CN115928014B - Beta-phase gallium oxide film and preparation and doping methods thereof - Google Patents
Beta-phase gallium oxide film and preparation and doping methods thereof Download PDFInfo
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- CN115928014B CN115928014B CN202211478522.3A CN202211478522A CN115928014B CN 115928014 B CN115928014 B CN 115928014B CN 202211478522 A CN202211478522 A CN 202211478522A CN 115928014 B CN115928014 B CN 115928014B
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- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 title claims abstract description 175
- 229910001195 gallium oxide Inorganic materials 0.000 title claims abstract description 175
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000758 substrate Substances 0.000 claims abstract description 154
- 238000001704 evaporation Methods 0.000 claims abstract description 82
- 239000000463 material Substances 0.000 claims abstract description 80
- 238000005566 electron beam evaporation Methods 0.000 claims abstract description 77
- 239000011701 zinc Substances 0.000 claims abstract description 53
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 50
- 238000000137 annealing Methods 0.000 claims abstract description 26
- 238000000151 deposition Methods 0.000 claims abstract description 22
- 230000008021 deposition Effects 0.000 claims abstract description 18
- 238000010894 electron beam technology Methods 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 62
- 238000000576 coating method Methods 0.000 claims description 59
- 239000011248 coating agent Substances 0.000 claims description 56
- 238000004140 cleaning Methods 0.000 claims description 51
- 239000011259 mixed solution Substances 0.000 claims description 31
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 230000000630 rising effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000007747 plating Methods 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 13
- 239000002184 metal Substances 0.000 abstract description 12
- 230000003287 optical effect Effects 0.000 abstract description 7
- 238000005424 photoluminescence Methods 0.000 abstract description 5
- 238000002834 transmittance Methods 0.000 abstract description 5
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 152
- 230000008020 evaporation Effects 0.000 description 73
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 36
- 239000008367 deionised water Substances 0.000 description 35
- 229910021641 deionized water Inorganic materials 0.000 description 35
- 239000012535 impurity Substances 0.000 description 20
- 238000002791 soaking Methods 0.000 description 15
- 238000001816 cooling Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 238000002844 melting Methods 0.000 description 11
- 239000007888 film coating Substances 0.000 description 10
- 238000009501 film coating Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 238000001237 Raman spectrum Methods 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 6
- 239000000428 dust Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 238000002189 fluorescence spectrum Methods 0.000 description 6
- 238000005086 pumping Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 3
- 238000004549 pulsed laser deposition Methods 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000001451 molecular beam epitaxy Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention belongs to the technical field of semiconductor films, and particularly relates to a beta-phase gallium oxide film and a preparation and doping method thereof. The preparation method provided by the invention comprises the following steps: evaporating gallium oxide materials on the surface of a substrate by adopting an electron beam to deposit a film; carrying out high-temperature annealing treatment on the obtained primary beta-phase gallium oxide film in air; or respectively evaporating the gallium oxide material and the metal zinc particles on the surface of the substrate by adopting an electron beam for deposition, and carrying out high-temperature annealing treatment on the formed sandwich structure multilayer film in air to obtain the zinc-doped gallium oxide film. The preparation method provided by the invention adopts electron beam evaporation to coat a film on the surface of the substrate, and then carries out high-temperature annealing treatment, so that the structure, morphology, optical and electrical properties of the beta-phase Ga 2O3 film and the zinc-doped gallium oxide film obtained by the electron beam evaporation are effectively improved, the grain boundary of the film is clear, the preferred orientation and the grain size are higher, and the photoluminescence intensity and the optical transmittance are greatly improved.
Description
Technical Field
The invention belongs to the technical field of semiconductor films, and particularly relates to a beta-phase gallium oxide film and a preparation and doping method thereof.
Background
As a third generation semiconductor material, ga 2O3 has received attention because of its high forbidden bandwidth of 4.9eV, high corrosion resistance and high thermal stability, and high optical transmittance in the wavelength range from visible light to ultraviolet light.
Ga 2O3 films are typically prepared using a variety of deposition techniques, such as Molecular Beam Epitaxy (MBE), pulsed Laser Deposition (PLD), sputter deposition (Sputtering), metal Organic Chemical Vapor Deposition (MOCVD), and Electron Beam Evaporation (EBE). Among these, MBE deposition rates are slow. The plasma beam intensity of PLD and spinning is high and may damage the substrate surface structure. MOCVD requires higher temperatures for the metal-organic source and O 2 to react. The EBE has the characteristics of high efficiency, low cost, convenience and high deposition rate, and the EBE also avoids the additional introduction of reactive gas (O 2) in the deposition process, and meanwhile, when the Ga 2O3 film is prepared by adopting the EBE, the structure of Ga 2O3 can be further changed by selecting proper doping elements, and defect energy levels are introduced, so that the optical band gap and the electrical property of the Ga 2O3 film are adjusted.
At present, when the Ga 2O3 film is prepared by adopting the EBE method, the Ga 2O3 film with good crystallinity is generally obtained by regulating the temperature (80-100 ℃) of a substrate, so that the photoluminescence intensity of the Ga 2O3 film is improved, but the crystallization performance of the prepared Ga 2O3 film is still poor, the grain size is small, and the photoluminescence intensity and the optical transmittance of the Ga 2O3 film are influenced.
Disclosure of Invention
Firstly, the invention provides a preparation method of a beta-phase gallium oxide film, which comprises the following steps: evaporating a gallium oxide material by adopting an electron beam, and depositing a film on the surface of a substrate to obtain a primary beta-phase gallium oxide film, wherein the temperature of the substrate is between room temperature and 400 ℃ when the electron beam evaporation film coating is adopted; and carrying out high-temperature annealing treatment on the primary beta-phase gallium oxide film in air to obtain the beta-phase gallium oxide film. The preparation method provided by the invention effectively improves the crystallinity of the primary beta-phase Ga 2O3 film, the beta-phase Ga 2O3 film has higher preferred crystal orientation and larger crystal grain size, the crystal boundary is clear, and the photoluminescence intensity and the optical transmittance of the film are greatly improved. The example results show that the size of beta-phase Ga 2O3 crystal grains in the beta-phase Ga 2O3 film provided by the invention is 30nm, and the intensity of the emitted blue light (430 nm) and green light (513 nm) is obviously increased.
