CN119221117B - P-type gallium oxide material and preparation method and application thereof - Google Patents
P-type gallium oxide material and preparation method and application thereof Download PDFInfo
- Publication number
- CN119221117B CN119221117B CN202411775740.2A CN202411775740A CN119221117B CN 119221117 B CN119221117 B CN 119221117B CN 202411775740 A CN202411775740 A CN 202411775740A CN 119221117 B CN119221117 B CN 119221117B
- Authority
- CN
- China
- Prior art keywords
- gallium oxide
- oxide material
- single crystal
- epitaxial layer
- type
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/18—Epitaxial-layer growth characterised by the substrate
- C30B25/20—Epitaxial-layer growth characterised by the substrate the substrate being of the same materials as the epitaxial layer
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/04—Pattern deposit, e.g. by using masks
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/18—Epitaxial-layer growth characterised by the substrate
- C30B25/186—Epitaxial-layer growth characterised by the substrate being specially pre-treated by, e.g. chemical or physical means
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
- C30B33/02—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
- C30B33/04—After-treatment of single crystals or homogeneous polycrystalline material with defined structure using electric or magnetic fields or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
- C30B33/08—Etching
- C30B33/10—Etching in solutions or melts
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)
Abstract
本发明涉及晶体材料技术领域，具体公开了一种p型氧化镓材料及其制备方法和应用。本发明通过在氧化镓外延层中构建二价金属掺杂氧化镓纳米柱结构，降低空穴激活能，增加空穴浓度，成功实现了p型氧化镓材料的制备。利用本发明有效解决了通过多元素共掺的方式来实现β‑Ga2O3单晶p型掺杂时，容易出现的材料产生晶格畸变，在材料表面形成非晶层，降低材料质量，影响器件性能的问题，为氧化镓材料的制备提供了一种新的思路。
The present invention relates to the technical field of crystal materials, and specifically discloses a p-type gallium oxide material and a preparation method and application thereof. The present invention successfully realizes the preparation of a p-type gallium oxide material by constructing a divalent metal-doped gallium oxide nanocolumn structure in a gallium oxide epitaxial layer to reduce the hole activation energy and increase the hole concentration. The present invention effectively solves the problem that when p-type doping of β- Ga2O3 single crystal is achieved by co-doping with multiple elements, the material easily produces lattice distortion, forms an amorphous layer on the surface of the material, reduces the material quality, and affects the device performance, and provides a new idea for the preparation of gallium oxide materials.
Description
Technical Field
The invention relates to the technical field of crystal materials, and particularly discloses a p-type gallium oxide material, and a preparation method and application thereof.
Background
The gallium oxide single crystal has a plurality of phases, wherein the beta phase is the most stable phase, and the melting point of the beta phase is about 1820 ℃, which means that the beta-Ga 2O3 single crystal material can be grown by adopting a melt method, and compared with other ultra-wide band gap semiconductor materials, the beta-Ga 2O3 single crystal has the advantages of large size, low cost, high quality and the like. The beta-Ga 2O3 monocrystal has forbidden band width of 4.9eV, theoretical breakdown field strength up to 8MV/cm, and bargain figure of merit more than ten times that of SiC and GaN, so that the gallium oxide-based power device can theoretically have higher breakdown voltage and lower on-resistance, and has wide application prospect in the fields of rail transit, high-voltage transmission, new energy automobiles, aerospace and the like.
At present, the beta-Ga 2O3 monocrystal material has N type controllable through Sn, si and other element doping, but the p type doping has no breakthrough, which directly limits the development of gallium oxide-based power devices, so that the withstand voltage and the on-resistance of the gallium oxide-based power devices are far lower than theoretical values. The p-type doping difficulty of the beta-Ga 2O3 monocrystal material has two reasons, namely, the activation energy of doping elements is high, and the self-binding effect exists in gallium oxide. Because of the extremely strong electronegativity of oxygen ions, holes are more stable in forming small polarons at a single oxygen ion site than large-area free holes, the former being more than 500meV lower in energy than the latter, meaning that the energy required to obtain free holes is equal to the acceptor ionization energy plus 500meV. The above two factors cause that shallow acceptors are difficult to exist in gallium oxide single crystal materials, and p-type conduction cannot be realized, which is a fatal defect for the materials, and severely limits the application of the materials in the field of high-ultrahigh pressure.
