CN115928014A - 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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- CN115928014A CN115928014A CN202211478522.3A CN202211478522A CN115928014A CN 115928014 A CN115928014 A CN 115928014A CN 202211478522 A CN202211478522 A CN 202211478522A CN 115928014 A CN115928014 A CN 115928014A
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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 188
- 229910001195 gallium oxide Inorganic materials 0.000 title claims abstract description 188
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000758 substrate Substances 0.000 claims abstract description 133
- 239000000463 material Substances 0.000 claims abstract description 83
- 238000001704 evaporation Methods 0.000 claims abstract description 82
- 238000005566 electron beam evaporation Methods 0.000 claims abstract description 78
- 239000011701 zinc Substances 0.000 claims abstract description 46
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 43
- 238000000137 annealing Methods 0.000 claims abstract description 27
- 238000000151 deposition Methods 0.000 claims abstract description 23
- 230000008021 deposition Effects 0.000 claims abstract description 18
- 238000010894 electron beam technology Methods 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 16
- 239000013078 crystal Substances 0.000 claims abstract description 4
- 239000010408 film Substances 0.000 claims description 155
- 238000004140 cleaning Methods 0.000 claims description 60
- 238000000576 coating method Methods 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- 239000011248 coating agent Substances 0.000 claims description 49
- 239000010409 thin film Substances 0.000 claims description 23
- 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
- 239000011259 mixed solution Substances 0.000 claims description 17
- 238000002791 soaking Methods 0.000 claims description 7
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 11
- 230000003287 optical effect Effects 0.000 abstract description 6
- 238000005424 photoluminescence Methods 0.000 abstract description 5
- 238000002834 transmittance Methods 0.000 abstract description 5
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 230000008020 evaporation Effects 0.000 description 73
- 239000008367 deionised water Substances 0.000 description 24
- 229910021641 deionized water Inorganic materials 0.000 description 24
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 21
- 238000001816 cooling Methods 0.000 description 14
- 239000007888 film coating Substances 0.000 description 14
- 238000009501 film coating Methods 0.000 description 14
- 230000008018 melting Effects 0.000 description 14
- 238000002844 melting Methods 0.000 description 14
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 13
- 239000012535 impurity Substances 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 7
- 238000001237 Raman spectrum Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000000103 photoluminescence spectrum Methods 0.000 description 6
- 238000005086 pumping Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 4
- 238000004321 preservation Methods 0.000 description 3
- 238000004549 pulsed laser deposition Methods 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000001451 molecular beam epitaxy Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 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
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 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
- 239000000428 dust Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
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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 method and a 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 and form a film; the obtained primary betaCarrying out high-temperature annealing treatment on the phase gallium oxide film in the air; or respectively evaporating gallium oxide materials and 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 multilayer film with the sandwich structure in the 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, thereby effectively improving beta-phase Ga obtained by electron beam evaporation 2 O 3 The film and the zinc-doped gallium oxide film have the advantages of clear crystal boundary, higher preferred orientation and larger grain size, and greatly improved photoluminescence intensity and optical transmittance.
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 method and a doping method thereof.
Background
As third generation semiconductor materials, ga 2 O 3 Has a high energy gap of 4.9eV, high corrosion resistance and high thermal stability, and a high optical transmittance in a wavelength range from visible light to ultraviolet light, and thus has received much attention.
Ga 2 O 3 Thin 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, the deposition rate of MBE is slow. The plasma intensity of PLD and Sputtering is high and can damage the substrate surface structure. MOCVD requires metals at higher temperatures-organic source and O 2 The reaction can take place. While EBE has the advantages of high efficiency, low cost, convenience and high deposition rate, EBE also avoids the additional introduction of reactive gas (O) during the deposition process 2 ) While simultaneously preparing Ga by using EBE 2 O 3 In the case of thin films, ga can be further changed by selecting appropriate doping elements 2 O 3 Introducing defect levels to adjust Ga 2 O 3 Optical band gap and electrical properties of the thin film.
At present, the EBE method is adopted to prepare Ga 2 O 3 In the case of a thin film, it is common to control the temperature of the substrate (80 to 100 ℃ C.) to obtain Ga having good crystallinity 2 O 3 Film of, thereby increasing Ga 2 O 3 Thin film photoluminescence intensity, but Ga produced 2 O 3 The crystallization property of the film is still poor, the grain size is small, and Ga is influenced 2 O 3 Photoluminescence intensity and optical transmittance of the film.
