CN116288260A - Atomization vapor deposition device comprising ultrasonic generator and atomization vapor deposition method - Google Patents

Atomization vapor deposition device comprising ultrasonic generator and atomization vapor deposition method Download PDF

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CN116288260A
CN116288260A CN202310552761.7A CN202310552761A CN116288260A CN 116288260 A CN116288260 A CN 116288260A CN 202310552761 A CN202310552761 A CN 202310552761A CN 116288260 A CN116288260 A CN 116288260A
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vapor deposition
ultrasonic generator
ultrasonic
inlet
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母凤文
郭超
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Qinghe Jingyuan Tianjin Semiconductor Materials Co ltd
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Qinghe Jingyuan Tianjin Semiconductor Materials 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
    • C23C16/44—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
    • 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
    • C23C16/4415—Acoustic wave CVD
    • 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
    • C23C16/455—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 introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45587—Mechanical means for changing the gas flow
    • C23C16/45591—Fixed means, e.g. wings, baffles

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Acoustics & Sound (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

The invention provides an atomization vapor deposition device comprising an ultrasonic generator and an atomization vapor deposition method. The atomized vapor deposition apparatus includes a housing; the shell comprises a rectifying section, a reaction section and a discharge section which are sequentially connected, the rectifying section is provided with an airflow converging structure, the discharge section is provided with an airflow diverging structure, the top surface of the reaction section is provided with an ultrasonic generator, the bottom of the reaction section is provided with a sample placing table, the top surface of the sample placing table is positioned in an inner cavity of the reaction section, and the sample placing table and the ultrasonic generator are arranged opposite to each other; the rectifying section is connected with an atomization mechanism through the inlet, and the atomization mechanism is connected with a carrier gas source. The ultrasonic generator is added in the atomization vapor deposition device, so that the low-temperature chemical vapor deposition without damage or with low damage can be realized.

Description

Atomization vapor deposition device comprising ultrasonic generator and atomization vapor deposition method
Technical Field
The invention belongs to the technical field of vapor deposition, and relates to an atomization vapor deposition device comprising an ultrasonic generator and an atomization vapor deposition method.
Background
Chemical vapor deposition (Chemical Vapor Deposition, CVD for short) refers to the process of synthesizing coatings or nanomaterials by reacting chemical gases or vapors on the surface of a substrate, and is the most widely used technique in the semiconductor industry for depositing a wide variety of materials, including a wide range of insulating materials, most metallic materials and metallic alloy materials.
CN102181845a discloses a chemical vapor deposition furnace, which comprises a furnace body, a furnace body lifting mechanism, a furnace cover lifting mechanism, a three-stage filtering system, a vacuum system and a heater, wherein the heater comprises an upper zone heating body, a middle zone heating body and a lower zone heating body; the furnace body adopts a vertical and internal heating structure and comprises a furnace cover, an upper furnace body, a lower furnace body and a furnace bottom. CN104342631B discloses a chemical vapor deposition furnace, which comprises: a furnace body; the upper furnace cover is arranged at the upper part of the furnace body, sealed with the furnace body and detachably and fixedly connected with the furnace body; the lower furnace cover is arranged at the lower part of the furnace body and is in sealing detachable fixed connection with the furnace body; and the lower furnace cover lifting mechanism is fixedly connected with the lower furnace cover, so that the lower furnace cover is driven to fall down after being separated from the fixed furnace body to perform lower discharging, and the lower furnace cover after the discharging is driven to rise to be combined with the furnace body. The chemical vapor deposition furnace may further include: the front-back pushing mechanism is arranged right below the lower furnace cover, and the front-back pushing mechanism enables the lower furnace cover lifting mechanism to drive the descending lower furnace cover to fall on the front-back pushing mechanism and move to the periphery front-back so as to carry out discharging and charging. The furnace body, the upper furnace cover and the lower furnace cover can all adopt a water-cooling interlayer and a heat preservation layer.
However, conventional chemical vapor deposition apparatus and methods perform deposition at very high temperatures, which can damage the substrate or deposited layer, resulting in defects. The deposition temperature can be reduced by adopting plasma enhanced chemical vapor deposition, but the plasma can damage the substrate and the deposited film, so that defects are generated. Moreover, in the existing chemical vapor deposition apparatus, uniformity of gas circulation is poor, which also affects quality of deposited thin films.