Aiming at the problem of p-type doping of the beta-Ga 2O3 monocrystal, a multi-element co-doping mode is adopted at present to solve the problem, a large amount of N elements are firstly doped into the beta-Ga 2O3 monocrystal in an ion implantation mode, high-temperature annealing is carried out to replace oxygen elements, electronegativity is reduced, self-binding effect is weakened, divalent metal elements are then doped in an ion implantation mode, and high-temperature annealing is carried out to activate the divalent metal elements, so that free holes are obtained. However, the method for realizing p-type conduction of the beta-Ga 2O3 monocrystal by the multi-element co-doping method has the biggest problem that a large amount of N element and divalent metal element are required to be doped by an ion implantation method, the ion implantation method is characterized in that a high-energy ion beam is used for being injected into a target material, the ion beam collides with atoms or molecules in the material, so that the incident ion energy is gradually consumed and stays in the material, lattice distortion can be necessarily generated in the material, an amorphous layer is formed on the surface of the material, the quality of the material is seriously damaged, and the performance of a device is influenced. In addition, gallium oxide has a large forbidden bandwidth, and the activation energy of divalent metal elements is high, so that the doping concentration of divalent metal is high, but the effective hole concentration is low.
Based on the above, the development of a p-type gallium oxide material has important significance for the development of beta-Ga 2O3 single crystals.
Disclosure of Invention
Aiming at the problems that when p-type doping of beta-Ga 2O3 single crystals is realized in a multielement co-doping mode, lattice distortion is easily generated in a material, an amorphous layer is formed on the surface of the material, the quality of the material is reduced and the performance of a device is affected, the invention provides a p-type gallium oxide material, and a preparation method and application thereof. According to the invention, by constructing the divalent metal doped gallium oxide nano columnar structure, the activation energy of the effective cavity is reduced, the concentration of the effective cavity is increased, and the preparation of the p-type gallium oxide material is successfully realized.
In order to achieve the above purpose, the present invention provides the following technical solutions:
The first aspect of the invention provides a preparation method of a p-type gallium oxide material, which comprises the following steps:
sequentially growing a gallium oxide single crystal epitaxial layer and a mask layer on a gallium oxide substrate to obtain a pretreated gallium oxide material;
step two, stamping a porous graph on the surface of the pretreated gallium oxide material, and then etching to remove the gallium oxide single crystal epitaxial layer and the mask layer in the porous graph to obtain the gallium oxide material with porous surface;
Growing a divalent metal doped gallium oxide nano column in a surface pore channel of the gallium oxide material with the porous surface, and removing a mask to obtain a secondary treatment gallium oxide material;
And step four, activating the secondary treatment gallium oxide material to obtain a p-type gallium oxide material.
Because the gallium oxide monocrystal has a double-chain structure, two GaO 6 octahedrons are connected by a GaO 4 tetrahedron, the existence of the divalent metal doped gallium oxide nano-pillar structure is beneficial to space localization of holes, the self-binding effect in gallium oxide is weakened, and the holes can be conducted along the chain structure, so that the mobility of the gallium oxide monocrystal is improved. Meanwhile, the bivalent metal doped gallium oxide nano-pillar structure can reduce the forbidden bandwidth of gallium oxide, so that the activation energy of effective holes is reduced, the concentration of the effective holes is increased, and the preparation of p-type gallium oxide materials is successfully realized. More importantly, the invention does not need to realize p-type doping by ion implantation, but adopts an epitaxial growth mode, so that the lattice distortion of a p-type layer can be effectively reduced, the generation of a surface amorphous layer is effectively avoided, and the improvement of the performance of a device is facilitated. By utilizing the technical scheme of the invention, the problems that when p-type doping of beta-Ga 2O3 single crystal is realized in a multielement co-doping mode, lattice distortion is easily generated by a material, an amorphous layer is formed on the surface of the material, the quality of the material is reduced, and the performance of a device is influenced are effectively solved. The method for preparing the p-type gallium oxide material is simple, simple and convenient to operate and low in cost, and provides a new thought for preparing the p-type gallium oxide material.
