing container 005's top surface, first air vent 006 is connected to the one end of giving vent to anger pipeline 009, the other end intercommunication mixing tube 010, it has diluent gas 002 to let in mixing tube 010, carrier gas 001 is with the fog in the atomizing container 005 in being discharged to mixing tube 010, make fog and diluent gas 002 mix and obtain the mist, mixing tube 010 connects the reaction unit, be used for sending the mist into the reaction unit in. The air inlet line 008 and the mixing line 010 are respectively provided with a first flow adjusting component 003 and a second flow adjusting component 004 to independently control the flow rates of the carrier gas 001 and the diluent gas 002.
As shown in fig. 3, the reaction unit includes a reaction chamber 19, and a rectification chamber 20, a reaction chamber 21, and a buffer chamber 25 are sequentially disposed in the reaction chamber 19 along the mist flow direction. The two ends of the reaction chamber 19 are respectively provided with an air inlet 28 and an air outlet 27, and the air inlet 28 is connected with a mixing pipeline 010 to send the mixed gas into the rectification chamber 20. A substrate 22 is disposed in the reaction chamber 21 for growing an oxide film layer, and the substrate 22 is c-plane sapphire. The top and bottom of the outer peripheral wall of the reaction chamber 21 are provided with a first heating member 23 and a second heating member 24, respectively, for heating the substrate 22. The outlet end of the buffer chamber 25 is also provided with a vacuumizing assembly 26 for vacuumizing, the mixed gas is driven to flow in the reaction chamber 19, the mixed gas flows in the rectification chamber 20 and enters the reaction chamber 21 after being rectified in the rectification chamber 20, an oxide film layer grows on the surface of the substrate 22, and the reacted mixed gas is discharged out of the reaction chamber 19 from the air outlet 27 under the action of the vacuumizing assembly 26 after entering the buffer chamber 25 again.
Example 2
The present embodiment provides a preparation system of a multisource atomized vapor deposition gallium oxide film, which is different from embodiment 1 in that: the number of atomizing modules in the atomizing container 005 is three, and the solution tanks 101 of the three atomizing modules are respectively referred to as a first solution tank, a second solution tank and a third solution tank, and the other device structures and connection modes are the same as those of embodiment 1.
Example 3
The present example provides a method for preparing a multisource atomized vapor deposition gallium oxide film, using the multisource atomized vapor deposition gallium oxide film preparation system provided in example 1 to perform α - (Al) x Ga 1-x ) 2 O 3 The preparation of the film specifically comprises the following steps:
(1) Providing a raw material solution 102: raw material solutions 102 with different Ga/Al ratios are respectively injected into the first solution tank, the second solution tank, the third solution tank and the fourth solution tank, wherein Ga (acac) in each solution tank 101 is injected into the first solution tank, the second solution tank, the third solution tank and the fourth solution tank respectively 3 The concentration of (C) is 0.05mol/L, al (acac) 3 The concentration of (2) is 0.08mol/L, 0.06mol/L, 0.04mol/L and 0.02mol/L respectively, and deionized water is added into the raw material solution 102 as a solvent;
(2) Setting growth parameters: setting the growth temperature to 500 ℃, the growth time to 30min, the carrier gas 001 to nitrogen, the carrier gas 001 flow rate to 5L/min, the diluent gas 002 to oxygen, and the diluent gas 002 flow rate to 1L/min;
(3) Growing an oxide film layer: the first heating component 23 and the second heating component 24 are started to heat until the temperature in the reaction chamber 21 rises to 500 ℃ and is stable, the first ultrasonic generator 104 and the second ultrasonic generator 105 at the bottom of the first solution tank are opened, the raw material solution 102 in the first solution tank is atomized, and the raw material solution is introduced into the reaction chamber 21 along with the carrier gas 001 and the diluent gas 002 to react;
(4) Switching an atomization source: after 30min of reaction, a first film layer is formed in the reaction chamber 21, the first ultrasonic generator 104 and the second ultrasonic generator 105 at the bottom of the first solution tank are closed, the first ultrasonic generator 104 and the second ultrasonic generator 105 at the bottom of the second solution tank are opened, the raw material solution 102 in the second solution tank is atomized, the raw material solution is introduced into the reaction chamber 21 along with carrier gas 001 and diluent gas 002 for reaction, after 30min of reaction, a second film layer grows on the surface of the first film layer, and the like, the opening and the closing of the first ultrasonic generator 104 and the second ultrasonic generator 105 at the bottom of the third solution tank and the fourth solution tank are sequentially controlled, the atomization of the raw material solution 102 in the third solution tank and the fourth solution tank is sequentially realized, and a third film layer and a fourth film layer which are sequentially laminated are grown on the surface of the second film layer, so that alpha- (Al) with four film layers is obtained x Ga 1-x ) 2 O 3 A film.