Disclosure of Invention
Firstly, the invention provides a preparation method of a beta-phase gallium oxide film, which comprises the following steps: evaporating gallium oxide materials by adopting an electron beam, depositing the gallium oxide materials on the surface of a substrate to form a film, and obtaining a primary beta-phase gallium oxide film, wherein the temperature of the substrate is between room temperature and 400 ℃ when the electron beam evaporation coating is adopted; and carrying out high-temperature annealing treatment on the primary beta-phase gallium oxide film in the air to obtain the beta-phase gallium oxide film. The preparation method provided by the invention effectively improves primary beta-phase Ga 2 O 3 Crystallinity of thin film, beta phase Ga 2 O 3 The film has higher preferred crystal orientation and larger grain size, the grain boundary is clear, and the photoluminescence intensity and the optical transmittance of the film are greatly improved. The results of the examples show that the invention provides beta-phase Ga 2 O 3 Beta phase Ga in thin film 2 O 3 The size of the crystal grains is 30nm, and the emitted blue light (430 nm) and green light (513 nm) are remarkably increased in intensity.
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 avoidance of additional introduction of reactive gas.
In order to achieve the above purpose, the invention provides the following technical scheme:
evaporating gallium oxide materials by adopting an electron beam, depositing the gallium oxide materials on the surface of a substrate to form a film, and obtaining a primary beta-phase gallium oxide film, wherein the temperature of the substrate is between room temperature and 400 ℃ when the electron beam evaporation coating is adopted;
and carrying out high-temperature annealing treatment on the primary beta-phase gallium oxide film in the air to obtain the beta-phase gallium oxide film.
Secondly, the invention provides a preparation method of the zinc-doped gallium oxide film, the method can also be used for doping other similar metal elements, and the method specifically comprises the following steps:
respectively evaporating gallium oxide materials 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 stacked; 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 the 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 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 heating rate from the room temperature to the temperature of the high-temperature annealing treatment 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
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; the pretreatment comprises the following steps:
immersing the substrate in NH 3 、H 2 O 2 Carrying out first cleaning in a mixed solution of water to obtain a first processing substrate;
immersing the first treated substrate in HCl, H 2 O 2 Carrying out second cleaning in the mixed solution of water to obtain a second processing substrate;
immersing the second handle substrate in H 2 SO 4 、H 2 O 2 Carrying out third cleaning in the mixed solution of water to obtain a third processing substrate;
and sequentially soaking the third treated substrate in acetone, ethanol and water to perform fourth, fifth and sixth cleaning.
The invention provides the beta-phase gallium oxide film obtained by the preparation method in the technical scheme, wherein the average grain size obtained by the beta-phase gallium oxide film according to the orientation calculation 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 technical scheme is uniform in appearance and 10-1000 nm in thickness.
Drawings
FIG. 1 is a schematic diagram of an experimental procedure for preparing a beta-phase gallium oxide film or a zinc-doped gallium oxide film according to examples 1 to 3;
FIGS. 2 and 3 are SEM images of a beta-phase gallium oxide film prepared in example 1 of the present invention;
FIG. 4 is an SEM image of a zinc-doped gallium oxide film prepared in example 3 of the present invention;
FIG. 5 is an SEM image of a zinc-doped gallium oxide film prepared by example 4 of the present invention;
FIG. 6 is an SEM image of a zinc-doped gallium oxide film prepared in example 5 of the present invention;
fig. 7 is an XRD spectrum of the surface of the beta-phase gallium oxide thin 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 film prepared in examples 3-5 of the present invention;
FIG. 9 is a Raman spectrum of a beta-phase gallium oxide thin film prepared in example 1 of the present invention;
FIG. 10 is a Raman spectrum of a 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 thin film prepared in example 3 of the present invention;
FIG. 12 is a graph showing the UV-VIS absorption spectrum of the surface of a beta-phase gallium oxide thin film prepared in example 1 of the present invention;
FIG. 13 is a photoluminescence spectrum of a beta-phase gallium oxide film prepared in example 1 of the present invention;
FIG. 14 is a photoluminescence spectrum of a beta-phase gallium oxide film prepared in example 2 of the present invention;
fig. 15 is a photoluminescence spectrum of the zinc-doped gallium oxide thin film prepared in example 3 of the present invention.