Preferably, in the first step, the gallium oxide substrate is a gallium oxide single crystal substrate or a gallium oxide single crystal substrate with a Cu epitaxial layer loaded on the surface.
Preferably, in the first step, the growth method of the gallium oxide single crystal epitaxial layer is any one of a metal organic compound chemical vapor deposition method, a hydride vapor phase epitaxy method or a molecular beam epitaxy method.
Preferably, in the first step, the growth method of the mask layer is an atomic layer deposition method or a low-pressure chemical vapor deposition method.
Preferably, in the first step, the thickness of the gallium oxide single crystal epitaxial layer is 90nm-110nm.
Preferably, in the first step, the thickness of the mask layer is 15nm-25nm.
Preferably, in the second step, the area of the holes of the porous pattern is 70nm 2-2000nm2, and the density of the holes is 20 holes/mm 2 -100 holes/mm 2.
Preferably, in the second step, the etching adopts a phosphoric acid solution with the mass fraction of 80% -90% as etching liquid.
Preferably, in the third step, the growth method of the divalent metal doped gallium oxide nano-pillar is any one of a metal organic compound chemical vapor deposition method, a hydride vapor phase epitaxy method and a molecular beam epitaxy method.
Preferably, in the third step, the metal in the divalent metal doped gallium oxide nano-pillar is any one of Mg, zn, cu or Fe.
Preferably, in the third step, the doping concentration of the metal in the divalent metal doped gallium oxide nano-pillar is 1×10 19/cm 3-1×1021/cm 3.
Preferably, in the third step, the height of the divalent metal doped gallium oxide nano-pillar is 90nm-110nm.
Preferably, in the third step, the mask is removed by using a hydrofluoric acid solution with the mass fraction of 2% -3%.
Preferably, in the fourth step, the activation treatment is performed by high-temperature annealing, illumination or irradiation.
Further preferably, in the fourth step, the temperature of the high-temperature annealing is 980 ℃ to 1020 ℃, and the time of the high-temperature annealing is 25min to 40min.
The second aspect of the invention provides a p-type gallium oxide material, which is prepared by the preparation method of the p-type gallium oxide material.
The third aspect of the invention provides application of the p-type gallium oxide material in preparing a conductive material in the field of ultrahigh voltage.
In summary, the divalent metal doped gallium oxide nano columnar structure is constructed in the gallium oxide epitaxial layer, so that the activation energy of effective holes is reduced, the concentration of the effective holes is increased, and the preparation of the p-type gallium oxide material is successfully realized. By utilizing the technical scheme of the invention, the problems that when p-type doping of beta-Ga 2O3 single crystal is realized in a multi-element co-doping mode, lattice distortion is easily generated in a material, an amorphous layer is formed on the surface of the material, the quality of the material is reduced and the performance of a device is influenced are effectively solved, and a new thought is provided for preparing p-type gallium oxide material.
Drawings
Fig. 1 is a schematic cross-sectional structure of a p-type gallium oxide material obtained in embodiment 1, wherein 1 is a Cu-doped gallium oxide nano-pillar structure, 2 is an unintentionally doped gallium oxide epitaxial layer, and 3 is a gallium oxide single crystal substrate;
Fig. 2 is a graph showing the results of high-resolution X-ray diffraction testing of the p-type gallium oxide material epitaxial layer obtained in example 1.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a preparation method of a p-type gallium oxide material, which specifically comprises the following steps:
firstly, growing an unintentionally doped gallium oxide single crystal epitaxial layer with the thickness of 100nm on a gallium oxide single crystal substrate by adopting a molecular beam epitaxy method, wherein the vacuum of a molecular beam epitaxy growth chamber is as low as 6 multiplied by 10 -7 mbar, the evaporation temperature set by a Ga metal evaporation source is 950 ℃, the rapid flow intensity is 5 multiplied by 10 -6 mbar, the oxygen source is ozone, the flow rate is 1.5sccm, the growth temperature is 750 ℃, the growth speed of the unintentionally doped gallium oxide single crystal epitaxial layer is 50nm/h, and the growth is 2h;