Therefore, it is needed to develop a vapor deposition apparatus to solve the problem of high deposition temperature of the chemical vapor deposition apparatus, reduce the damage of the substrate and the deposited film, and improve the uniformity of the gas flow field in the vapor deposition apparatus.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide an atomization vapor deposition device and an atomization vapor deposition method comprising an ultrasonic generator. According to the invention, the ultrasonic generator is added in the atomization vapor deposition device, ultrasonic waves emitted by the ultrasonic generator can provide energy for the deposition reaction process, and the probability of damaging the substrate and the deposited film is small, so that low-temperature CVD without damage or with low damage can be realized, and meanwhile, the uniformity of a gas flow field in the reaction chamber can be improved by arranging the rectifying section and the discharging section.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an atomized vapor deposition apparatus comprising an ultrasonic generator, the atomized vapor deposition apparatus comprising a housing;
the shell comprises a rectifying section, a reaction section and a discharge section which are sequentially connected, the rectifying section is provided with an airflow converging structure, the discharge section is provided with an airflow diverging structure, the small-size end of the rectifying section is in butt joint with the input end of the reaction section, and the output end of the reaction section is in butt joint with the small-size end of the discharge section;
the top surface of the reaction section is provided with an ultrasonic generator, the bottom of the reaction section is provided with a sample placing table, the top surface of the sample placing table is positioned in the inner cavity of the reaction section, and the sample placing table and the ultrasonic generator are arranged opposite to each other;
the rectifying section is connected with an atomization mechanism through the inlet, and the atomization mechanism is connected with a carrier gas source.
The invention provides an atomization vapor deposition device comprising an ultrasonic generator, wherein an atomization mechanism can convert raw materials into mist, carrier gas provided by a carrier gas source can carry the mist into an inner cavity of a shell, ultrasonic waves emitted by the ultrasonic generator can be utilized to provide energy for a deposition reaction process, so that the raw material mist can react at low temperature, a film is deposited on the surface of a substrate, the damage probability of the ultrasonic waves to the substrate and the deposited film is small, thereby realizing low-temperature CVD without damage or low damage, even realizing room-temperature CVD, greatly improving the quality of the deposited film, and being green and energy-saving;
meanwhile, the rectifying section is provided with an airflow converging structure, so that fog entering the reaction chamber can be rectified, and the airflow before the fog flows into the reaction section is more stable, so that the uniformity of a gas flow field in a subsequent reaction section is improved; the exhaust section of the device has an airflow divergence structure, so that the gas flow at the output end of the reaction section can be prevented from being too fast, the gas flow is prevented from directly striking the inner wall of the output end to form an unstable flow field, the buffer space is increased, the uniformity of the gas flow field in the reaction chamber can be greatly improved, and the quality of a deposited film is further improved.
Optionally, part or all of the sample placement stage is disposed in the interior cavity of the reaction section.
Preferably, the rectifying section is provided with at least 1 (e.g. 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 etc.) of said inlets, and the discharge section is provided with at least 1 (e.g. 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 etc.) of said outlets.
Preferably, the distance between the emitting end of the ultrasonic generator and the top surface of the sample placing table is 2-20mm, for example, 2mm, 4mm, 6mm, 8mm, 10mm, 12mm, 14mm, 16mm, 18mm or 20mm, etc.
Preferably, the distance between the top surface of the sample placement stage and the top surface of the inner cavity of the reaction section is 0.5-5mm, for example, 0.5mm, 0.7mm, 1mm, 1.5mm, 2mm, 2.5mm, 3mm, 3.5mm, 4mm, 4.5mm or 5mm, etc.
In the invention, when the distance between the top surface of the sample placing table and the top surface of the inner cavity of the reaction section is controlled to be 0.5-5mm, the substrate is placed on the top surface of the sample placing table, and a narrow slit can be formed above the substrate, and the narrow slit can enable the air flow above the substrate to be laminar, so that the uniformity of film deposition can be improved.
Preferably, the frequency of the ultrasonic generator is 20-1000kHz, and can be 20kHz, 30kHz, 50kHz, 70kHz, 100kHz, 150kHz, 200kHz, 300kHz, 400kHz, 500kHz, 600kHz, 700kHz, 800kHz, 900kHz, 1000kHz, etc., for example. The energy of the organic molecule is higher than the bond energy of most organic molecules, so that the raw materials in the fog can be decomposed and deposited.
The power of the ultrasonic generator is 20-200mW/cm 2 For example, it may be 20mW/cm 2 、30mW/cm 2 、50mW/cm 2 、70mW/cm 2 、100mW/cm 2 、120mW/cm 2 、140mW/cm 2 、160mW/cm 2 、180mW/cm 2 Or 200mW/cm 2 Etc.
Preferably, the sample placement stage is disposed coaxially with the ultrasonic generator.
Preferably, a temperature control assembly is arranged in the inner cavity of the sample placing table, and the temperature control assembly comprises a heating assembly and/or a cooling assembly. And the temperature of the sample placing table is used as a set value, and the temperature of the sample placing table is regulated and controlled through the temperature control component, so that the temperature of the substrate is regulated and controlled.
Optionally, a rotating component is disposed at the bottom of the sample placement table, and the rotating component is used for driving the sample placement table to rotate, so as to drive the substrate to rotate.