The embodiment adopts a preparation system of the multisource atomization vapor deposition gallium oxide film, and can conveniently control alpha- (Al) x Ga 1-x ) 2 O 3 Growth of the film and Al content in the film, a high Al composition and high crystallinity of alpha- (Al) with four film layers are obtained x Ga 1-x ) 2 O 3 A film.
Example 4
The present example provides a method for preparing a multisource atomized vapor deposition gallium oxide film, using the multisource atomized vapor deposition gallium oxide film preparation system provided in example 1 to perform α - (Al) x Ga 1-x ) 2 O 3 The preparation of the film differs from example 3 in that:
in the step (1), HCl with mass fraction of 1% is further added to the raw material solutions 102 of the first solution tank, the second solution tank, the third solution tank and the fourth solution tank, so as to obtain better growth quality;
in step (2), the carrier gas 001 and the diluent gas 002 are oxygen, and the other process parameters are the same as in example 3.
Example 5
The present example provides a method for preparing a multisource atomized vapor deposition gallium oxide film, using the multisource atomized vapor deposition gallium oxide film preparation system provided in example 1 to perform α - (Fe) x Ga 1-x ) 2 O 3 The preparation of the film differs from example 3 in that:
in the step (1), gallium acetylacetonate and iron acetylacetonate with different Ga and Fe concentration ratios are respectively injected into the first solution tank, the second solution tank, the third solution tank and the fourth solution tank as raw material solutions 102, and a small amount of HCl (mass fraction is 1%) is added into the raw material solutions 102;
In the step (2), the carrier gas 001 and the diluent gas 002 are oxygen, so that the alpha-Ga with different Fe doping concentrations is realized 2 O 3 Film growth to obtain alpha- (Fe) film with four film layers x Ga 1-x ) 2 O 3 The film and the remaining process parameters were the same as in example 3.
Example 6
The embodiment provides a preparation method of a multisource atomization vapor deposition gallium oxide film, which adopts the embodiment1, and alpha- (In) is carried out by the preparation system of the multisource atomization vapor deposition gallium oxide film x Ga 1-x ) 2 O 3 The preparation of the film differs from example 3 in that:
in the step (1), gallium acetylacetonate and indium acetylacetonate with different Ga and In concentration ratios are respectively injected into the first solution tank, the second solution tank, the third solution tank and the fourth solution tank as raw material solutions 102, and a small amount of HCl (mass fraction is 1%) is added into the raw material solutions 102;
in the step (2), the carrier gas 001 and the diluent gas 002 are oxygen, so that the alpha-Ga with different In doping concentrations is realized 2 O 3 Growth of the film, a- (In) having four film layers was obtained x Ga 1-x ) 2 O 3 The film and the remaining process parameters were the same as in example 3.
Example 7
The present example provides a method for preparing a multisource atomized vapor deposition gallium oxide film, using the multisource atomized vapor deposition gallium oxide film preparation system provided in example 1 to perform α - (Sn) x Ga 1-x ) 2 O 3 The preparation of the film differs from example 3 in that:
in the step (1), gallium acetylacetonate and tin chloride with different Ga and Sn concentration ratios are respectively injected into the first solution tank, the second solution tank, the third solution tank and the fourth solution tank as raw material solutions 102, and a small amount of HCl (1% by mass) and hydrogen peroxide (1.5% by mass) are added into the raw material solutions 102 to realize alpha-Ga with different Sn doping concentrations 2 O 3 Growth of the film, a- (In) having four film layers was obtained x Sn 1-x ) 2 O 3 The film and the remaining process parameters were the same as in example 3.