Detailed Description
The invention firstly provides a preparation method of a beta-phase gallium oxide film, which comprises the following steps:
evaporating gallium oxide materials by adopting an electron beam, depositing the gallium oxide materials on the surface of a substrate to form a film, and obtaining a primary beta-phase gallium oxide film, wherein the temperature of the substrate is between room temperature and 400 ℃ when the electron beam evaporation 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 the preparation starting materials/components are commercially available products well known to those skilled in the art unless otherwise specified.
The gallium oxide material is particularly preferably gallium oxide bulk material.
The substrate is particularly preferably a monocrystalline silicon substrate.
Before the electron beam evaporation coating is carried out, the substrate is preferably pretreated by the method.
The pretreatment preferably comprises the steps of:
immersing the substrate in NH 3 、H 2 O 2 Carrying out first cleaning in a mixed solution of water to obtain a first processing substrate;
immersing the first substrate in HCl, H 2 O 2 Carrying out second cleaning in the mixed solution of water to obtain a second processing substrate;
immersing the second handle substrate in H 2 SO 4 、H 2 O 2 Carrying out third cleaning in the mixed solution of water to obtain a third treated substrate;
and sequentially immersing the third processing substrate in acetone, ethanol and water for fourth, fifth and sixth cleaning.
Immersing the substrate in NH 3 、H 2 O 2 And performing a first cleaning in the mixed solution of water to obtain a first processed substrate.
The NH 3 、H 2 O 2 NH in mixed solution with water 3 、H 2 O 2 And water are preferably in a molar ratio of 1.
The time of the first washing is preferably 4 hours.
The first cleaning is preferably a static cleaning.
The first cleaning water is preferably deionized water.
After obtaining a first processed substrate, the first substrate is immersed in HCl, H 2 O 2 And performing second cleaning in the mixed solution of water to obtain a second processed substrate.
The HCl, H 2 O 2 HCl and H in a mixed solution with water 2 O 2 And water are preferably in a molar ratio of 1.
The time of the second washing is preferably 4 hours.
The second cleaning is preferably a static cleaning.
The second cleaning water is preferably deionized water.
The present invention preferably removes dust and metal cations from the surface of the substrate by the first cleaning and the second cleaning.
After obtaining a second processed substrate, immersing the second processed substrate in H 2 SO 4 、H 2 O 2 And performing third cleaning in the mixed solution of water 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 carried out by immersing the second treated substrate in water and ultrasonically washing the substrate. The water is preferably deionized water, and the ultrasonic water washing time is preferably 25-35 min.
Said H 2 SO 4 、H 2 O 2 H in mixed solution with water 2 SO 4 、H 2 O 2 And water are preferably in a molar ratio of 4.
The time of the third washing is preferably 4 hours.
The third washing is preferably a standing washing.
The third cleaning water is preferably deionized water.
The invention preferably removes the organic impurities on the surface of the substrate by the third cleaning.
And after a third processing substrate is obtained, sequentially dipping the third processing substrate into a mixed solution of acetone, ethanol and deionized water for fourth cleaning, fifth cleaning and sixth cleaning.
The fourth cleaning is preferably carried out under the condition of ultrasonic waves, and the time of the fourth cleaning is preferably 5min.
The fifth cleaning is preferably performed under ultrasonic conditions, and the time of the fifth cleaning is preferably 5min.
The sixth cleaning is preferably performed under the condition of ultrasonic waves, and the time of the sixth cleaning is preferably 5min.
During 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 rack in an electron beam evaporation chamber.
The vacuum degree of the electron beam evaporation is preferably less than or equal to 5 × 10 -3 Pa。
When the electron beam evaporation coating is adopted, the invention preselects and starts the vacuum system, 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 less than or equal to 5 x 10 -3 Pa, the invention preferably performs pre-melting treatment on the gallium oxide material.
When the gallium oxide material is subjected to pre-melting treatment, the cleaning treatment is preferably performed on the electron beam evaporation vacuum chamber at the same time.
The specific implementation process of the invention for pre-melting the gallium oxide material is preferably as follows: closing the evaporation source baffle, opening a filament power supply of the electron gun, and pre-melting the gallium oxide material in the crucible.
The specific process of cleaning the electron beam steam chamber is preferably as follows: and opening an ion source, and cleaning residual gas in the electron beam evaporation chamber and residual impurities on the surface of the substrate.
After the gallium oxide material is melted, the evaporation source baffle is preferably opened, the automatic film coating program is started, and the molten gallium oxide material in the crucible is subjected to evaporation film coating.
When electron beam evaporation coating is adopted, the temperature of the substrate is between room temperature and 400 ℃, and preferably between room temperature and 100 ℃.
When the electron beam evaporation is adopted to coat the film on the surface of the substrate, the filament current of an electron gun is preferably 90 to 160mA, more preferably 90 to 155mA, and further preferably 90 to 150mA.
When electron beam evaporation coating is adopted, the deposition rate of the gallium oxide material on the surface of the substrate is preferably
More preferably is->
When electron beam evaporation coating is adopted, the distance between the gallium oxide material and the substrate is preferably 75-100 mm, more preferably 80-95 mm, and further preferably 82-93 mm.
When electron beam evaporation coating is adopted, the distance between the gallium oxide material and the filament of the electron gun is preferably 20-30 mm, more preferably 22-28 mm, and further 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 preferably sets the working parameters of the electron beam evaporation coating film reasonably, which is beneficial to obtaining the beta-phase gallium oxide film with high purity, good crystallinity and high stability.
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 the film is sampled to obtain the primary beta-phase gallium oxide film.
After the primary beta-phase gallium oxide film is obtained, the primary beta-phase gallium oxide film is subjected to high-temperature annealing treatment to obtain the beta-phase gallium oxide film.
The temperature of the high-temperature annealing treatment is preferably 900-1000 ℃, and more preferably 950-1000 ℃.
The heat preservation time of the high-temperature annealing treatment is preferably 0.5 to 2 hours, and more preferably 1 to 2 hours.
The rate of temperature increase 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 of the technical scheme, wherein the average grain size obtained by the beta-phase gallium oxide film through calculation 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, the method can also be used for doping other similar metals, and the method specifically comprises the following steps:
respectively evaporating gallium oxide materials and zinc particles by adopting electron beams, 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 stacked; 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 requirement of doping concentration, 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 the air to obtain the zinc-doped gallium oxide film.
According to the invention, gallium oxide materials 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 stacked; 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 requirement of doping concentration, 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 ℃.
Before the electron beam evaporation coating is carried out, the substrate is preferably subjected to pretreatment. The pretreatment is preferably the same as the pretreatment of the substrate in the preparation method of the beta-phase gallium oxide film, and details are not repeated here.
When the sandwich structure multilayer film is prepared by adopting electron beam evaporation coating, preferably, the gallium oxide material and the zinc particles are respectively arranged in a water-cooled crucible of an evaporation chamber, and the substrate is arranged on a sample rack in an electron beam evaporation chamber.
The invention adopts electron beams to evaporate gallium oxide materials, and when a first gallium oxide film is formed on the surface of a substrate, 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 started in advance, 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 less than or equal to 5X 10 -3 Pa, preferably pre-melting the gallium oxide material. 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 pre-melting treatment of the gallium oxide material is preferably as follows: the evaporation source baffle plate is closed,and turning on a filament power supply of the electron gun, and performing premelting treatment on the gallium oxide material in the crucible. The specific process of cleaning the electron beam steam chamber is preferably as follows: and opening an ion source, and cleaning residual gas in the electron beam evaporation chamber and residual impurities on the surface of the substrate. After the gallium oxide material is melted, preferably opening an evaporation source baffle, starting an automatic film coating program, and carrying out evaporation film coating 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 ℃, and preferably between room temperature and 100 ℃. When the electron beam evaporation is adopted to coat the film on the surface of the substrate, the filament current of an electron gun is preferably 90 to 160mA, more preferably 90 to 155mA, and further preferably 90 to 150mA. When electron beam evaporation coating is adopted, the deposition rate of the gallium oxide material on the surface of the substrate is preferably
More preferably
When electron beam evaporation coating is adopted, the distance between the gallium oxide material and the substrate is preferably 75-100 mm, more preferably 80-95 mm, and further preferably 82-93 mm. When electron beam evaporation coating is adopted, the distance between the gallium oxide material and the filament of the electron gun is preferably 20-30 mm, more preferably 22-28 mm, and further preferably 24-26 mm. And after the film coating is finished, preferably closing the evaporation source baffle, closing the electron gun, cooling along with the furnace, and cooling to room temperature to obtain a first gallium oxide film.
After the first gallium oxide film is obtained, zinc particles are evaporated by adopting an electron beam, and a zinc film is formed on the surface of the first gallium oxide film, wherein the thickness of the zinc film is 10nm, 25nm or 50nm or is correspondingly changed according to the doping concentration requirement.