Preferably, at least 1 of said atomizing mechanisms is connected to said rectifying section, said "at least 1" may be, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, etc. When the shell is connected with at least 2 atomization mechanisms, the at least 2 atomization mechanisms are arranged in parallel.
Preferably, the atomizing mechanism comprises an atomizing chamber; the atomizing chamber comprises a shell, a carrier gas inlet and a carrier gas outlet are formed in the shell, the carrier gas inlet is communicated with the carrier gas source, and the carrier gas outlet is communicated with the inlet of the shell.
Preferably, an air inlet branch is led out from a communicating pipeline of the carrier gas outlet and the inlet, an air inlet end of the air inlet branch is communicated with a gas source, and gas provided by the gas source can be used for transporting mist generated by the atomization mechanism together with carrier gas provided by the carrier gas source.
Preferably, the carrier gas source and the gas source independently comprise any one or a combination of at least two of nitrogen, argon, helium or hydrogen.
The term "independently" means that the carrier gas source may be any one or a combination of at least two of nitrogen, argon, helium and hydrogen, and the two components do not interfere with each other when they are selected.
Preferably, the composition of the carrier gas source is the same as the composition of the gas source.
Preferably, a first ultrasonic assembly is provided at the bottom of the housing, a portion of the first ultrasonic assembly being located in the interior cavity of the housing. The inner cavity of the shell can be filled with raw material liquid, the first ultrasonic assembly is in direct contact with the raw material liquid, the raw material liquid is excited by emitted ultrasonic waves to be atomized, and the mist consists of fine liquid drop particles.
Preferably, the first ultrasonic assembly comprises an ultrasonic vibrator.
Preferably, the frequency of the first ultrasonic component is 1-10MHz, for example, 1MHz, 2MHz, 3MHz, 4MHz, 5MHz, 6MHz, 7MHz, 8MHz, 9MHz or 10MHz, etc.
Preferably, the atomization mechanism further comprises a container, an ultrasonic medium is contained in the container, the bottom of the atomization chamber is located in the inner cavity of the container, a second ultrasonic assembly is arranged at the bottom of the container, and part of the second ultrasonic assembly is located in the inner cavity of the container.
In the invention, the ultrasonic wave emitted by the second ultrasonic component can be transmitted to the shell through the ultrasonic medium in the container, the ultrasonic medium can be pure water, the ultrasonic wave can excite the raw material liquid in the inner cavity of the shell to form fog, and the fog consists of fine liquid drop particles; the second ultrasonic component is in direct contact with the ultrasonic medium and is not in direct contact with the raw material liquid, so that the corrosion of the raw material liquid to the second ultrasonic component is avoided.
Preferably, the second ultrasonic assembly comprises an ultrasonic vibrator.
Preferably, the frequency of the second ultrasonic component is 1-10MHz, for example, 1MHz, 2MHz, 3MHz, 4MHz, 5MHz, 6MHz, 7MHz, 8MHz, 9MHz or 10MHz, etc.
Preferably, the rectifying section comprises a first straight barrel section and a tapered section which are in butt joint in sequence, the cross-sectional area of the tapered section gradually decreases along the flow direction of the mist, and the small-size end of the tapered section is in butt joint with the input end of the reaction section.
Preferably, the inclined surface of the tapered section forms an angle of 25 ° -75 ° with the cross section, for example 25 °, 27 °, 30 °, 32 °, 35 °, 37 °, 40 °, 42 °, 45 °, 50 °, 60 °, 65 °, 70 ° or 75 °.
Preferably, the structure of the reaction section comprises a straight cylinder structure with two open ends.
Preferably, the discharge section comprises a divergent section and a second straight section which are in butt joint in sequence, the cross-sectional area of the divergent section is gradually increased along the flow direction of the mist, and the small-size end of the divergent section is in butt joint with the output end of the reaction section.
Preferably, the inclined plane of the diverging section forms an angle with the cross section of 25 ° -75 °, for example 25 °, 27 °, 30 °, 32 °, 35 °, 37 °, 40 °, 42 °, 45 °, 50 °, 60 °, 65 °, 70 ° or 75 °.
Preferably, the first straight section is provided with at least 1 (e.g. 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 etc.) of said inlets, and the second straight section is provided with at least 1 (e.g. 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 etc.) of said outlets.
Preferably, the outer side wall of the first straight barrel section is provided with 2 inlets, which are respectively marked as a first inlet and a second inlet, and the first inlet and the second inlet are oppositely arranged.
In the invention, the first gas inlet and the second gas inlet are oppositely arranged, so that the carrier gas carrying the fog enters the rectifying section in two paths, and in the rectifying section, the two paths of gas flows collide, thereby achieving better rectifying effect.