Example 8
The embodiment provides a preparation method of a multisource atomization vapor deposition gallium oxide film, which adopts the preparation system of the multisource atomization vapor deposition gallium oxide film provided in the embodiment 1 to grow different types of alpha-phase oxide films, and specifically comprises the following steps:
(1) Providing a raw material solution 102: respectively injecting gallium chloride, aluminum chloride, ferric chloride and indium chloride into the first solution tank, the second solution tank, the third solution tank and the fourth solution tank as raw material solutions 102, wherein deionized water and a small amount of HCl (mass fraction is 1%) are added into the raw material solutions 102 as solvents;
(2) Setting growth parameters: setting the growth temperature to 500 ℃, the growth time to 30min, the carrier gas 001 to nitrogen, the carrier gas 001 flow rate to 5L/min, the diluent gas 002 to nitrogen, and the diluent gas 002 flow rate to 1L/min;
(3) Growing an oxide film layer: starting a first heating component 23 and a second heating component 24 to heat until the temperature in a reaction chamber 21 rises to 500 ℃ and is stable, simultaneously starting ultrasonic generators 104 and 105 at the bottoms of a first solution tank and a second solution tank, keeping the ultrasonic generators 104 and 105 at the bottoms of a third solution tank and a fourth solution tank closed, atomizing gallium chloride in the first solution tank, atomizing aluminum chloride in the second solution tank to form mixed mist containing gallium and aluminum in an atomization container 005, introducing carrier gas 001 and diluent gas 002 into the reaction chamber 21 to react, and forming a first alloy oxide film with two metals doped with gallium and aluminum on a substrate 22 after 30min of reaction;
(4) Switching an atomization source: taking out the first alloy oxide film formed in the step (3), without replacing the raw material solution 102, closing the ultrasonic generators 104 and 105 at the bottoms of the first solution tank and the second solution tank, simultaneously opening the ultrasonic generators 104 and 105 at the bottoms of the third solution tank and the fourth solution tank, atomizing ferric chloride in the third solution tank, atomizing indium chloride in the fourth solution tank to form mixed mist containing iron and indium in the atomizing container 005, introducing carrier gas 001 and diluent gas 002 into the reaction chamber 21 for reaction, and after 30 minutes of reaction, forming the second alloy oxide film with two doping metals of iron and indium on the substrate 22.
In this embodiment, four different atomizing modules are placed in the same atomizing container 005, the starting of the different atomizing modules can be directly switched without changing the raw materials, two different alloy oxide films containing gallium and aluminum doped metals and containing iron and indium doped metals can be obtained by growth, and the two single-layer films can be grown on different substrates 22.
Example 9
The present embodiment provides a method for preparing a multisource atomized vapor deposition gallium oxide film, which uses the preparation system of the multisource atomized vapor deposition gallium oxide film provided in embodiment 1 to grow different kinds of alpha-phase oxide films, and differs from embodiment 8 in that:
in the step (4), after the first alloy oxide film formed in the step (3) is taken out, the ultrasonic generators 104 and 105 at the bottoms of the first solution tank and the third solution tank are turned on, the ultrasonic generators 104 and 105 at the bottoms of the second solution tank and the fourth solution tank are kept off, gallium chloride in the first solution tank is atomized, ferric chloride in the third solution tank is atomized, mixed mist containing gallium and iron is formed in the atomization container 005, carrier gas 001 and diluent gas 002 are introduced into the reaction chamber 21 for reaction, after 30 minutes of reaction, a second alloy oxide film containing two doped metals of gallium and iron is formed on the substrate 22, and the other process parameters are the same as in the example 8.
In this embodiment, four different atomizing modules are placed in the same atomizing container, the starting of the different atomizing modules can be directly switched without changing the raw materials, two different alloy oxide films containing gallium and aluminum doped metals and containing gallium and iron doped metals can be grown, and the two single-layer films can be grown on different substrates 22.