step two, stamping a porous pattern on the surface of the pretreated gallium oxide material by adopting a nano stamping method, wherein the pore area is 235.5nm 2, the pore density is 70 pores/mm 2, removing an unintentionally doped gallium oxide epitaxial layer and a mask layer in a pore channel by adopting a phosphoric acid solution with the mass fraction of 85%, and exposing a gallium oxide monocrystal substrate at 150 ℃ to obtain the gallium oxide material with a porous surface;
growing Cu doped gallium oxide nano columns in surface pore channels of the gallium oxide material with porous surfaces by adopting a molecular beam epitaxy method, wherein the vacuum of a molecular beam epitaxy growth chamber is as low as 6×10 -9 mbar, the set evaporation temperature of a Ga metal evaporation source is 950 ℃, the rapid flow strength is 8×10 -8 mbar, the oxygen source is ozone, the flow rate is 0.5sccm, the growth temperature is 800 ℃, the growth speed of a divalent metal doped gallium oxide single crystal epitaxial layer is 20nm/h, the growth time is 5h, the heights of the divalent metal doped gallium oxide nano columns in round holes are flush with the unintended doped gallium oxide single crystal epitaxial layer, the set evaporation temperature of a Cu metal evaporation source is 1200 ℃, the rapid flow strength is 2×10 -9 mbar, the doping concentration is 5×10 19/cm 3, and then removing the mask by adopting a hydrofluoric acid solution with the mass fraction of 2% to obtain the secondary treatment gallium oxide material;
and fourthly, heating the secondary treatment gallium oxide material to 1000 ℃ for annealing treatment for 30min to obtain the p-type gallium oxide material.
Example 2
The embodiment provides a preparation method of a p-type gallium oxide material, which specifically comprises the following steps:
Firstly, growing an unintentionally doped gallium oxide single crystal epitaxial layer with the thickness of 110nm on a gallium oxide single crystal substrate by adopting a molecular beam epitaxy method, wherein the vacuum of a molecular beam epitaxy growth chamber is as low as 6 multiplied by 10 -7 mbar, the evaporation temperature set by a Ga metal evaporation source is 950 ℃, the rapid flow intensity is 5 multiplied by 10 -6 mbar, the oxygen source is ozone, the flow rate is 1.5sccm, the growth temperature is 750 ℃, the growth speed of the unintentionally doped gallium oxide single crystal epitaxial layer is 50nm/h, and the growth is 2h;
Step two, stamping a porous pattern on the surface of the pretreated gallium oxide material by adopting a nano stamping method, wherein the pore area is 1600nm 2, and the pore density is 50 pores/mm 2; removing the unintentionally doped gallium oxide epitaxial layer and the mask layer in the pore canal by adopting a phosphoric acid solution with the mass fraction of 90 percent at 150 ℃ to expose the gallium oxide monocrystalline substrate, thereby obtaining a gallium oxide material with porous surface;
Growing Zn-doped gallium oxide nano columns in surface pore channels of the surface porous gallium oxide material by adopting a molecular beam epitaxy method, wherein the vacuum of a molecular beam epitaxy growth chamber is as low as 6×10 -9 mbar, the set evaporation temperature of a Ga metal evaporation source is 950 ℃, the rapid flow strength is 8×10 -8 mbar, the oxygen source is ozone, the flow rate is 0.5sccm, the growth temperature is 800 ℃, the growth speed of a divalent metal-doped gallium oxide single crystal epitaxial layer is 20nm/h, the growth time is 5h, the heights of the divalent metal-doped gallium oxide nano columns in round holes are flush with the unintended doped gallium oxide single crystal epitaxial layer, the set evaporation temperature of a Zn metal evaporation source is 1200 ℃, the rapid flow strength is 2×10 -9 mbar, the doping concentration is 5×10 19/cm 3, and then removing the mask by adopting a hydrofluoric acid solution with the mass fraction of 2% to obtain the secondary treatment gallium oxide material;
And fourthly, heating the secondary treatment gallium oxide material to 1020 ℃ for annealing treatment for 30min to obtain the p-type gallium oxide material.