In the invention, when the electron beam evaporation coating is adopted to prepare 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 started in advance, and the vacuum degree is pumped to be less than or equal to 5 multiplied by 10 - 3 Pa. When the electron beam is evaporatedThe preferred degree of hollowness is ≤ 5 × 10 -3 When Pa, the zinc particles are preferably subjected to a pre-melting treatment. When the zinc particles are subjected to the preliminary melting treatment, it is preferable to simultaneously perform the cleaning treatment on the electron beam evaporation vacuum chamber. The specific implementation process of performing pre-melting treatment on the zinc particles is preferably as follows: and closing the evaporation source baffle, and opening a filament power supply of the electron gun to pre-melt the zinc particles in the crucible. The specific process of cleaning the electron beam steam chamber is preferably as follows: and opening an ion source, and cleaning residual gas in the electron beam evaporation chamber and residual impurities on the surface of the substrate. After the zinc particles are melted, the evaporation source baffle is preferably opened, and the automatic coating program is started to carry out evaporation coating on the molten zinc particles in the crucible. When the electron beam evaporation coating is adopted, the temperature of the substrate is between room temperature and 400 ℃, and preferably between room temperature and 100 ℃. When the electron beam evaporation is adopted to coat the film on the surface of the substrate, the filament current of an electron gun is preferably 90 to 160mA, more preferably 90 to 155mA, and further preferably 90 to 150mA. When electron beam evaporation coating is adopted, the deposition rate of the zinc particles on the surface of the substrate is preferably
More preferably is->
When electron beam evaporation coating is adopted, the distance between the zinc particles and the substrate is preferably 75-100 mm, more preferably 80-95 mm, and further preferably 82-93 mm. When electron beam evaporation coating is adopted, the distance between the zinc particles and the filament of the electron gun is preferably 20-30 mm, more preferably 22-28 mm, and further preferably 24-26 mm. And after the film coating is finished, preferably closing the evaporation source baffle, closing the electron gun, cooling along with the furnace, and cooling to room temperature to obtain the zinc film.
After obtaining the zinc film, the invention continuously adopts the electron beam to evaporate the gallium oxide material, 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 started in advance, 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 less than or equal to 5 x 10 -3 Pa, preferably pre-melting the gallium oxide material. 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 pre-melting treatment of the gallium oxide material is preferably as follows: closing the evaporation source baffle, opening a filament power supply of the electron gun, and pre-melting the gallium oxide material in the crucible. The specific process of cleaning the electron beam steam chamber is preferably as follows: and opening an ion source, and cleaning residual gas in the electron beam evaporation chamber and residual impurities on the surface of the substrate. After the gallium oxide material is melted, preferably opening an evaporation source baffle, starting an automatic film coating program, and carrying out evaporation film coating on the melted gallium oxide material in the crucible. When electron beam evaporation coating is adopted, the temperature of the substrate is between room temperature and 400 ℃, and preferably between room temperature and 100 ℃. When the electron beam evaporation is adopted to coat the film on the surface of the substrate, the filament current of an electron gun is preferably 90-160 mA, more preferably 90-155 mA, and further preferably 90-150 mA. When electron beam evaporation coating is adopted, the deposition rate of the gallium oxide material on the surface of the substrate is preferably
More preferably is->
When electron beam evaporation coating is adopted, the distance between the gallium oxide material and the substrate is preferably 75-100 mm, more preferably 80-95 mm, and further preferably 82-93 mm. In the present invention, when the electron beam evaporation coating is adopted, the distance between the gallium oxide material and the filament of the electron gun is preferably 20 to 30mm, more preferably 22 to 28mm, and further 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 film is cooled to room temperature to obtain a second gallium oxide film. After the above steps are completed, the sandwich structure multilayer film is formed on the surface of the substrate.
After the multilayer film with the sandwich structure is obtained, the multilayer film with the sandwich structure is subjected to high-temperature annealing treatment in the air to obtain the zinc-doped gallium oxide film. The temperature of the high-temperature annealing treatment is preferably 900-1000 ℃, and more preferably 950-1000 ℃. The heat preservation time of the high-temperature annealing treatment is preferably 0.5 to 2 hours, and more preferably 1 to 2 hours. The rate of temperature increase 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 technical scheme is uniform in appearance and 10-1000 nm in thickness.