Example 10
The embodiment provides a preparation method of a multisource atomization vapor deposition gallium oxide film, which adopts the preparation system of the multisource atomization vapor deposition gallium oxide film provided in the embodiment 2 to grow different types of alpha-phase oxide films, and specifically comprises the following steps:
(1) Providing a raw material solution 102: respectively injecting gallium acetylacetonate, aluminum acetylacetonate and indium acetylacetonate into the first solution tank, the second solution tank and the third solution tank as raw material solutions 102, wherein deionized water and a small amount of HCl (mass fraction is 1%) are added into the raw material solutions 102 as solvents;
(2) Setting growth parameters: setting the growth temperature at 600 ℃, the growth time at 30min, the carrier gas 001 being nitrogen, the carrier gas 001 flow rate being 5L/min, the diluent gas 002 being nitrogen, the diluent gas 002 flow rate being 1L/min;
(3) Growing an oxide film layer: the first heating component 23 and the second heating component 24 are started to heat until the temperature in the reaction chamber 21 rises to 600 ℃ and is stable, the first ultrasonic generator 104 and the second ultrasonic generator 105 at the bottom of the first solution tank, the first ultrasonic generator 104 and the second ultrasonic generator 105 at the bottom of the second solution tank, the first ultrasonic generator 104 and the second ultrasonic generator 105 at the bottom of the third solution tank, the gallium acetylacetonate in the first solution tank, the aluminum acetylacetonate in the second solution tank, the indium acetylacetonate in the third solution tank, the mixed mist containing gallium, aluminum and indium is formed in the atomization container 005, and the mixed mist is introduced into the reaction chamber 21 along with the carrier gas 001 and the diluent gas 002 to react, so that the alloy oxide film containing three metals of gallium, aluminum and indium is obtained.
According to the invention, different raw material solutions 102 are switched for atomization, so that mist with different material concentrations and proportions is formed, multiple atomization sources are provided, and a plurality of sequentially laminated oxide film layers are formed in the reaction chamber 21, so that the component concentration in the raw material solution 102 can be controlled, and a high-quality oxide film with high doped metal combination and high crystallinity is obtained.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.

Claims (10)

1. The preparation system of the multisource atomization vapor deposition gallium oxide film is characterized by comprising an atomization unit and a reaction unit which are connected in sequence;
the atomizing unit comprises at least one atomizing container, at least two atomizing modules are arranged in the atomizing container, the at least two atomizing modules respectively and independently comprise a solution tank and an ultrasonic generating mechanism, the solution tank is provided with an open structure, raw material solutions are contained in the solution tank, the ultrasonic generating mechanisms of different atomizing modules are switched to atomize the raw material solutions in the solution tank to form mist, and the mist flows into the reaction unit to grow at least two oxide film layers which are sequentially laminated or grow alloy oxide films with at least two doping metals.
2. The system for preparing a multisource atomized vapor deposition gallium oxide film according to claim 1, wherein the atomizing unit further comprises an air inlet pipeline, an air outlet pipeline and a mixing pipeline;
the air inlet pipeline is connected with the atomization container and is used for providing carrier gas;
the mixing pipeline is internally circulated with diluent gas;
one end of the air outlet pipeline is connected with the atomization container, and the other end of the air outlet pipeline is communicated with the mixing pipeline and is used for discharging fog in the atomization container into the mixing pipeline and mixing the fog with diluent gas to obtain mixed gas;
the mixing pipeline is connected with the reaction unit and is used for sending mixed gas into the reaction unit.
3. The system for preparing a multisource atomized vapor deposition gallium oxide film according to claim 1, wherein the ultrasonic wave generating mechanism comprises a base, the base is arranged at the bottom of the solution tank, and at least one ultrasonic wave generating component is arranged in the base;
the base is close to one side surface of solution jar has seted up the holding tank, hold the medium liquid in the holding tank, ultrasonic wave that the ultrasonic wave subassembly produced passes through the medium liquid passes through the solution jar.
4. The preparation system of the multisource atomization vapor deposition gallium oxide film according to claim 3, wherein a first vent hole is formed in the top surface of the atomization container, and the first vent hole is used for discharging mist;
a second vent hole is formed in the side wall of the atomization container, and the second vent hole is used for circulating carrier gas;
a diaphragm is arranged on the bottom surface of the solution tank, and contacts the medium liquid;
the separator comprises polyethylene, polytetrafluoroethylene or polyvinylidene fluoride.
5. The preparation system of the multisource atomization vapor deposition gallium oxide film according to claim 1, wherein the reaction unit comprises a reaction chamber, and a rectification chamber, a reaction chamber and a buffer chamber are sequentially arranged in the reaction chamber along the flow direction of mist;
a substrate is arranged in the reaction chamber and is used for growing the oxide film layer;
the substrate comprises c-plane sapphire;
the top and the bottom of the peripheral wall of the reaction chamber are respectively provided with a first heating component and a second heating component;
and the outlet end of the buffer chamber is also provided with a vacuumizing assembly.
6. A method for preparing a multisource atomized vapor deposition gallium oxide film, which is characterized in that the preparation method adopts the preparation system of the multisource atomized vapor deposition gallium oxide film according to any one of claims 1 to 5, and the preparation method comprises the following steps:
Providing at least two atomizing modules containing different raw material solutions, and placing the atomizing modules in the same atomizing container;
(II) switching different atomizing modules to independently perform ultrasonic atomization treatment to form mist;
(iii) feeding the mist into a reaction unit to grow at least two oxide film layers stacked in sequence, or to grow an alloy oxide film having at least two doping metals.
7. The method for preparing a multisource atomized vapor deposition gallium oxide film according to claim 6, wherein different raw material solutions of the at least two atomization modules contain the same gallium source and doped metal source, and the molar ratio of gallium to doped metal in the raw material solutions is different from each other;
the molar ratio of gallium/doped metal in the raw material solution is 1 (0.2-2.5);
the doping metal element of the doping metal source comprises at least one of Fe, al, in and Sn;
the raw material solution is also added with a solvent;
the solvent comprises deionized water.
8. The method for preparing a multisource atomized vapor deposition gallium oxide film according to claim 6, wherein different raw material solutions of the at least two atomizing modules are at least one gallium source and at least one doped metal source respectively;
The doping metal element of the doping metal source comprises at least one of Fe, al, in and Sn;
the raw material solution is also added with a solvent;
the solvent comprises deionized water.
9. The method for preparing a multisource atomized vapor deposition gallium oxide film according to claim 6, further comprising:
independently introducing carrier gas and diluent gas into the atomization unit, taking out mist by the carrier gas, mixing the mist with the diluent gas to obtain mixed gas, and sending the mixed gas into the reaction unit to grow an oxide film layer;
the flow rate of the carrier gas is 2-8L/min;
the carrier gas comprises nitrogen, argon, air or oxygen;
the flow rate of the dilution gas is 0.3-2L/min;
the diluent gas comprises air, oxygen or nitrogen.
10. The method for preparing a multisource atomized vapor deposition gallium oxide film according to claim 6, wherein the growth temperature of the oxide film layer is 400-600 ℃;
the growth time of the oxide film layer is 20-60 min;
the thickness of the oxide film layer is 200-500 nm.
CN202310601968.9A 2023-05-26 2023-05-26 Preparation system and method of multisource atomization vapor deposition gallium oxide film Pending CN116334582A (en)

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CN114342086A (en) * 2019-07-12 2022-04-12 株式会社Flosfia Oxide semiconductor film and semiconductor device
CN116024550A (en) * 2023-03-06 2023-04-28 青禾晶元(天津)半导体材料有限公司 Device system and method for growing oxide film by utilizing mist chemical vapor deposition

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JP2005305233A (en) * 2004-04-19 2005-11-04 Shizuo Fujita Atomization apparatus for forming film
JP2009199757A (en) * 2008-02-19 2009-09-03 Konica Minolta Holdings Inc Method of manufacturing organic electroluminescent panel
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