Example 3
The embodiment provides a preparation method of a p-type gallium oxide material, which specifically comprises the following steps:
Firstly, growing an unintentionally doped gallium oxide single crystal epitaxial layer with the thickness of 90nm on a gallium oxide single crystal substrate by adopting a molecular beam epitaxy method, wherein the vacuum of a molecular beam epitaxy growth chamber is as low as 6 multiplied by 10 -7 mbar, the evaporation temperature set by a Ga metal evaporation source is 950 ℃, the rapid flow intensity is 5 multiplied by 10 -6 mbar, the oxygen source is ozone, the flow rate is 1.5sccm, the growth temperature is 750 ℃, the growth speed of the unintentionally doped gallium oxide single crystal epitaxial layer is 50nm/h, and the growth is 2h;
Step two, stamping a porous pattern on the surface of the pretreated gallium oxide material by adopting a nano stamping method, wherein the pore area is 1962.5nm 2, the pore density is 20 pores/mm 2, and removing an unintentionally doped gallium oxide epitaxial layer and a mask layer in a pore channel by adopting a phosphoric acid solution with the mass fraction of 80 ℃ at 150 ℃ to expose a gallium oxide monocrystal substrate to obtain the gallium oxide material with a porous surface;
growing Mg-doped gallium oxide nano columns in surface pore channels of the gallium oxide material with porous surfaces by adopting a molecular beam epitaxy method, wherein the vacuum of a molecular beam epitaxy growth chamber is as low as 6×10 -9 mbar, the set evaporation temperature of a Ga metal evaporation source is 950 ℃, the rapid flow strength is 8×10 -8 mbar, the oxygen source is ozone, the flow rate is 0.5sccm, the growth temperature is 800 ℃, the growth speed of a divalent metal-doped gallium oxide single crystal epitaxial layer is 20nm/h, the growth time is 5h, the heights of the divalent metal-doped gallium oxide nano columns in round holes are flush with the unintended doped gallium oxide single crystal epitaxial layer, the set evaporation temperature of the Mg metal evaporation source is 1200 ℃, the rapid flow strength is 2×10 -9 mbar, the doping concentration is 5×10 19/cm 3, and then removing the mask by adopting a hydrofluoric acid solution with the mass fraction of 2% to obtain the secondary treatment gallium oxide material;
and fourthly, heating the secondary treatment gallium oxide material to 980 ℃ for annealing treatment for 30min to obtain the p-type gallium oxide material.
Example 4
The embodiment provides a preparation method of a p-type gallium oxide material, which specifically comprises the following steps:
Firstly, growing an unintentionally doped gallium oxide single crystal epitaxial layer with the thickness of 95nm on a gallium oxide single crystal substrate by adopting a molecular beam epitaxy method, wherein the vacuum of a molecular beam epitaxy growth chamber is as low as 6 multiplied by 10 -7 mbar, the evaporation temperature set by a Ga metal evaporation source is 950 ℃, the rapid flow intensity is 5 multiplied by 10 -6 mbar, the oxygen source is ozone, the flow rate is 1.5sccm, the growth temperature is 750 ℃, the growth speed of the unintentionally doped gallium oxide single crystal epitaxial layer is 50nm/h, and the growth is 2h;
Step two, stamping a porous pattern on the surface of the pretreated gallium oxide material by adopting a nano stamping method, wherein the pore area is 78.5nm 2, the pore density is 100 pores/mm 2, and removing an unintentionally doped gallium oxide epitaxial layer and a mask layer in a pore channel by adopting a phosphoric acid solution with the mass fraction of 85% at 150 ℃ to expose a gallium oxide single crystal substrate to obtain the gallium oxide material with a porous surface;
Growing Fe-doped gallium oxide nano columns in surface pore channels of the gallium oxide material with porous surfaces by adopting a molecular beam epitaxy method, wherein the vacuum of a molecular beam epitaxy growth chamber is as low as 6×10 -9 mbar, the set evaporation temperature of a Ga metal evaporation source is 950 ℃, the rapid flow strength is 8×10 -8 mbar, the oxygen source is ozone, the flow rate is 0.5sccm, the growth temperature is 800 ℃, the growth speed of a divalent metal-doped gallium oxide single crystal epitaxial layer is 20nm/h, the growth time is 5h, the heights of the divalent metal-doped gallium oxide nano columns in round holes are flush with the unintentionally-doped gallium oxide single crystal epitaxial layer, the set evaporation temperature of a Fe metal evaporation source is 1200 ℃, the rapid flow strength is 2×10 -9 mbar, the doping concentration is 5×10 19/cm 3, and then removing the mask by adopting a hydrofluoric acid solution with the mass fraction of 2% to obtain the secondary treatment gallium oxide material;
and fourthly, heating the secondary treatment gallium oxide material to 1010 ℃ for annealing treatment for 30min to obtain the p-type gallium oxide material.