To further illustrate the present invention, the β -phase gallium oxide thin film and the doping method thereof provided by the present invention are described in detail below with reference to the drawings and examples, but they should not be construed as limiting the scope of the present invention.
Example 1
According to the experimental scheme shown in fig. 1: firstly, a single crystal silicon substrate is placed in NH under room temperature condition 3 、H 2 O 2 And deionized water (molar ratio 1 2 O 2 And deionized water (the molar ratio is 1.
Then, a single crystal silicon substrate is placed in H 2 SO 4 、H 2 O 2 And deionized water (the molar ratio is 4.
And finally, sequentially soaking the monocrystalline silicon substrate in acetone, ethanol and deionized water, and cleaning for 5min in an ultrasonic cleaner to finish the cleaning work of the substrate.
And placing the granular gallium oxide solid evaporation material into a water-cooled crucible of an evaporation chamber, and then placing the cleaned monocrystalline silicon substrate on a sample rack in the cavity.
Starting a vacuum system, and pumping the vacuum degree in the chamber 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 pre-melted. And simultaneously, opening the ion source, and cleaning residual gas in the electron beam evaporation cavity and impurities on the surface of the substrate.
Opening an evaporation source baffle, starting an automatic coating program, and carrying out evaporation coating on an evaporation material in a crucible, wherein in the process of electron beam evaporation coating, the temperature of a 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 is
The film deposition thickness was set to 300nm. And after the film coating is finished, immediately closing the evaporation source baffle, closing the electron gun, cooling along with the furnace to room temperature, 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 ℃ in air at a speed of 5 ℃/min, keeping the temperature for 30min, then closing the muffle furnace, and naturally cooling the sample in the air to obtain the beta-phase gallium oxide film.
Example 2
According to the experimental scheme shown in fig. 1: firstly, a single crystal silicon substrate is placed in NH under room temperature condition 3 、H 2 O 2 And deionized water (molar ratio 1 2 O 2 And deionized water (the molar ratio is 1.
Then, a single crystal silicon substrate is placed in H 2 SO 4 、H 2 O 2 And deionized water (molar ratio is 4And (5) continuously removing the organic impurities on the surface of the substrate for 35min.
And finally, sequentially soaking the monocrystalline silicon substrate in acetone, ethanol and deionized water, and cleaning for 5min in an ultrasonic cleaner to finish the cleaning work of the substrate.
And placing the granular gallium oxide solid evaporation material into a water-cooled crucible of an evaporation chamber, and then placing the cleaned monocrystalline silicon substrate on a sample rack in the cavity.
Starting a vacuum system, and pumping the vacuum degree in the chamber 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 pre-melted. And simultaneously, opening the ion source, and cleaning residual gas in the electron beam evaporation cavity and impurities on the surface of the substrate.
Opening an evaporation source baffle, starting an automatic coating program, and carrying out evaporation coating on an evaporation material in a crucible, wherein in the process of electron beam evaporation coating, the temperature of a 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 is
The film deposition thickness was set to 300nm. 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 primary gallium oxide film.
And (3) placing the primary gallium oxide film in a muffle furnace, heating to 950 ℃ at the speed of 5 ℃/min in the air, keeping the temperature for 90min, then closing the muffle furnace, and naturally cooling the sample in the air to obtain the beta-phase gallium oxide film.
Example 3
According to the experimental scheme shown in fig. 1: firstly, a monocrystalline silicon substrate is placed in NH under room temperature condition 3 、H 2 O 2 And deionized water (molar ratio 1 2 O 2 And deionized waterSoaking in the mixed solution (the molar ratio is 1.
Then, a single crystal silicon substrate is placed in H 2 SO 4 、H 2 O 2 And deionized water (the molar ratio is 4.
And finally, sequentially soaking the monocrystalline silicon substrate in acetone, ethanol and deionized water, and cleaning for 5min in an ultrasonic cleaner to finish the cleaning work of the substrate.
Granular gallium oxide and metal zinc solid evaporation materials are respectively placed in a water-cooled crucible of an evaporation chamber, and then the cleaned monocrystalline silicon substrate is placed on a sample rack in a cavity.
Starting a vacuum system, and pumping the vacuum degree in the chamber 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 material in the crucible are pre-melted respectively. And simultaneously, opening the ion source, and cleaning residual gas in the electron beam evaporation cavity and impurities on the surface of the substrate.
Opening an evaporation source baffle, starting an automatic coating program, 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 is
The film coating sequence and the thickness are Ga 2 O 3 100 nm、Zn 10nm、Ga 2 O 3 100 And (5) 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 the speed of 5 ℃/min in the air, keeping the temperature for 90min, then closing the muffle furnace, and naturally cooling the sample in the air to obtain the zinc-doped gallium oxide film.
Example 4
According to the experimental scheme shown in fig. 1: firstly, a single crystal silicon substrate is placed in NH under room temperature condition 3 、H 2 O 2 And deionized water (molar ratio 1 2 O 2 And deionized water (the molar ratio is 1.
Then, a single crystal silicon substrate is placed in H 2 SO 4 、H 2 O 2 And deionized water (the molar ratio is 4.
And finally, sequentially soaking the monocrystalline silicon substrate in acetone, ethanol and deionized water, and cleaning for 5min in an ultrasonic cleaner to finish the cleaning work of the substrate.
Granular gallium oxide and metal zinc solid evaporation materials are respectively placed in a water-cooled crucible of an evaporation chamber, and then the cleaned monocrystalline silicon substrate is placed on a sample rack in a cavity.
Starting a vacuum system, and pumping the vacuum degree in the chamber 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 material in the crucible are pre-melted respectively. And simultaneously, opening the ion source, and cleaning residual gas in the electron beam evaporation cavity and impurities on the surface of the substrate.
Opening an evaporation source baffle, starting an automatic coating program, 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 material and the filament of the electron gun is 25mm, and the deposition rate of the evaporation material obtained under the above conditions is
The film coating sequence and the thickness are Ga 2 O 3 100 nm、Zn 25nm、Ga 2 O 3 100 And (5) 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 ℃ in air at a speed of 5 ℃/min, keeping the temperature for 90min, then closing the muffle furnace, and naturally cooling the sample in the air to obtain the zinc-doped gallium oxide film.
Example 5
According to the experimental scheme shown in fig. 1: firstly, a single crystal silicon substrate is placed in NH under room temperature condition 3 、H 2 O 2 And deionized water (molar ratio 1 2 O 2 And deionized water (the molar ratio is 1.
Then, a single crystal silicon substrate is placed in H 2 SO 4 、H 2 O 2 And deionized water (the molar ratio is 4.
And finally, sequentially soaking the monocrystalline silicon substrate in acetone, ethanol and deionized water, and cleaning for 5min in an ultrasonic cleaner to finish the cleaning work of the substrate.
Granular gallium oxide and metal zinc solid evaporation materials are respectively placed in a water-cooled crucible of an evaporation chamber, and then the cleaned monocrystalline silicon substrate is placed on a sample rack in a cavity.
Starting a vacuum system, and pumping the vacuum degree in the chamber 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 material in the crucible are pre-melted respectively. And simultaneously, opening the ion source, and cleaning residual gas in the electron beam evaporation cavity and impurities on the surface of the substrate.
Opening an evaporation source baffle, starting an automatic coating program, 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 is
The coating sequence and the thickness are Ga 2 O 3 100 nm、Zn 50nm、Ga 2 O 3 100 And (5) nm. And after the film coating is finished, immediately closing the evaporation source baffle, closing the electron gun, cooling the electron gun to room temperature along with the furnace, and taking out the sample to obtain the multilayer film with the sandwich structure.
And (3) placing the sandwich structure multilayer film in a muffle furnace, heating to 950 ℃ at the speed of 5 ℃/min in the air, keeping the temperature for 90min, then closing the muffle furnace, and naturally cooling the sample in the air to obtain the zinc-doped gallium oxide film.
Comparative example 1
The preparation method is basically the same as that of example 1, except that: high temperature annealing treatment in air was not performed.
Test example
FIG. 1 is a flow chart of experiments on the preparation of beta-phase gallium oxide films according to examples 1-2 and the preparation of zinc-doped gallium oxide films according to examples 3-5;
FIGS. 2 and 3 are SEM images of a beta-phase gallium oxide film prepared in example 1 of the present invention;
FIG. 4 is an SEM image of a zinc-doped gallium oxide film prepared by example 3 of the present invention;
FIG. 5 is an SEM image of a zinc-doped gallium oxide film prepared in example 4 of the present invention;
FIG. 6 is an SEM image of a zinc-doped gallium oxide film prepared in example 5 of the present 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 7, in the embodiment 1 of the present invention, by reasonably setting the operating parameters of the electron beam evaporation, and simultaneously performing the high temperature annealing treatment on the primary gallium oxide thin film, and reasonably setting the operating parameters of the annealing treatment, the prepared beta-phase gallium oxide thin film has a higher preferred orientation and a larger grain size, and the grain boundary becomes clearer.
FIG. 8 is an XRD spectrum of the zinc-doped gallium oxide thin films prepared in examples 3-5 of the present invention;
as can be seen from fig. 8, when the plating order and thickness of the zinc-doped gallium oxide film in example 4 are 100nm gallium oxide, 25nm zinc, and 100nm gallium oxide, the crystalline quality of the zinc-doped gallium oxide film is the best;
FIG. 9 is a Raman spectrum of a beta-phase gallium oxide film prepared in example 1 of the present invention;
FIG. 10 is a Raman spectrum of a 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 thin film prepared in example 3 of the present invention.
Fig. 12 is a uv-vis absorption spectrum of the surface of the β -phase gallium oxide thin film prepared in example 1 of the present invention.
FIG. 13 is a photoluminescence spectrum of a beta-phase gallium oxide film prepared in example 1 of the present invention;
FIG. 14 is a photoluminescence spectrum of a beta-phase gallium oxide film prepared in example 2 of the present invention;
fig. 15 is a photoluminescence spectrum of a β -phase gallium oxide thin film prepared in example 3 of the present invention.
As can be seen from fig. 9 to fig. 11, the intensities of the blue peak (430 nm) and the green peak (513 nm) of the beta-phase gallium oxide thin film obtained by the preparation method provided by the invention are significantly increased, and the photoluminescence intensity and the optical transmittance are both greatly improved.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and all of the embodiments belong to the protection scope of the present invention.
Claims (10)
1. The preparation method of the beta-phase gallium oxide film is characterized by comprising the following steps:
evaporating gallium oxide materials by adopting an electron beam, depositing the gallium oxide materials on the surface of a substrate to form a film, and obtaining a primary beta-phase gallium oxide film, wherein the temperature of the substrate is between room temperature and 400 ℃ when the electron beam evaporation coating is adopted;
and carrying out high-temperature annealing treatment on the primary beta-phase gallium oxide film in the air to obtain the beta-phase gallium oxide film.
2. The preparation method of the zinc-doped gallium oxide film is characterized by comprising the following steps of:
respectively evaporating gallium oxide materials 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 stacked; 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 the air to obtain the zinc-doped gallium oxide film.
3. The method of claim 2, wherein the zinc film has a thickness of 10nm, 25nm, or 50nm.
4. The production method according to claim 1 or 2, wherein the temperature of the high-temperature annealing treatment is 900 to 1000 ℃, the holding time of the high-temperature annealing treatment is 0.5 to 2 hours, and the temperature increase rate from room temperature to the temperature of the high-temperature annealing treatment is 1 to 10 ℃/min.
5. The production method according to claim 1 or 2The method is characterized in that when electron beam evaporation coating is adopted, the deposition rate of the gallium oxide material on the surface of the substrate is
6. The method according to claim 1 or 2, wherein when the electron beam evaporation coating is adopted, the filament current of the electron gun is 90 to 160mA; the distance between the gallium oxide material and the filament of the electron gun is 20-30 mm.
7. The method according to claim 1 or 2, wherein the distance between the gallium oxide material and the substrate is 75-100 mm.
8. The production method according to claim 1 or 2, wherein the substrate is subjected to pretreatment before the electron beam evaporation coating; the pretreatment comprises the following steps:
immersing the substrate in NH 3 、H 2 O 2 Carrying out first cleaning in a mixed solution of water to obtain a first processing substrate;
immersing the first processing substrate in HCl and H 2 O 2 Carrying out second cleaning in the mixed solution of water to obtain a second processing substrate;
dipping the second handle substrate in H 2 SO 4 、H 2 O 2 Carrying out third cleaning in the mixed solution of water to obtain a third processing substrate;
and sequentially soaking the third treated substrate in acetone, ethanol and water to perform fourth, fifth and sixth cleaning.
9. The beta-phase gallium oxide thin film produced by the production method according to claim 1 and any one of claims 4 to 8, wherein the average crystal grain size of the beta-phase gallium oxide thin film calculated from 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.
10. The zinc-doped gallium oxide film prepared by the preparation method of any one of claims 2 to 8, wherein the zinc-doped gallium oxide film has uniform appearance and thickness of 10 to 1000nm.
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