The preparation method of the beta-phase gallium oxide film provided by the invention has the characteristics of high efficiency, low cost, convenience, high deposition rate and capability of avoiding the additional introduction of reactive gas.
In order to achieve the above object, the present invention provides the following technical solutions:
evaporating a gallium oxide material by adopting an electron beam, and depositing a film on the surface of a substrate to obtain a primary beta-phase gallium oxide film, wherein the temperature of the substrate is between room temperature and 400 ℃ when the electron beam evaporation film coating is adopted;
and carrying out high-temperature annealing treatment on the primary beta-phase gallium oxide film in air to obtain the beta-phase gallium oxide film.
Secondly, the invention provides a preparation method of the zinc doped gallium oxide film, which can be used for doping other similar metal elements, and specifically comprises the following steps:
respectively evaporating the gallium oxide material and zinc particles by adopting an electron beam, and forming a sandwich structure multilayer film on the surface of the substrate, wherein the sandwich structure multilayer film is a first gallium oxide film, a zinc film and a second gallium oxide film which are sequentially laminated; the thickness of the first gallium oxide film is 100nm, and the thickness of the second gallium oxide film is 100nm; when the electron beam evaporation coating is adopted, the temperature of the substrate is between room temperature and 400 ℃;
And carrying out high-temperature annealing treatment on the sandwich structure multilayer film in air to obtain the zinc-doped gallium oxide film.
Preferably, the thickness of the zinc film is 10nm, 25nm, 50nm or the thickness of the zinc film is correspondingly changed according to the doping concentration requirement.
Preferably, the temperature of the high-temperature annealing treatment is 900-1000 ℃, the heat preservation time of the high-temperature annealing treatment is 0.5-2 h, and the temperature rising rate from the room temperature to the high-temperature annealing treatment temperature is 1-10 ℃/min.
Preferably, when the electron beam evaporation coating is adopted, the deposition rate of the gallium oxide material on the surface of the substrate is as follows
Preferably, when the electron beam evaporation coating is adopted, the filament current of the electron gun is 90-160 mA; the distance between the gallium oxide material and the filament of the electron gun is 20-30 mm. .
Preferably, the distance between the gallium oxide material and the substrate is 75-100 mm.
Preferably, the substrate is pretreated before the electron beam evaporation coating is carried out; the pretreatment comprises the following steps:
immersing the substrate in a mixed solution of NH 3、H2O2 and water for first cleaning to obtain a first processed substrate;
immersing the first treatment substrate in a mixed solution of HCl, H 2O2 and water for second cleaning to obtain a second treatment substrate;
Immersing the second treatment substrate in a mixed solution of H 2SO4、H2O2 and water for third cleaning to obtain a third treatment substrate;
And immersing the third treatment substrate in acetone, ethanol and water in sequence to carry out fourth, fifth and sixth cleaning.
The invention provides the beta-phase gallium oxide film obtained by the preparation method, wherein the average grain size of the beta-phase gallium oxide film calculated according to the orientation of the strongest peak (111) of the beta-phase gallium oxide is 30nm; the thickness of the beta-phase gallium oxide film is 10-1000 nm.
The zinc-doped gallium oxide film prepared by the preparation method provided by the invention has uniform appearance and thickness of 10-1000 nm.
Drawings
FIG. 1 is a schematic diagram of the experimental flow of the beta-phase gallium oxide film or zinc-doped gallium oxide film prepared in examples 1 to 3;
FIGS. 2 and 3 are SEM images of a beta-phase gallium oxide thin film prepared in example 1 of the present invention;
FIG. 4 is an SEM image of a zinc-doped gallium oxide film prepared according to example 3 of the invention;
FIG. 5 is an SEM image of a zinc-doped gallium oxide film prepared according to example 4 of the invention;
FIG. 6 is an SEM image of a zinc-doped gallium oxide film prepared according to example 5 of the invention;
FIG. 7 is an XRD spectrum of the surface of a beta-phase gallium oxide film prepared in example 1 of the present invention;
FIG. 8 is an XRD spectrum of the surface of the zinc-doped gallium oxide thin films prepared in examples 3 to 5 of the present invention;
FIG. 9 is a Raman spectrum of the beta-phase gallium oxide film prepared in example 1 of the present invention;
FIG. 10 is a Raman spectrum of the beta-phase gallium oxide film prepared in example 2 of the present invention;
FIG. 11 is a Raman spectrum of the zinc-doped gallium oxide film prepared in example 3 of the present invention;
FIG. 12 is a graph showing the UV-visible absorption spectrum of the surface of a beta-phase gallium oxide film prepared in example 1 of the present invention;
FIG. 13 is a photo-induced fluorescence spectrum of a beta-phase gallium oxide film prepared in example 1 of the invention;
FIG. 14 is a photo-induced fluorescence spectrum of a beta-phase gallium oxide film prepared in example 2 of the invention;
FIG. 15 is a photo-induced fluorescence spectrum of a zinc-doped gallium oxide film prepared in example 3 of the invention.
Detailed Description
The invention firstly provides a preparation method of a beta-phase gallium oxide film, which comprises the following steps:
evaporating a gallium oxide material by adopting an electron beam, and depositing a film on the surface of a substrate to obtain a primary beta-phase gallium oxide film, wherein the temperature of the substrate is between room temperature and 400 ℃ when the electron beam evaporation film coating is adopted;
And carrying out high-temperature annealing treatment on the primary beta-phase gallium oxide film to obtain the beta-phase gallium oxide film.
In the present invention, all preparation materials/components are commercially available products well known to those skilled in the art unless specified otherwise.