In a second aspect, the present invention provides a method for performing atomized vapor deposition using the atomized vapor deposition apparatus including the ultrasonic generator according to the first aspect, the method for atomized vapor deposition comprising:
placing a substrate on a sample placing table, and placing raw material liquid in an atomization mechanism; and starting an atomization mechanism to enable the raw material liquid to form mist to flow into the inner cavity of the shell, starting an ultrasonic generator, and transmitting ultrasonic waves to the surface of the substrate to perform atomization vapor deposition.
The material of the substrate is not limited in the invention, and the material includes any one of sapphire, silicon, germanium, silicon carbide, quartz or metal.
The invention is not limited to the components of the raw material liquid, including but not limited to GaCl 3 、AlCl 3 、ZnCl 2 、FeCl 3 、GaBr 3 、AlBr 3 、ZnBr 2 、FeBr 3 At least one of Ga acetoacetate, al acetoacetate, in acetoacetate, fe acetylacetonate, al vinylacetone, ga vinylacetone, tetraethyl orthosilicate (TEOS), and octamethyl cyclotetrasiloxane (OMCTS); thereby forming a metal oxide thin film material including Ga on the substrate 2 O 3 、Al 2 O 3 、ZnO、(Al x Ga 1-x ) 2 O 3 、(Fe x Ga 1-x ) 2 O 3 Or SiO 2 Etc.
Preferably, the temperature of the substrate is 20-400 ℃, for example, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 70 ℃, 100 ℃, 150 ℃, 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃, or the like can be used.
Preferably, the diameter of the droplets in the mist is 1-5 μm, and may be, for example, 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, or 5 μm, etc.
Preferably, the air pressure in the inner cavity of the shell is 10-110kPa, for example, 10kPa, 20kPa, 30kPa, 40kPa, 50kPa, 60kPa, 70kPa, 80kPa, 90kPa, 100kPa or 110kPa, etc.
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.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides an atomization vapor deposition device comprising an ultrasonic generator, wherein an atomization mechanism can convert raw materials into mist, carrier gas provided by a carrier gas source can carry the mist into an inner cavity of a shell, ultrasonic waves emitted by the ultrasonic generator can be utilized to provide energy for a deposition reaction process, so that the raw material mist can react at low temperature, a film is deposited on the surface of a substrate, the damage probability of the ultrasonic waves to the substrate and the deposited film is small, thereby realizing low-temperature CVD without damage or low damage, even realizing room-temperature CVD, greatly improving the quality of the deposited film, and being green and energy-saving;
meanwhile, the rectifying section is provided with an airflow converging structure, so that fog entering the reaction chamber can be rectified, and the airflow before the fog flows into the reaction section is more stable, so that the uniformity of a gas flow field in a subsequent reaction section is improved; the exhaust section of the device has an airflow divergence structure, so that the gas flow at the output end of the reaction section can be prevented from being too fast, the gas flow is prevented from directly striking the inner wall of the output end to form an unstable flow field, the buffer space is increased, the uniformity of the gas flow field in the reaction chamber can be greatly improved, and the quality of a deposited film is further improved.
Drawings
FIG. 1 is a schematic view of an atomized vapor deposition apparatus including an ultrasonic generator according to embodiment 1 of the present invention;
FIG. 2 is a schematic view of an atomized vapor deposition apparatus including an ultrasonic generator according to embodiment 2 of the present invention;
FIG. 3 is a schematic view of an atomized vapor deposition apparatus including an ultrasonic generator according to embodiment 3 of the present invention;
fig. 4 is a front view of a housing provided in embodiment 3 of the present invention;
FIG. 5 is a top view of a housing provided in embodiment 3 of the present invention;
wherein, 1-atomizing chamber; 2-a first ultrasonic assembly; 3-a carrier gas inlet; 4-a carrier gas outlet; 5-a housing; 501-rectifying section; 502-a reaction section; 503-an exhaust section; 505-inlet; 5051—first inlet; 5052-a second inlet; 506-outlet; 6-an ultrasonic generator; 7-a sample placement stage; 8-an air inlet branch; 9-an air inlet end; 10-a container; 11-a second ultrasound assembly.
Detailed Description
It is to be understood that in the description of the present invention, the terms "center", "longitudinal", "lateral", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc. indicate orientations or positional relationships based on the drawings, are merely for convenience in describing the present invention and simplifying 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 are not to 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 by the following specific embodiments.
Example 1
The present embodiment provides an atomized vapor deposition apparatus including an ultrasonic generator, as shown in fig. 1, the atomized vapor deposition apparatus including a housing 5;
the shell 5 comprises a rectifying section 501, a reaction section 502 and a discharge section 503 which are sequentially connected, wherein the rectifying section 501 is provided with an airflow converging structure, namely, the rectifying section 501 comprises a first barrel section and a tapering section which are sequentially connected, the cross section area of the tapering section is gradually reduced along the flow direction of fog, the included angle between the inclined plane of the tapering section and the cross section is 25 degrees, and the small-size end of the tapering section is connected with the input end of the reaction section 502 in a butt joint mode; the outer side wall of the first straight barrel section is provided with 1 inlet 505;
the structure of the reaction section 502 is a straight cylinder structure with two open ends; the bottom of the reaction section 502 is provided with a sample placing table 7, the top surface of the sample placing table 7 is positioned in the inner cavity of the reaction section 502, and a temperature control assembly is arranged in the inner cavity of the sample placing table 7; the top surface of reaction section 502 is provided with ultrasonic generator 6, sample place the platform 7 with ultrasonic generator 6 coaxial arrangement, ultrasonic generator 6's transmitting end with the distance of the top surface of sample place the platform 7 is 2mm, just the distance between the top surface of sample place the platform 7 and the inner chamber top surface of reaction section 502 is 0.5mm, ultrasonic generator 6's frequency is 200kHz, its power is 50mW/cm 2 ；
The exhaust section 503 has an airflow divergent structure, that is, the exhaust section 503 includes a divergent section and a second straight section that are in butt joint in sequence, the cross-sectional area of the divergent section gradually increases along the flow direction of the mist, the included angle between the inclined plane of the divergent section and the cross-section is 25 °, and the small-sized end of the divergent section is in butt joint with the output end of the reaction section 502; the outer side wall of the second straight barrel section is provided with 1 outlet 506;
the rectification section 501 is connected with an atomization mechanism through the inlet 505, the atomization mechanism comprises an atomization chamber 1, the atomization chamber 1 is used for containing raw material liquid, a first ultrasonic assembly 2 is arranged at the bottom of the atomization chamber 1, part of the first ultrasonic assembly 2 is positioned in an inner cavity of the atomization chamber 1, the first ultrasonic assembly 2 is an ultrasonic vibrator, the ultrasonic frequency of the ultrasonic vibrator is 3MHz, and ultrasonic waves emitted by the ultrasonic vibrator can excite the raw material liquid to form mist; the outer side wall and the top surface of the atomization chamber 1 are provided with a carrier gas inlet 3 and a carrier gas outlet 4, the carrier gas inlet 3 is communicated with a first carrier gas source, and the carrier gas outlet 4 is communicated with the inlet 505; a gas inlet branch 8 is led out from a communicating pipeline of the carrier gas outlet 4 and the inlet 505, and a gas inlet end 9 of the gas inlet branch 8 is communicated with a gas source; the carrier gas source and the gas source are both nitrogen.
Example 2
The present embodiment provides an atomized vapor deposition apparatus including an ultrasonic generator, as shown in fig. 2, the atomized vapor deposition apparatus including a housing 5;
the shell 5 comprises a rectifying section 501, a reaction section 502 and a discharge section 503 which are sequentially connected, wherein the rectifying section 501 is provided with an airflow converging structure, namely, the rectifying section 501 comprises a first barrel section and a tapering section which are sequentially connected, the cross section area of the tapering section is gradually reduced along the flow direction of fog, the included angle between the inclined plane of the tapering section and the cross section is 35 degrees, and the small-size end of the tapering section is connected with the input end of the reaction section 502 in a butt joint mode; the outer side wall of the first straight barrel section is provided with 1 inlet 505;
the structure of the reaction section 502 is a straight cylinder structure with two open ends; the bottom of the reaction section 502 is provided with a sample placing table 7, the top surface of the sample placing table 7 is positioned in the inner cavity of the reaction section 502, and a temperature control assembly is arranged in the inner cavity of the sample placing table 7; the top surface of reaction section 502 is provided with ultrasonic generator 6, sample place the platform 7 with ultrasonic generator 6 coaxial arrangement, ultrasonic generator 6's transmitting end with the distance of the top surface of sample place the platform 7 is 8mm, just the distance between the top surface of sample place the platform 7 and the inner chamber top surface of reaction section 502 is 2.5mm, ultrasonic generator 6's frequency is 600kHz, and its power is 100mW/cm 2 ；
The exhaust section 503 has an airflow divergent structure, that is, the exhaust section 503 includes a divergent section and a second straight section that are in butt joint in sequence, the cross-sectional area of the divergent section gradually increases along the flow direction of the mist, the included angle between the inclined plane of the divergent section and the cross-section is 35 °, and the small-sized end of the divergent section is in butt joint with the output end of the reaction section 502; the outer side wall of the second straight barrel section is provided with 1 outlet 506;
the rectifying section 501 is connected with an atomization mechanism through the inlet 505, the atomization mechanism comprises an atomization chamber 1 and a container 10, the atomization chamber 1 is used for containing raw material liquid, the container 10 is used for containing a medium, the medium is pure water, and the bottom of the atomization chamber 1 is positioned in an inner cavity of the container 10; the bottom of the container 10 is provided with a second ultrasonic assembly 11, a part of the second ultrasonic assembly 11 is positioned in the inner cavity of the container 10, the second ultrasonic assembly 11 is an ultrasonic vibrator, and the ultrasonic frequency of the second ultrasonic assembly 11 is 5MHz; the outer side wall and the top surface of the atomizing chamber 1 are provided with a carrier gas inlet 3 and a carrier gas outlet 4, the carrier gas inlet 3 is communicated with a carrier gas source, and the carrier gas outlet 4 is communicated with the inlet 505; a gas inlet branch 8 is led out from a communicating pipeline of the carrier gas outlet 4 and the inlet 505, and a gas inlet end 9 of the gas inlet branch 8 is communicated with a gas source; the carrier gas source and the gas source are both argon.
Example 3
The present embodiment provides an atomized vapor deposition apparatus including an ultrasonic generator, as shown in fig. 3, the atomized vapor deposition apparatus including a housing 5;
the shell 5 comprises a rectifying section 501, a reaction section 502 and a discharge section 503 which are sequentially connected, wherein the rectifying section 501 is provided with an airflow converging structure, namely, the rectifying section 501 comprises a first barrel section and a tapering section which are sequentially connected, the cross section area of the tapering section is gradually reduced along the flow direction of fog, the included angle between the inclined plane of the tapering section and the cross section is 45 degrees, and the small-size end of the tapering section is connected with the input end of the reaction section 502 in a butt joint mode; 2 inlets are formed in the outer side wall of the first straight barrel section and are respectively marked as a first inlet 5051 and a second inlet 5052, and the first inlet 5051 and the second inlet 5052 are oppositely arranged, as shown in fig. 4 and 5;
the structure of the reaction section 502 is a straight cylinder structure with two open ends; a sample placing table 7 is arranged at the bottom of the reaction section 502 and is used for placing a sample7 is located in the inner cavity of the reaction section 502, and a temperature control component is arranged in the inner cavity of the sample placing table 7; the top surface of the reaction section 502 is provided with an ultrasonic generator 6, the sample placing table 7 and the ultrasonic generator 6 are coaxially arranged, the distance between the transmitting end of the ultrasonic generator 6 and the top surface of the sample placing table 7 is 12mm, the distance between the top surface of the sample placing table 7 and the top surface of the inner cavity of the reaction section 502 is 5mm, the frequency of the ultrasonic generator 6 is 1000kHz, and the power of the ultrasonic generator 6 is 200mW/cm 2 ；
The exhaust section 503 has an airflow divergent structure, that is, the exhaust section 503 includes a divergent section and a second straight section that are in butt joint in sequence, the cross-sectional area of the divergent section gradually increases along the flow direction of the mist, the included angle between the inclined plane of the divergent section and the cross-section is 45 °, and the small-sized end of the divergent section is in butt joint with the output end of the reaction section 502; the outer side wall of the second straight barrel section is provided with 1 outlet 506;
the rectifying section 501 is connected with an atomization mechanism through the first inlet 5051 and the second inlet 5052, the atomization mechanism comprises an atomization chamber 1 and a container 10, the atomization chamber 1 is used for containing raw material liquid, the container 10 is used for containing a medium, the medium is pure water, and the bottom of the atomization chamber 1 is positioned in an inner cavity of the container 10; the bottom of the container 10 is provided with a second ultrasonic assembly 11, a part of the second ultrasonic assembly 11 is positioned in the inner cavity of the container 10, the second ultrasonic assembly 11 is an ultrasonic vibrator, and the ultrasonic frequency of the second ultrasonic assembly is 10MHz; the outer side wall and the top surface of the atomizing chamber 1 are provided with a carrier gas inlet 3 and a carrier gas outlet 4, the carrier gas inlet 3 is communicated with a carrier gas source, the carrier gas outlet 4 is connected with an air inlet pipeline, the output end of the air inlet pipeline is connected with 2 branch pipelines, and the two branch pipelines are respectively communicated with a first inlet 5051 and a second inlet 5052; an air inlet branch 8 is led out of the air inlet pipeline, and an air inlet end 9 of the air inlet branch 8 is communicated with a gas source; the carrier gas source and the gas source are both argon.
Comparative example 1
This comparative example provides an atomized vapor deposition apparatus differing from example 1 in that the ultrasonic generator is omitted and the remainder is exactly the same as example 1.
Application example 1
The present application example provides a method for performing atomized vapor deposition using the atomized vapor deposition apparatus including an ultrasonic generator according to example 1, comprising:
placing a substrate on a sample placing table, and placing raw material liquid into an atomization mechanism, wherein the raw material liquid is acetoacetic acid Ga; starting an atomization mechanism to form a mist of raw material liquid, wherein the diameter of liquid drops in the mist is 3 mu m, and a carrier gas source and gas provided by the carrier gas source carry the mist to flow into a shell, and the air pressure in the shell is controlled at 50kPa; and starting a temperature control assembly, adjusting the temperature of the substrate to be 200 ℃, starting an ultrasonic generator, and transmitting ultrasonic waves to the surface of the substrate to perform atomization vapor deposition.
For vapor deposited Ga 2 O 3 The film is subjected to X-ray diffraction (XRD) rocking curve detection, the XRD rocking curve is a common method for representing the crystallization quality of crystals, and the smaller the half-width is, the less damage and defects in the crystals are, and the higher the crystallization quality is. The results of this application example show that the half width is 0.53 °, and the crystal quality of the thin film is high.
Application example 2
The present application example provides a method for performing atomized vapor deposition using the atomized vapor deposition apparatus including an ultrasonic generator according to example 2, comprising:
placing a substrate on a sample placing table, and placing raw material liquid into an atomization mechanism, wherein the raw material liquid is acetoacetic acid Ga; starting an atomization mechanism to form a mist of raw material liquid, wherein the diameter of liquid drops in the mist is 2 mu m, and a carrier gas source and gas provided by the carrier gas source carry the mist to flow into a shell, and the air pressure in the shell is controlled at 110kPa; and starting a temperature control assembly, adjusting the temperature of the substrate to 400 ℃, starting an ultrasonic generator, and transmitting ultrasonic waves to the surface of the substrate to perform atomization vapor deposition.
For vapor deposited Ga 2 O 3 XRD rocking curve detection is carried out on the film, and the result shows that the half width is 0.62 degrees, and the crystal quality of the film is higher.
Application example 3
The present application example provides a method for performing atomized vapor deposition using the atomized vapor deposition apparatus including an ultrasonic generator according to example 3, comprising:
placing a substrate on a sample placing table, and placing raw material liquid into an atomization mechanism, wherein the raw material liquid is acetoacetic acid Ga; starting an atomization mechanism to form a mist of raw material liquid, wherein the diameter of liquid drops in the mist is 1 mu m, and a carrier gas source and gas provided by the carrier gas source carry the mist to flow into a shell, and the air pressure in the shell is controlled at 110kPa; and starting a temperature control assembly, adjusting the temperature of the substrate to 400 ℃, starting an ultrasonic generator, and transmitting ultrasonic waves to the surface of the substrate to perform atomization vapor deposition.
For vapor deposited Ga 2 O 3 XRD rocking curve detection is carried out on the film, and the result shows that the half width is 0.57 degrees, and the crystal quality of the film is higher.
Comparative application example 1
The present comparative application example provides a method of performing atomized vapor deposition using the atomized vapor deposition apparatus described in comparative example 1, comprising:
placing a substrate on a sample placing table, and placing raw material liquid into an atomization mechanism, wherein the raw material liquid is acetoacetic acid Ga; starting an atomization mechanism to form a mist of raw material liquid, wherein the diameter of liquid drops in the mist is 5 mu m, and nitrogen provided by a carrier gas source and a gas source carries the mist to flow into a reaction chamber, and the air pressure in the reaction chamber is controlled at 10kPa; and starting the temperature control assembly, adjusting the temperature of the substrate to 600 ℃, and performing atomization vapor deposition.
For vapor deposited Ga 2 O 3 XRD rocking curve detection is carried out on the film, and the result shows that the half width is 0.92 degrees, the crystal lattice is damaged by high-temperature deposition, and the crystal quality of the film is poor.
In summary, according to the atomization vapor deposition device including the ultrasonic generator provided by the invention, the atomization mechanism can convert raw materials into mist, the carrier gas provided by the carrier gas source can carry the mist into the inner cavity of the shell, and ultrasonic waves emitted by the ultrasonic generator can be utilized to provide energy for the deposition reaction process, so that the raw material mist can react at low temperature, a film is deposited on the surface of the substrate, the damage probability of the ultrasonic waves to the substrate and the deposited film is small, thereby realizing low-temperature CVD without damage or low damage, even realizing room-temperature CVD, greatly improving the quality of the deposited film, and being green and energy-saving.
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. An atomized vapor deposition apparatus comprising an ultrasonic generator, wherein the atomized vapor deposition apparatus comprises a housing;
the shell comprises a rectifying section, a reaction section and a discharge section which are sequentially connected, the rectifying section is provided with an airflow converging structure, the discharge section is provided with an airflow diverging structure, the small-size end of the rectifying section is in butt joint with the input end of the reaction section, and the output end of the reaction section is in butt joint with the small-size end of the discharge section;
the top surface of the reaction section is provided with an ultrasonic generator, the bottom of the reaction section is provided with a sample placing table, the top surface of the sample placing table is positioned in the inner cavity of the reaction section, and the sample placing table and the ultrasonic generator are arranged opposite to each other;
the rectifying section is connected with an atomization mechanism through the inlet, and the atomization mechanism is connected with a carrier gas source.
2. The atomizing vapor deposition apparatus incorporating an ultrasonic generator according to claim 1, wherein a distance between a transmitting end of the ultrasonic generator and a top surface of the sample placement stage is 2 to 20mm;
the distance between the top surface of the sample placing table and the top surface of the inner cavity of the reaction section is 0.5-5mm;
the frequency of the ultrasonic generator is 20-1000kHz;
the power of the ultrasonic generator is 20-200mW/cm 2 。
3. The atomizing vapor deposition apparatus incorporating an ultrasonic generator according to claim 1, wherein said sample placement stage is disposed coaxially with said ultrasonic generator;
a temperature control component is arranged in the inner cavity of the sample placing table.
4. The atomizing vapor deposition apparatus incorporating an ultrasonic generator according to claim 1, wherein at least 1 of the atomizing mechanisms are connected to the rectifying section;
the atomization mechanism comprises an atomization chamber; the atomizing chamber comprises a shell, a carrier gas inlet and a carrier gas outlet are formed in the shell, the carrier gas inlet is communicated with the carrier gas source, and the carrier gas outlet is communicated with the inlet of the shell;
an air inlet branch is led out from a communicating pipeline of the carrier gas outlet and the inlet, and an air inlet end of the air inlet branch is communicated with a gas source;
the carrier gas source and the gas source independently comprise any one or a combination of at least two of nitrogen, argon, helium, or hydrogen.
5. The atomizing vapor deposition apparatus incorporating an ultrasonic generator of claim 4, wherein a bottom of said housing is provided with a first ultrasonic assembly, a portion of said first ultrasonic assembly being located in an interior cavity of said housing;
the frequency of the first ultrasonic assembly is 1-10MHz.
6. The atomizing vapor deposition apparatus incorporating an ultrasonic generator of claim 4, wherein said atomizing mechanism further comprises a container having an ultrasonic medium contained therein, a bottom of said atomizing chamber being located in an interior cavity of said container, a bottom of said container being provided with a second ultrasonic assembly, a portion of said second ultrasonic assembly being located in said interior cavity of said container;
the frequency of the second ultrasonic assembly is 1-10MHz.
7. The atomizing vapor deposition apparatus incorporating an ultrasonic generator according to claim 1, wherein the rectifying section includes a first cylindrical section and a tapered section which are butted in order, a cross-sectional area of the tapered section gradually decreases in a flow direction of mist, and a small-sized end of the tapered section is butted with an input end of the reaction section;
the structure of the reaction section comprises a straight cylinder structure with two open ends;
the discharge section comprises a divergent section and a second straight section which are in butt joint in sequence, the cross section area of the divergent section is gradually increased along the flow direction of the fog, and the small-size end of the divergent section is in butt joint with the output end of the reaction section;
at least 1 inlet is formed in the first straight barrel section, and at least 1 outlet is formed in the second straight barrel section.
8. The atomizing vapor deposition apparatus incorporating an ultrasonic generator according to claim 7, wherein 2 of said inlets are provided in an outer sidewall of said first cylinder section, respectively designated as a first inlet and a second inlet, said first inlet and said second inlet being disposed opposite each other.
9. A method of aerosol vapor deposition using the aerosol vapor deposition apparatus comprising an ultrasonic generator according to any one of claims 1 to 8, characterized in that the method of aerosol vapor deposition comprises:
placing a substrate on a sample placing table, and placing raw material liquid in an atomization mechanism; and starting an atomization mechanism to enable the raw material liquid to form mist to flow into the inner cavity of the shell, starting an ultrasonic generator, and transmitting ultrasonic waves to the surface of the substrate to perform atomization vapor deposition.
10. The method of atomizing vapor deposition according to claim 9, wherein the temperature of the substrate is 20 to 400 ℃;
the diameter of the liquid drops in the fog is 1-5 mu m;
the air pressure in the inner cavity of the shell is 10-110kPa.
CN202310552761.7A 2023-05-17 2023-05-17 Atomization vapor deposition device comprising ultrasonic generator and atomization vapor deposition method Pending CN116288260A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109306477A (en) * 2018-11-26 2019-02-05 南京航空航天大学 A kind of the nanometer sensitive thin film preparation facilities and preparation method of ultrasonic wave added
JP2020147464A (en) * 2019-03-13 2020-09-17 サムコ株式会社 Manufacturing method of metal nitride film
CN115862750A (en) * 2022-12-23 2023-03-28 南京邮电大学 Research on alpha-Ga 2 O 3 Growing aerosol chemical deposition system and method of construction thereof
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109306477A (en) * 2018-11-26 2019-02-05 南京航空航天大学 A kind of the nanometer sensitive thin film preparation facilities and preparation method of ultrasonic wave added
JP2020147464A (en) * 2019-03-13 2020-09-17 サムコ株式会社 Manufacturing method of metal nitride film
CN115862750A (en) * 2022-12-23 2023-03-28 南京邮电大学 Research on alpha-Ga 2 O 3 Growing aerosol chemical deposition system and method of construction thereof
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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