Comparative example 1
The comparative example provides a preparation method of a p-type gallium oxide material, which is different from the embodiment 1 in that the second step is omitted, and a metal doped gallium oxide nano columnar structure is directly grown on the surface of a gallium oxide single crystal epitaxial layer, and the preparation method specifically comprises the following steps:
Firstly, growing an unintentionally doped gallium oxide single crystal epitaxial layer with the thickness of 100nm on a gallium oxide single crystal substrate by adopting a molecular beam epitaxy method, wherein the vacuum of a molecular beam epitaxy growth chamber is as low as 6 multiplied by 10 -7 mbar, the evaporation temperature set by a Ga metal evaporation source is 950 ℃, the rapid flow intensity is 5 multiplied by 10 -6 mbar, the oxygen source is ozone, the flow rate is 1.5sccm, the growth temperature is 750 ℃, and the growth speed of the unintentionally doped gallium oxide single crystal epitaxial layer is 50nm/h, and the growth time is 2h;
Secondly, growing Cu doped gallium oxide nano columns on the surface of the pretreated gallium oxide material by adopting a molecular beam epitaxy method, wherein the vacuum of a molecular beam epitaxy growth chamber is as low as 6×10 -9 mbar, the evaporation temperature set by a Ga metal evaporation source is 950 ℃, the rapid flow intensity is 8×10 -8 mbar, the oxygen source is ozone, the flow rate is 0.5sccm, the growth temperature is 800 ℃, the growth speed of a divalent metal doped gallium oxide single crystal epitaxial layer is 20nm/h, the growth time is 5h, the evaporation temperature set by a Cu metal evaporation source is 1200 ℃, the rapid flow intensity is 2×10 -9 mbar, the doping concentration is 5×10 19/cm 3, and the secondary treatment gallium oxide material is obtained;
And thirdly, heating the secondary treatment gallium oxide material to 1000 ℃ for annealing treatment for 30min to obtain the p-type gallium oxide material.
Comparative example 2
The comparative example provides a preparation method of gallium oxide material, which is different from the embodiment 1 in that a metal doped gallium oxide nano columnar structure is directly grown on a gallium oxide single crystal substrate, and specifically comprises the following steps:
Firstly, growing Cu doped gallium oxide nano columns on a gallium oxide single crystal substrate by adopting a molecular beam epitaxy method, wherein the vacuum of a molecular beam epitaxy growth chamber is as low as 6 multiplied by 10 -9 mbar, the evaporation temperature set by a Ga metal evaporation source is 950 ℃, the rapid flow intensity is 8 multiplied by 10 -8 mbar, the oxygen source is ozone, the flow rate is 0.5sccm, the growth temperature is 800 ℃, the growth speed of a divalent metal doped gallium oxide single crystal epitaxial layer is 20nm/h, and the growth time is 5h, so that the heights of the divalent metal doped gallium oxide nano columns in round holes are flush with the unintentionally doped gallium oxide single crystal epitaxial layer, the evaporation temperature set by the Cu metal evaporation source is 1200 ℃, the rapid flow intensity is2 multiplied by 10 -9 mbar, and the doping concentration is 5 multiplied by 10 19/cm 3, thereby obtaining a once treated gallium oxide material;
And step two, heating the secondary treatment gallium oxide material to 1000 ℃ for annealing treatment for 30min to obtain the p-type gallium oxide material.
In order to embody the technical effects of the invention, the electrical properties of the gallium oxide materials obtained in examples 1-4 and the gallium oxide materials obtained in comparative examples 1-2 are characterized by using an HL5500 type Hall effect tester, and specific data are shown in Table 1. The p-type gallium oxide material obtained in example 1 was also subjected to high-resolution X-ray diffraction test, and the result is shown in FIG. 2. As can be seen from fig. 2, the rocking curve half width of the p-type gallium oxide obtained in example 1 is less than 50 arcsec, which indicates that the epitaxial layer of the p-type gallium oxide has good crystallization quality.