The gallium oxide material is particularly preferably a gallium oxide block material.
The substrate is particularly preferably a monocrystalline silicon substrate.
The substrate is preferably pretreated in the present invention before the electron beam evaporation coating is performed.
The pretreatment preferably comprises the steps of:
immersing the substrate in a mixed solution of NH 3、H2O2 and water for first cleaning to obtain a first processed substrate;
Immersing the first substrate in a mixed solution of HCl, H 2O2 and water for second cleaning to obtain a second processed substrate;
Immersing the second treatment substrate in a mixed solution of H 2SO4、H2O2 and water for third cleaning to obtain a third treatment substrate;
And immersing the third treatment substrate in acetone, ethanol and water in sequence for performing fourth, fifth and sixth cleaning.
And immersing the substrate in a mixed solution of NH 3、H2O2 and water for first cleaning to obtain a first processed substrate.
The molar ratio of NH 3、H2O2 to water in the mixed solution of NH 3、H2O2 and water is preferably 1:1:5.
The time of the first washing is preferably 4 hours.
The first washing is preferably a stationary washing.
The first cleaning water is preferably deionized water.
After the first processed substrate is obtained, the first substrate is immersed in a mixed solution of HCl, H 2O2 and water for second cleaning, and a second processed substrate is obtained.
The molar ratio of HCl to H 2O2 to water in the mixed solution of HCl, H 2O2 and water is preferably 1:1:6.
The time of the second washing is preferably 4 hours.
The second washing is preferably a stationary washing.
The second cleaning water is preferably deionized water.
The present invention preferably removes dust and metal cations from the surface of the substrate by a first cleaning and a second cleaning.
And after the second processed substrate is obtained, immersing the second processed substrate in a mixed solution of H 2SO4、H2O2 and water for third cleaning to obtain a third processed substrate.
Before the third cleaning, the second treated substrate is preferably subjected to a first pretreatment, and the first pretreatment is preferably performed by immersing the second treated substrate in water and performing ultrasonic water cleaning. The water is preferably deionized water, and the ultrasonic washing time is preferably 25-35 min.
The molar ratio of H 2SO4、H2O2 to water in the mixed solution of H 2SO4、H2O2 and water is preferably 4:1:8.
The time of the third washing is preferably 4 hours.
The third washing is preferably a stationary washing.
The third cleaning water is preferably deionized water.
The invention preferably removes the organic impurities from the substrate surface by the third cleaning.
And after the third processing substrate is obtained, the third processing substrate is immersed in a mixed solution of acetone, ethanol and deionized water in sequence to carry out fourth cleaning, fifth cleaning and sixth cleaning.
The fourth cleaning is preferably performed under ultrasonic conditions, and the time of the fourth cleaning is preferably 5 minutes.
The fifth cleaning is preferably performed under ultrasonic conditions, and the time of the fifth cleaning is preferably 5 minutes.
The sixth cleaning is preferably performed under ultrasonic conditions, and the time of the sixth cleaning is preferably 5 minutes.
In the electron beam evaporation, the gallium oxide material is preferably placed in a water-cooled crucible of an evaporation chamber, and the substrate is placed on a sample holder in the electron beam evaporation chamber.
The vacuum degree of the electron beam evaporation is preferably equal to or less than 5×10 -3 Pa.
When the electron beam evaporation coating is adopted, the vacuum system is pre-selected to be started, and the vacuum degree is pumped to be less than or equal to 5 multiplied by 10 - 3 Pa.
When the vacuum degree of electron beam evaporation is preferably less than or equal to 5×10 -3 Pa, the gallium oxide material is preferably subjected to pre-melting treatment.
When the gallium oxide material is subjected to pre-melting treatment, the electron beam evaporation vacuum chamber is preferably cleaned at the same time.
The specific implementation process of the premelting treatment of the gallium oxide material is preferably as follows: closing the evaporation source baffle, opening the filament power supply of the electron gun, and pre-melting the gallium oxide material in the crucible.
The specific implementation process of the cleaning treatment of the electron beam steam chamber is preferably as follows: and opening an ion source to clean residual gas in the electron beam evaporation cavity and residual impurities on the surface of the substrate.
After the gallium oxide material is melted, the evaporation source baffle is preferably opened, an automatic coating program is started, and evaporation coating is carried out on the melted gallium oxide material in the crucible.
When the electron beam evaporation coating is adopted, the temperature of the substrate is between room temperature and 400 ℃, preferably between room temperature and 100 ℃.
When the electron beam evaporation is used to coat a film on the surface of the substrate, the filament current of the electron gun is preferably 90 to 160mA, more preferably 90 to 155mA, and even more preferably 90 to 150mA.
When the electron beam evaporation coating is adopted, the deposition rate of the gallium oxide material on the surface of the substrate is preferablyMore preferably/>
When the electron beam evaporation coating is used, the distance between the gallium oxide material and the substrate is preferably 75 to 100mm, more preferably 80 to 95mm, and even more preferably 82 to 93mm.
When the electron beam evaporation coating is adopted, the distance between the gallium oxide material and the electron gun filament is preferably 20-30 mm, more preferably 22-28 mm, and even more preferably 24-26 mm.
When the electron beam evaporation coating is adopted, the deposition thickness of the beta-phase gallium oxide film is preferably 300nm.
The invention is favorable for obtaining the beta-phase gallium oxide film with high purity, good crystallinity and high stability by reasonably setting the working parameters of the electron beam evaporation coating.
After the film coating is finished, the evaporation source baffle is preferably closed, the electron gun is closed, the film is cooled along with the furnace, and the temperature is reduced and sampled, so that the primary beta-phase gallium oxide film is obtained.
After the primary beta-phase gallium oxide film is obtained, the primary beta-phase gallium oxide film is subjected to high-temperature annealing treatment, and the beta-phase gallium oxide film is obtained.
The temperature of the high-temperature annealing treatment is preferably 900 to 1000 ℃, more preferably 950 to 1000 ℃.
The holding time of the high-temperature annealing treatment is preferably 0.5 to 2 hours, more preferably 1 to 2 hours.
The heating rate from room temperature to the high-temperature annealing treatment temperature is preferably 1 to 10 ℃/min, more preferably 5 ℃/min.
The invention provides the beta-phase gallium oxide film prepared by the preparation method, wherein the average grain size of the beta-phase gallium oxide film calculated according to the orientation of the strongest peak (111) of the beta-phase gallium oxide is 30nm; the thickness of the beta-phase gallium oxide film is 10-1000 nm.
Secondly, the invention provides a preparation method of the zinc doped gallium oxide film, which can be used for doping other similar metals, and specifically comprises the following steps:
Respectively evaporating the gallium oxide material and zinc particles by adopting an electron beam, and forming a sandwich structure multilayer film on the surface of the substrate, wherein the sandwich structure multilayer film is a first gallium oxide film, a zinc film and a second gallium oxide film which are sequentially laminated; the thickness of the first gallium oxide film is 100nm, the thickness of the zinc film is 10nm, 25nm and 50nm or the thickness of the zinc film is correspondingly changed according to the doping concentration requirement, and the thickness of the second gallium oxide film is 100nm; when the electron beam evaporation coating is adopted, the temperature of the substrate is between room temperature and 400 ℃;
And carrying out high-temperature annealing treatment on the sandwich structure multilayer film in air to obtain the zinc-doped gallium oxide film.
According to the invention, a gallium oxide material and zinc particles are respectively evaporated by adopting an electron beam, and a sandwich structure multilayer film is formed on the surface of a substrate, wherein the sandwich structure multilayer film is a first gallium oxide film, a zinc film and a second gallium oxide film which are sequentially laminated; the thickness of the first gallium oxide film is 100nm, the thickness of the zinc film is 10nm, 25nm and 50nm or the thickness of the zinc film is correspondingly changed according to the doping concentration requirement, and the thickness of the second gallium oxide film is 100nm; when the electron beam evaporation coating is adopted, the temperature of the substrate is between room temperature and 400 ℃.
The substrate is preferably pretreated before the electron beam evaporation coating is performed. The pretreatment is preferably the same as the pretreatment method of the substrate in the preparation method of the beta-phase gallium oxide film, and will not be described in detail here.
When the sandwich structure multilayer film is prepared by adopting electron beam evaporation coating, preferably, gallium oxide materials and zinc particles are respectively placed in a water-cooling crucible of an evaporation chamber, and the substrate is placed on a sample frame in the electron beam evaporation chamber.
According to the invention, the gallium oxide material is evaporated by adopting the electron beam, and the vacuum degree of the electron beam evaporation is preferably less than or equal to 5 multiplied by 10 -3 Pa when the first gallium oxide film is formed on the surface of the substrate. When the electron beam evaporation coating is adopted, a vacuum system is pre-selected and started, and the vacuum degree is pumped to be less than or equal to 5 multiplied by 10 -3 Pa. When the vacuum degree of electron beam evaporation is preferably equal to or less than 5×10 -3 Pa, the gallium oxide material is preferably subjected to pre-melting treatment. When the gallium oxide material is subjected to the premelting treatment, the electron beam evaporation vacuum chamber is preferably cleaned at the same time. The specific implementation process of the premelting treatment of the gallium oxide material is preferably as follows: closing the evaporation source baffle, opening the filament power supply of the electron gun, and pre-melting the gallium oxide material in the crucible. The specific implementation process of cleaning the electron beam vapor chamber is preferably as follows: and opening an ion source to clean residual gas in the electron beam evaporation cavity and residual impurities on the surface of the substrate. After the gallium oxide material is melted, an evaporation source baffle is preferably opened, an automatic coating program is started, and evaporation coating is carried out on the melted gallium oxide material in the crucible. When the electron beam evaporation coating is adopted, the temperature of the substrate is between room temperature and 400 ℃, preferably between room temperature and 100 ℃. When the electron beam evaporation is used to coat a film on the surface of the substrate, the filament current of the electron gun is preferably 90 to 160mA, more preferably 90 to 155mA, and even more preferably 90 to 150mA. When the electron beam evaporation coating is adopted, the deposition rate of the gallium oxide material on the surface of the substrate is preferablyMore preferablyWhen the electron beam evaporation coating is used, the distance between the gallium oxide material and the substrate is preferably 75 to 100mm, more preferably 80 to 95mm, and even more preferably 82 to 93mm. When the electron beam evaporation coating is adopted, the distance between the gallium oxide material and the electron gun filament is preferably 20-30 mm, more preferably 22-28 mm, and even more preferably 24-26 mm. After the film coating is finished, the evaporation source baffle is preferably closed, the electron gun is closed, the film is cooled along with the furnace, and the film is cooled to room temperature, so that the first gallium oxide film is obtained.
And evaporating zinc particles by adopting an electron beam after the first gallium oxide film is obtained, and forming a zinc film on the surface of the first gallium oxide film, wherein the thickness of the zinc film is 10nm, 25nm and 50nm or the thickness of the zinc film is correspondingly changed according to the doping concentration requirement.
In the invention, when the zinc film is prepared by adopting electron beam evaporation coating, the vacuum degree of electron beam evaporation is preferably less than or equal to 5 multiplied by 10 -3 Pa. When the electron beam evaporation coating is adopted, a vacuum system is pre-selected and started, and the vacuum degree is pumped to be less than or equal to 5 multiplied by 10 - 3 Pa. When the vacuum degree of the electron beam evaporation is preferably 5×10 -3 Pa or less, the zinc particles are preferably subjected to a pre-melting treatment. When the zinc particles are subjected to the pre-melting treatment, the electron beam evaporation vacuum chamber is preferably simultaneously cleaned. The specific implementation process of the pre-melting treatment of the zinc particles is preferably as follows: closing the evaporation source baffle, opening the filament power supply of the electron gun, and pre-melting zinc particles in the crucible. The specific implementation process of cleaning the electron beam vapor chamber is preferably as follows: and opening an ion source to clean residual gas in the electron beam evaporation cavity and residual impurities on the surface of the substrate. After the zinc particles are melted, an evaporation source baffle is preferably opened, an automatic coating program is started, and evaporation coating is carried out on the melted zinc particles in the crucible. When the electron beam evaporation coating is adopted, the temperature of the substrate is between room temperature and 400 ℃, preferably between room temperature and 100 ℃. When the electron beam evaporation is used to coat a film on the surface of the substrate, the filament current of the electron gun is preferably 90 to 160mA, more preferably 90 to 155mA, and even more preferably 90 to 150mA. When the electron beam evaporation coating is adopted, the deposition rate of the zinc particles on the surface of the substrate is preferablyMore preferably/>When the electron beam evaporation coating is used, the distance between the zinc particles and the substrate is preferably 75 to 100mm, more preferably 80 to 95mm, and even more preferably 82 to 93mm. When the electron beam evaporation coating is used, the distance between the zinc particles and the electron gun filament is preferably 20 to 30mm, more preferably 22 to 28mm, and even more preferably 24 to 26mm. After the film coating is finished, the evaporation source baffle is preferably closed, the electron gun is closed, the film is cooled along with the furnace, and the zinc film is obtained after the film is cooled to room temperature.
After the zinc film is obtained, the invention continuously adopts electron beams to evaporate the gallium oxide material, and when a second gallium oxide film is formed on the surface of the zinc film, the vacuum degree of the electron beam evaporation is preferably less than or equal to 5 multiplied by 10 -3 Pa. When the electron beam evaporation coating is adopted, a vacuum system is pre-selected and started, and the vacuum degree is pumped to be less than or equal to 5 multiplied by 10 -3 Pa. When the vacuum degree of electron beam evaporation is preferably equal to or less than 5×10 -3 Pa, the gallium oxide material is preferably subjected to pre-melting treatment. When the gallium oxide material is subjected to the premelting treatment, the electron beam evaporation vacuum chamber is preferably cleaned at the same time. The specific implementation process of the premelting treatment of the gallium oxide material is preferably as follows: closing the evaporation source baffle, opening the filament power supply of the electron gun, and pre-melting the gallium oxide material in the crucible. The specific implementation process of the cleaning treatment of the electron beam steam chamber is preferably as follows: and opening an ion source to clean residual gas in the electron beam evaporation cavity and residual impurities on the surface of the substrate. After the gallium oxide material is melted, an evaporation source baffle is preferably opened, an automatic coating program is started, and evaporation coating is carried out on the melted gallium oxide material in the crucible. When the electron beam evaporation coating is adopted, the temperature of the substrate is between room temperature and 400 ℃, preferably between room temperature and 100 ℃. When the electron beam evaporation is used to coat a film on the surface of the substrate, the filament current of the electron gun is preferably 90 to 160mA, more preferably 90 to 155mA, and even more preferably 90 to 150mA. When the electron beam evaporation coating is adopted, the deposition rate of the gallium oxide material on the surface of the substrate is preferablyMore preferably/>When the electron beam evaporation coating is used, the distance between the gallium oxide material and the substrate is preferably 75 to 100mm, more preferably 80 to 95mm, and even more preferably 82 to 93mm. In the present invention, when the electron beam evaporation coating is used, the distance between the gallium oxide material and the electron gun filament is preferably 20 to 30mm, more preferably 22 to 28mm, and even more preferably 24 to 26mm. After the film coating is finished, the evaporation source baffle is preferably closed, the electron gun is closed, the furnace is cooled, and the second gallium oxide film is obtained after the temperature is reduced to the room temperature. After the steps are completed, the sandwich structure multilayer film is formed on the surface of the substrate.
After the sandwich structure multilayer film is obtained, the zinc doped gallium oxide film is obtained by carrying out high-temperature annealing treatment on the sandwich structure multilayer film in air. The temperature of the high-temperature annealing treatment is preferably 900 to 1000 ℃, more preferably 950 to 1000 ℃. The holding time of the high-temperature annealing treatment is preferably 0.5 to 2 hours, more preferably 1 to 2 hours. The heating rate from room temperature to the high-temperature annealing treatment temperature is preferably 1 to 10 ℃/min, more preferably 5 ℃/min.
The zinc-doped gallium oxide film prepared by the preparation method provided by the invention has uniform appearance and thickness of 10-1000 nm.
For further explanation of the present invention, the β -phase gallium oxide thin film and the doping method thereof according to the present invention will be described in detail with reference to the accompanying drawings and examples, which should not be construed as limiting the scope of the present invention.
Example 1
According to the experimental procedure shown in fig. 1: firstly, under the condition of room temperature, placing a monocrystalline silicon substrate into a mixed solution of NH 3、H2O2 and deionized water (the molar ratio is 1:1:5), standing for 4 hours, taking out, placing into a mixed solution of HCl, H 2O2 and deionized water (the molar ratio is 1:1:6), soaking, standing for 4 hours, taking out, soaking with deionized water, ultrasonically cleaning for 25-35 minutes, and removing impurities such as dust and metal cations on the surface of the substrate.
Then, the monocrystalline silicon substrate is placed in a mixed solution of H 2SO4、H2O2 and deionized water (the molar ratio is 4:1:8) for soaking, the monocrystalline silicon substrate is taken out after standing for 4 hours, the monocrystalline silicon substrate is soaked in the deionized water and is ultrasonically cleaned for 25-35 min, and organic impurities on the surface of the substrate are continuously removed.
And finally, sequentially immersing the monocrystalline silicon substrate in acetone, ethanol and deionized water, and cleaning the monocrystalline silicon substrate in an ultrasonic cleaner for 5 minutes to finish the cleaning work of the substrate.
Placing the granular gallium oxide solid evaporation material into a water-cooled crucible of an evaporation chamber, and placing the cleaned monocrystalline silicon substrate into a sample holder in the chamber.
And starting a vacuum system, and pumping the vacuum degree in the cavity to be less than or equal to 5 multiplied by 10 -3 Pa.
When the set vacuum degree is reached, the evaporation source baffle is closed, the filament of the electron gun is opened, and the gallium oxide evaporation material in the crucible is subjected to premelting treatment. And simultaneously, the ion source is turned on to clean residual gas in the electron beam evaporation cavity and impurities on the surface of the substrate.
Opening an evaporation source baffle plate, starting an automatic coating procedure, and carrying out evaporation coating on the evaporation material in the crucible, wherein in the process of electron beam evaporation coating, the temperature of the substrate is room temperature, the filament current of an electron gun is 90mA, the distance between the evaporation material and the substrate is 87mm, the distance between the evaporation material and the filament of the electron gun is 25mm, and the deposition rate of the evaporation material obtained under the conditions isThe film deposition thickness was set to 300nm. And after coating, immediately closing the evaporation source baffle, closing the electron gun, cooling to room temperature along with the furnace, and taking out the sample to obtain the primary gallium oxide film.
And (3) placing the primary gallium oxide film in a muffle furnace, heating to 950 ℃ at a speed of 5 ℃/min in air, keeping the temperature for 30min, closing the muffle furnace, and naturally cooling the sample in air to obtain the beta-phase gallium oxide film.
Example 2
According to the experimental procedure shown in fig. 1: firstly, under the condition of room temperature, placing a monocrystalline silicon substrate into a mixed solution of NH 3、H2O2 and deionized water (the molar ratio is 1:1:5), standing for 4 hours, taking out, placing into a mixed solution of HCl, H 2O2 and deionized water (the molar ratio is 1:1:6), soaking, standing for 4 hours, taking out, soaking with deionized water, ultrasonically cleaning for 25-35 minutes, and removing impurities such as dust and metal cations on the surface of the substrate.
Then, the monocrystalline silicon substrate is placed in a mixed solution of H 2SO4、H2O2 and deionized water (the molar ratio is 4:1:8) for soaking, the monocrystalline silicon substrate is taken out after standing for 4 hours, the monocrystalline silicon substrate is soaked in the deionized water and is ultrasonically cleaned for 25-35 min, and organic impurities on the surface of the substrate are continuously removed.
And finally, sequentially immersing the monocrystalline silicon substrate in acetone, ethanol and deionized water, and cleaning the monocrystalline silicon substrate in an ultrasonic cleaner for 5 minutes to finish the cleaning work of the substrate.
Placing the granular gallium oxide solid evaporation material into a water-cooled crucible of an evaporation chamber, and placing the cleaned monocrystalline silicon substrate into a sample holder in the chamber.
And starting a vacuum system, and pumping the vacuum degree in the cavity to be less than or equal to 5 multiplied by 10 -3 Pa.
When the set vacuum degree is reached, the evaporation source baffle is closed, the filament of the electron gun is opened, and the gallium oxide evaporation material in the crucible is subjected to premelting treatment. And simultaneously, the ion source is turned on to clean residual gas in the electron beam evaporation cavity and impurities on the surface of the substrate.
Opening an evaporation source baffle plate, starting an automatic coating procedure, and carrying out evaporation coating on the evaporation material in the crucible, wherein in the process of electron beam evaporation coating, the temperature of the substrate is room temperature, the filament current of an electron gun is 90mA, the distance between the evaporation material and the substrate is 87mm, the distance between the evaporation material and the filament of the electron gun is 25mm, and the deposition rate of the evaporation material obtained under the conditions isThe film deposition thickness was set to 300nm. And after coating, immediately closing the evaporation source baffle, closing the electron gun, cooling to room temperature along with the furnace, and taking out the sample to obtain the primary gallium oxide film.
And (3) placing the primary gallium oxide film in a muffle furnace, heating to 950 ℃ at a speed of 5 ℃/min in air, keeping the temperature for 90min, closing the muffle furnace, and naturally cooling the sample in air to obtain the beta-phase gallium oxide film.
Example 3
According to the experimental procedure shown in fig. 1: firstly, under the condition of room temperature, placing a monocrystalline silicon substrate into a mixed solution of NH 3、H2O2 and deionized water (the molar ratio is 1:1:5), standing for 4 hours, taking out, placing into a mixed solution of HCl, H 2O2 and deionized water (the molar ratio is 1:1:6), soaking, standing for 4 hours, taking out, soaking with deionized water, ultrasonically cleaning for 25-35 minutes, and removing impurities such as dust and metal cations on the surface of the substrate.
Then, the monocrystalline silicon substrate is placed in a mixed solution of H 2SO4、H2O2 and deionized water (the molar ratio is 4:1:8) for soaking, the monocrystalline silicon substrate is taken out after standing for 4 hours, the monocrystalline silicon substrate is soaked in the deionized water and is ultrasonically cleaned for 25-35 min, and organic impurities on the surface of the substrate are continuously removed.
And finally, sequentially immersing the monocrystalline silicon substrate in acetone, ethanol and deionized water, and cleaning the monocrystalline silicon substrate in an ultrasonic cleaner for 5 minutes to finish the cleaning work of the substrate.
And respectively placing the granular gallium oxide and the metallic zinc solid evaporation materials into a water-cooled crucible of an evaporation chamber, and then placing the cleaned monocrystalline silicon substrate on a sample rack in the chamber.
And starting a vacuum system, and pumping the vacuum degree in the cavity to be less than or equal to 5 multiplied by 10 -3 Pa.
When the set vacuum degree is reached, the evaporation source baffle is closed, the filament of the electron gun is opened, and the gallium oxide and the metal zinc evaporation materials in the crucible are respectively pre-melted. And simultaneously, the ion source is turned on to clean residual gas in the electron beam evaporation cavity and impurities on the surface of the substrate.
Opening an evaporation source baffle plate, starting an automatic coating procedure, and respectively carrying out evaporation coating on gallium oxide and zinc evaporation materials in a crucible, wherein in the coating process, the temperature of a substrate is room temperature, the filament current of an electron gun is 90mA, the distance between the evaporation materials and the substrate is 87mm, the distance between the evaporation materials and the filament of the electron gun is 25mm, and the deposition rate of the evaporation materials obtained under the conditions isThe coating sequence and thickness were set to Ga 2O3100 nm、Zn 10nm、Ga2O3 100, 100 nm. And after the film coating is finished, immediately closing the evaporation source baffle, closing the electron gun, cooling to room temperature along with the furnace, and taking out the sample to obtain the sandwich-structure multilayer film.
And (3) placing the sandwich structure multilayer film in a muffle furnace, heating to 950 ℃ at a speed of 5 ℃/min in air, keeping the temperature for 90min, closing the muffle furnace, and naturally cooling the sample in air to obtain the zinc doped gallium oxide film.
Example 4
According to the experimental procedure shown in fig. 1: firstly, under the condition of room temperature, placing a monocrystalline silicon substrate into a mixed solution of NH 3、H2O2 and deionized water (the molar ratio is 1:1:5), standing for 4 hours, taking out, placing into a mixed solution of HCl, H 2O2 and deionized water (the molar ratio is 1:1:6), soaking, standing for 4 hours, taking out, soaking with deionized water, ultrasonically cleaning for 25-35 minutes, and removing impurities such as dust and metal cations on the surface of the substrate.
Then, the monocrystalline silicon substrate is placed in a mixed solution of H 2SO4、H2O2 and deionized water (the molar ratio is 4:1:8) for soaking, the monocrystalline silicon substrate is taken out after standing for 4 hours, the monocrystalline silicon substrate is soaked in the deionized water and is ultrasonically cleaned for 25-35 min, and organic impurities on the surface of the substrate are continuously removed.
And finally, sequentially immersing the monocrystalline silicon substrate in acetone, ethanol and deionized water, and cleaning the monocrystalline silicon substrate in an ultrasonic cleaner for 5 minutes to finish the cleaning work of the substrate.
And respectively placing the granular gallium oxide and the metallic zinc solid evaporation materials into a water-cooled crucible of an evaporation chamber, and then placing the cleaned monocrystalline silicon substrate on a sample rack in the chamber.
And starting a vacuum system, and pumping the vacuum degree in the cavity to be less than or equal to 5 multiplied by 10 -3 Pa.
When the set vacuum degree is reached, the evaporation source baffle is closed, the filament of the electron gun is opened, and the gallium oxide and the metal zinc evaporation materials in the crucible are respectively pre-melted. And simultaneously, the ion source is turned on to clean residual gas in the electron beam evaporation cavity and impurities on the surface of the substrate.
Opening an evaporation source baffle plate, starting an automatic coating procedure, and respectively carrying out evaporation coating on gallium oxide and zinc evaporation materials in a crucible, wherein in the coating process, the temperature of a substrate is room temperature, the filament current of an electron gun is 90mA, the distance between the evaporation materials and the substrate is 87mm, the distance between the evaporation materials and the filament of the electron gun is 25mm, and the deposition rate of the evaporation materials obtained under the conditions isThe coating sequence and thickness were set to Ga 2O3100 nm、Zn 25nm、Ga2O3 100, 100 nm. And after the film coating is finished, immediately closing the evaporation source baffle, closing the electron gun, cooling to room temperature along with the furnace, and taking out the sample to obtain the sandwich-structure multilayer film.
And (3) placing the sandwich structure multilayer film in a muffle furnace, heating to 950 ℃ at a speed of 5 ℃/min in air, keeping the temperature for 90min, closing the muffle furnace, and naturally cooling the sample in air to obtain the zinc doped gallium oxide film.
Example 5
According to the experimental procedure shown in fig. 1: firstly, under the condition of room temperature, placing a monocrystalline silicon substrate into a mixed solution of NH 3、H2O2 and deionized water (the molar ratio is 1:1:5), standing for 4 hours, taking out, placing into a mixed solution of HCl, H 2O2 and deionized water (the molar ratio is 1:1:6), soaking, standing for 4 hours, taking out, soaking with deionized water, ultrasonically cleaning for 25-35 minutes, and removing impurities such as dust and metal cations on the surface of the substrate.
Then, the monocrystalline silicon substrate is placed in a mixed solution of H 2SO4、H2O2 and deionized water (the molar ratio is 4:1:8) for soaking, the monocrystalline silicon substrate is taken out after standing for 4 hours, the monocrystalline silicon substrate is soaked in the deionized water and is ultrasonically cleaned for 25-35 min, and organic impurities on the surface of the substrate are continuously removed.
And finally, sequentially immersing the monocrystalline silicon substrate in acetone, ethanol and deionized water, and cleaning the monocrystalline silicon substrate in an ultrasonic cleaner for 5 minutes to finish the cleaning work of the substrate.
And respectively placing the granular gallium oxide and the metallic zinc solid evaporation materials into a water-cooled crucible of an evaporation chamber, and then placing the cleaned monocrystalline silicon substrate on a sample rack in the chamber.
And starting a vacuum system, and pumping the vacuum degree in the cavity to be less than or equal to 5 multiplied by 10 -3 Pa.
When the set vacuum degree is reached, the evaporation source baffle is closed, the filament of the electron gun is opened, and the gallium oxide and the metal zinc evaporation materials in the crucible are respectively pre-melted. And simultaneously, the ion source is turned on to clean residual gas in the electron beam evaporation cavity and impurities on the surface of the substrate.
Opening an evaporation source baffle plate, starting an automatic coating procedure, and respectively carrying out evaporation coating on gallium oxide and zinc evaporation materials in a crucible, wherein in the coating process, the temperature of a substrate is room temperature, the filament current of an electron gun is 90mA, the distance between the evaporation materials and the substrate is 87mm, the distance between the evaporation materials and the filament of the electron gun is 25mm, and the deposition rate of the evaporation materials obtained under the conditions isThe coating sequence and thickness were set to Ga 2O3100 nm、Zn 50nm、Ga2O3 100, 100 nm. And after the film coating is finished, immediately closing the evaporation source baffle, closing the electron gun, cooling to room temperature along with the furnace, and taking out the sample to obtain the sandwich-structure multilayer film.
And (3) placing the sandwich structure multilayer film in a muffle furnace, heating to 950 ℃ at a speed of 5 ℃/min in air, keeping the temperature for 90min, closing the muffle furnace, and naturally cooling the sample in air to obtain the zinc doped gallium oxide film.
Comparative example 1
The preparation process was essentially the same as in example 1, except that: high temperature annealing treatment in air is not performed.
Test case
FIG. 1 is a flow chart of the experiment of preparing zinc-doped gallium oxide film in examples 3-5 of preparing beta-phase gallium oxide film in examples 1-2;
FIGS. 2 and 3 are SEM images of a beta-phase gallium oxide thin film prepared in example 1 of the present invention;
FIG. 4 is an SEM image of a zinc-doped gallium oxide film prepared according to example 3 of the invention;
FIG. 5 is an SEM image of a zinc-doped gallium oxide film prepared according to example 4 of the invention;
FIG. 6 is an SEM image of a zinc-doped gallium oxide film prepared according to example 5 of the invention;
FIG. 7 is an XRD spectrum of a beta-phase gallium oxide film prepared in example 1 of the present invention;
As can be seen from fig. 2 and fig. 7, in embodiment 1 of the present invention, by reasonably setting the working parameters of electron beam evaporation, and simultaneously performing high-temperature annealing treatment on the primary gallium oxide film, the working parameters of annealing treatment are reasonably set, and the prepared β -phase gallium oxide film has a higher preferred orientation and a larger grain size, and the grain boundary becomes clearer.
FIG. 8 is an XRD spectrum of a zinc-doped gallium oxide film prepared in examples 3-5 of the present invention;
As can be seen from FIG. 8, in example 4, the zinc-doped gallium oxide film has the best crystallization quality when the coating sequence and thickness are 100nm of gallium oxide, 25nm of zinc and 100nm of gallium oxide;
FIG. 9 is a Raman spectrum of the beta-phase gallium oxide film prepared in example 1 of the present invention;
FIG. 10 is a Raman spectrum of the beta-phase gallium oxide film prepared in example 2 of the present invention;
FIG. 11 is a Raman spectrum of a zinc-doped gallium oxide film prepared in example 3 of the present invention.
FIG. 12 is a graph showing the UV-visible absorption spectrum of the surface of the beta-phase gallium oxide film prepared in example 1 of the present invention.
FIG. 13 is a photo-induced fluorescence spectrum of a beta-phase gallium oxide film prepared in example 1 of the invention;
FIG. 14 is a photo-induced fluorescence spectrum of a beta-phase gallium oxide film prepared in example 2 of the invention;
fig. 15 is a photo-induced fluorescence spectrum of the beta-phase gallium oxide thin film prepared in example 3 of the present invention.
As can be seen from FIGS. 9 to 11, the blue light peak (430 nm) and the green light peak (513 nm) of the beta-phase gallium oxide film obtained by the preparation method provided by the invention have obviously increased intensity, and the photoluminescence intensity and the optical transmittance are greatly improved.
Although the foregoing embodiments have been described in some, but not all embodiments of the invention, other embodiments may be obtained according to the present embodiments without departing from the scope of the invention.
Claims (8)
1. The preparation method of the zinc-doped gallium oxide film is characterized by comprising the following steps of:
respectively evaporating the gallium oxide material and zinc particles by adopting an electron beam, and forming a sandwich structure multilayer film on the surface of the substrate, wherein the sandwich structure multilayer film is a first gallium oxide film, a zinc film and a second gallium oxide film which are sequentially laminated; the thickness of the first gallium oxide film is 100nm, and the thickness of the second gallium oxide film is 100nm; when the electron beam evaporation coating is adopted, the temperature of the substrate is between room temperature and 400 ℃;
And carrying out high-temperature annealing treatment on the sandwich structure multilayer film in air to obtain the zinc-doped gallium oxide film.
2. The method for producing a zinc-doped gallium oxide film according to claim 1, wherein the thickness of the zinc film is 10nm, 25nm or 50nm.
3. The method according to claim 1, wherein the high-temperature annealing treatment is performed at a temperature of 900 to 1000 ℃, the heat-preserving time of the high-temperature annealing treatment is 0.5 to 2 hours, and the temperature rising rate from room temperature to the high-temperature annealing treatment temperature is 1 to 10 ℃/min.
4. The method according to claim 1, wherein the deposition rate of the gallium oxide material on the surface of the substrate is
5. The method according to claim 1, wherein the electron gun filament current is 90-160 mA when the electron beam evaporation coating is adopted; the distance between the gallium oxide material and the filament of the electron gun is 20-30 mm.
6. The method of claim 1, wherein the gallium oxide material is spaced from the substrate by a distance of 75-100 mm.
7. The method according to claim 1, wherein the substrate is subjected to pretreatment before the electron beam evaporation plating; the pretreatment comprises the following steps:
immersing the substrate in a mixed solution of NH 3、H2O2 and water for first cleaning to obtain a first processed substrate;
immersing the first treatment substrate in a mixed solution of HCl, H 2O2 and water for second cleaning to obtain a second treatment substrate;
Immersing the second treatment substrate in a mixed solution of H 2SO4、H2O2 and water for third cleaning to obtain a third treatment substrate;
And immersing the third treatment substrate in acetone, ethanol and water in sequence to carry out fourth, fifth and sixth cleaning.
8. The zinc-doped gallium oxide film prepared by the preparation method of any one of claims 1 to 7, which is characterized in that the appearance of the zinc-doped gallium oxide film is uniform, and the thickness is 10 to 1000nm.
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