TABLE 1 results of electrical property tests of gallium oxide materials obtained in examples 1-4 and comparative examples 1-2
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the invention.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202411775740.2A CN119221117B (en) | 2024-12-05 | 2024-12-05 | P-type gallium oxide material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202411775740.2A CN119221117B (en) | 2024-12-05 | 2024-12-05 | P-type gallium oxide material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN119221117A CN119221117A (en) | 2024-12-31 |
| CN119221117B true CN119221117B (en) | 2025-03-14 |
Family
ID=94069086
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202411775740.2A Active CN119221117B (en) | 2024-12-05 | 2024-12-05 | P-type gallium oxide material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN119221117B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116884829A (en) * | 2023-06-29 | 2023-10-13 | 湖北九峰山实验室 | A p-type gallium oxide film and its preparation method |
| CN117497590A (en) * | 2023-07-28 | 2024-02-02 | 山东省工业技术研究院 | MOSFET device based on p-type Ga2O3 and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118315413A (en) * | 2024-04-01 | 2024-07-09 | 西安电子科技大学 | Vertical structure Ga2O3 field effect transistor based on regrowth stable ion injection current aperture and preparation method thereof |
-
2024
- 2024-12-05 CN CN202411775740.2A patent/CN119221117B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116884829A (en) * | 2023-06-29 | 2023-10-13 | 湖北九峰山实验室 | A p-type gallium oxide film and its preparation method |
| CN117497590A (en) * | 2023-07-28 | 2024-02-02 | 山东省工业技术研究院 | MOSFET device based on p-type Ga2O3 and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN119221117A (en) | 2024-12-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4126332B2 (en) | Low resistance p-type single crystal zinc oxide and method for producing the same | |
| DE112007001605B4 (en) | P-type zinc oxide thin film and method of forming the same and light-emitting element | |
| CN103000535B (en) | A kind of preparation method of other grid graphene field effect transistor | |
| CN109411328B (en) | Preparation method of gallium oxide film with crystallization temperature reduced by doping iron | |
| CN102386246A (en) | P-type conductive zinc oxide film material and preparation method thereof | |
| CN105140283A (en) | Silicon carbide MOSEFTs (metal-oxide-semiconductor field-effect transistors) power device and manufacturing method therefor | |
| CN106847934A (en) | The gallium nitride PN junction and its manufacture method realized using fluorine ion injection | |
| CN101368288B (en) | A kind of manufacturing method of p-type ZnO thin film | |
| CN114477105B (en) | Two-dimensional BiCuSeO nanosheet and its preparation method, semiconductor device | |
| CN119221117B (en) | P-type gallium oxide material and preparation method and application thereof | |
| US20240410047A1 (en) | P-type gallium oxide film, and preparation method and application thereof | |
| US10388751B2 (en) | Semiconductor device and method for forming n-type conductive channel in diamond using heterojunction | |
| TWI698397B (en) | Method of purifying silicon carbide powder | |
| WO2022061484A1 (en) | Method for regulating defects and doping characteristics of wide-bandgap semiconductor material, and use thereof | |
| CN112233973B (en) | Method for regulating and controlling defects and doping characteristics of wide bandgap semiconductor material | |
| CN107369707B (en) | Heterojunction spin field effect transistor based on 4H-SiC substrate and manufacturing method thereof | |
| CN1317749C (en) | Three-dopant contained P-type zinc oxide film and method for making same | |
| KR20190087861A (en) | Semiconductor Structure for improvement of surface roughness and methods for production thereof | |
| Liu et al. | Optimization of high-quality gallium nitride thin films deposited on silicon substrates with an aluminum nitride buffer layer through radio-frequency magnetron sputtering | |
| CN113555422A (en) | Based on supercritical CO2Treated Ga2O3Metal oxide semiconductor field effect transistor and preparation method thereof | |
| CN111081762A (en) | Novel epitaxial structure of HEMT device | |
| CN1177335C (en) | Method for preparing AlN-based diluted magnetic semiconductor material by ion implantation | |
| CN103972105A (en) | MOSFET with SiGe channel and forming method of MOSFET | |
| JP5979625B2 (en) | Manufacturing method of semiconductor substrate | |
| CN118621440B (en) | Semiconductor material, semiconductor device and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |