CN112111711A - Gallium oxide nanorod, preparation method thereof and photoelectric detector - Google Patents
Gallium oxide nanorod, preparation method thereof and photoelectric detector Download PDFInfo
- Publication number
- CN112111711A CN112111711A CN202010868714.XA CN202010868714A CN112111711A CN 112111711 A CN112111711 A CN 112111711A CN 202010868714 A CN202010868714 A CN 202010868714A CN 112111711 A CN112111711 A CN 112111711A
- Authority
- CN
- China
- Prior art keywords
- gallium oxide
- cavity
- substrate
- preparation
- nanorod
- 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.)
- Granted
Links
- 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 110
- 229910001195 gallium oxide Inorganic materials 0.000 title claims abstract description 110
- 239000002073 nanorod Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 47
- 238000000151 deposition Methods 0.000 claims abstract description 33
- 230000008021 deposition Effects 0.000 claims abstract description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000001301 oxygen Substances 0.000 claims abstract description 27
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 23
- 239000013077 target material Substances 0.000 claims abstract description 17
- 239000011261 inert gas Substances 0.000 claims abstract description 14
- 238000004549 pulsed laser deposition Methods 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052594 sapphire Inorganic materials 0.000 claims description 3
- 239000010980 sapphire Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims 1
- 239000001307 helium Substances 0.000 claims 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims 1
- 229910052743 krypton Inorganic materials 0.000 claims 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052754 neon Inorganic materials 0.000 claims 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims 1
- 229910052704 radon Inorganic materials 0.000 claims 1
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 claims 1
- 229910052724 xenon Inorganic materials 0.000 claims 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims 1
- 239000002086 nanomaterial Substances 0.000 abstract description 17
- 239000013078 crystal Substances 0.000 abstract description 10
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 238000005844 autocatalytic reaction Methods 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 description 9
- 238000011160 research Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000002950 deficient Effects 0.000 description 5
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000000825 ultraviolet detection Methods 0.000 description 4
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 238000000608 laser ablation Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 229910005535 GaOx Inorganic materials 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011224 oxide ceramic Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- VZPPHXVFMVZRTE-UHFFFAOYSA-N [Kr]F Chemical compound [Kr]F VZPPHXVFMVZRTE-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910014032 c-Al2O3 Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000011900 installation process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/28—Vacuum evaporation by wave energy or particle radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G15/00—Compounds of gallium, indium or thallium
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0352—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
- H01L31/035209—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures
- H01L31/035227—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures the quantum structure being quantum wires, or nanorods
-
- 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
Abstract
The application relates to the technical field of semiconductor material preparation, and provides a gallium oxide nanorod, a preparation method thereof and a photoelectric detector. The preparation method provided by the application comprises the following steps: providing a substrate and a gallium oxide target material, and fixing the substrate and the gallium oxide target material in a cavity capable of being vacuumized; and introducing oxygen and inert gas into the cavity at the oxygen introduction speed of 1-10 sccm and the inert gas introduction speed of 3-30 sccm, keeping the pressure of the cavity at 0.11-2.0 Pa, and then starting a pulse laser to perform pulse laser deposition to form the gallium oxide nanorod. The method utilizes a pulse laser deposition technology, realizes autocatalysis of the gallium oxide nano structure and modulation of the crystal morphology by controlling the relative content of oxygen in the cavity and controlling the pressure of the cavity to be 0.11-2.0 Pa, and successfully prepares the high-quality gallium oxide nano rod. Compared with the prior art, the method has the advantages that the catalytic reaction by noble metal is not needed, the introduction of a heterogeneous seed crystal layer is not needed, the method is simple and optimized, the operation is controllable, and the large-scale production of the gallium oxide nanorod can be realized.
Description
Technical Field
The application belongs to the technical field of semiconductor material preparation, and particularly relates to a gallium oxide nanorod, a preparation method thereof and a photoelectric detector.
Background
Gallium oxide of the formula Ga2O3The material is an n-type wide bandgap oxide semiconductor material, and the bandgap is as high as 4.4-5.3 eV. The material has excellent thermal stability, chemical stability and higher breakdown voltage, is highly transparent in a visible light region, is extremely sensitive to ultraviolet light, and is an ideal photosensitive material for solar blind ultraviolet detection.
In the research of the gallium oxide-based photoelectric detection device, people adopt gallium oxide films prepared by various methods to prepare different types of ultraviolet detection devices, and research the influence of different crystalline states and synthesis processes on the responsivity, the light dark current and other performance indexes of the gallium oxide-based photoelectric detection device. The larger the specific surface area of the nano-structure material is, the stronger the scattering capability is, and the corresponding ultraviolet detection device can obtain higher light responsivity, so that the growth of the gallium oxide nano-rod has very important research significance for the field of ultraviolet detection. However, since the growth of gallium oxide nanorods is very difficult, the growth temperature is generally high, and the use of a noble metal catalyst or a heterogeneous seed layer brings cost and manufacturing process challenges, the research on gallium oxide nanostructures in the existing research is very limited, which hinders the application of gallium oxide nanostructures in the field of photodetector devices.
Disclosure of Invention
The application aims to provide a preparation method of a gallium oxide nanorod and the gallium oxide nanorod prepared by the preparation method, and aims to solve the problem of a novel preparation method of the gallium oxide nanorod.
Further, the application also provides a photoelectric detector.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
the application provides a preparation method of gallium oxide nanorods, which comprises the following steps:
providing a substrate and a gallium oxide target material, and fixing the substrate and the gallium oxide target material in a cavity capable of being vacuumized;
and introducing oxygen and inert gas into the cavity at the oxygen introduction speed of 1-10 sccm and the inert gas introduction speed of 3-30 sccm, keeping the pressure of the cavity at 0.11-2.0 Pa, and then starting a pulse laser to perform pulse laser deposition to form the gallium oxide nanorod.
According to the preparation method of the gallium oxide nanorod, the pulsed laser deposition technology is utilized, the relative content of oxygen in the cavity is controlled, and the pressure of the cavity is controlled to be 0.11-2.0 Pa, so that autocatalysis of the gallium oxide nanostructure and modulation of the crystal morphology are realized, and the high-quality gallium oxide nanorod is successfully prepared. Compared with the prior art, the method has the advantages that the catalytic reaction by noble metal is not needed, the introduction of a heterogeneous seed crystal layer is not needed, the method is simple and optimized, the operation is controllable, and the large-scale production of the gallium oxide nanorod can be realized.
Further, the application also provides a gallium oxide nanorod prepared by the preparation method.
The gallium oxide nanorod provided by the application has an obvious rod-like structure, is high in crystallinity, large in specific surface area and strong in light scattering capacity, and can be applied to preparation of a photoelectric detection device with good light responsivity.
Still further, the present application also provides a photodetector device comprising a photosensitive material comprising the above-described gallium oxide nanorods.
The photosensitive material of the photoelectric detector provided by the application comprises the gallium oxide nanorod, and the photoelectric detector has high light responsivity.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is an SEM image of gallium oxide nanomaterials prepared in an oxygen deficient environment, wherein the oxygen pressures are (a) 5X 10- 1Pa,(b)5×10-2Pa,(c)5×10-3Pa,(d)5×10-4Pa;
FIG. 2 is a schematic diagram of the growth process of gallium oxide nanorods, wherein 1-3 are deposition processes of gallium oxide, and 4-6 are processes of forming alloy droplets and supersaturation precipitation rod formation in an oxygen-deficient state;
FIG. 3 is an SEM image of gallium oxide nanomaterials prepared at different chamber pressures during deposition;
FIG. 4 is an XRD spectrum of gallium oxide nanomaterials prepared at different chamber pressures during deposition.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
It should be understood that, in various embodiments of the present application, the sequence number of each step does not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not limit the implementation process of the embodiments of the present application.
During the previous research on the preparation of gallium oxide thin films by pulsed laser deposition (abbreviated as PLD), the applicant has creatively found that, in an oxygen-deficient environment, when the oxygen pressure in the chamber is reduced to 5X 10-4~5×10-1The surface morphology of the gallium oxide film formed under Pa shows obvious condensation nucleation, as shown in FIG. 1, wherein the oxygen pressure is (a) 5X 10-1Pa,(b)5×10-2Pa,(c)5×10-3Pa,(d)5×10-4Pa, and the thicknesses of the gallium oxide thin films thus formed were (a)204.6nm, (b)157.8nm, (c)153.6nm, and (d)105.9nm, respectively. Based on this finding, the present applicant has guessed this phenomenon or facilitated the preparation of gallium oxide nanorods, and has searched for a synthesis process of gallium oxide nanorods, thereby providing a technical solution for preparing gallium oxide nanorods as follows.
In the present specification, the "oxygen-deficient atmosphere" refers to an oxygen-containing atmosphere in which the oxygen content in the chamber is lower than that in the case of producing a gallium oxide thin film by a pulsed laser deposition technique.
A preparation method of gallium oxide nanorods comprises the following steps:
s01, providing a substrate and a gallium oxide target material, and fixing the substrate and the gallium oxide target material in a vacuum chamber;
s02, introducing oxygen and inert gas into the cavity, wherein the introduction speed of the oxygen is 1-10 sccm, the introduction speed of the inert gas is 3-30 sccm, the pressure of the cavity is kept at 0.11-2.0 Pa, and then starting a pulse laser to perform pulse laser deposition to form the gallium oxide nanorod.
The preparation method of the gallium oxide nanorod provided by the embodiment of the application utilizes a pulse laser deposition technology, realizes autocatalysis of the gallium oxide nanostructure and modulation of the crystal morphology by controlling the relative content of oxygen in the cavity and the pressure of the cavity to be 0.11-2.0 Pa, and successfully prepares the high-quality gallium oxide nanorod. Compared with the prior art, the method has the advantages that the catalytic reaction by noble metal is not needed, the introduction of a heterogeneous seed crystal layer is not needed, the method is simple and optimized, the operation is controllable, and the large-scale production of the gallium oxide nanorod can be realized.
Specifically, in step S01, the substrate is used as a carrier for growing the gallium oxide nanorods, and may be selected as a conventional substrate in the art, and in some embodiments, the substrate is selected as a sapphire substrate. The sapphire substrate is well matched with gallium oxide in the aspects of lattice matching, preferred orientation and the like in the epitaxial growth process of materials, and is favorable for forming high-quality gallium oxide nanorods. Further, the substrate should be pretreated to serve as a surface-cleaned gallium oxide nanomaterial growth substrate, including but not limited to cleaning the substrate surface and removing the oxidation layer.
The gallium oxide target material is used as a raw material for forming the gallium oxide nanorod, and can be selected as a commercially available gallium oxide ceramic target material, and in some embodiments, the purity of the gallium oxide target material is 99.99% -99.999%, so that the gallium oxide nanorod with high purity and high quality can be prepared.
The substrate and the gallium oxide target material are installed by being fixed in a vacuum-pumping cavity. The cavity structures of different types of pulse laser deposition equipment are different to a greater or lesser extent, and the specific positions of the substrate and the gallium oxide target can be adjusted according to the types of the equipment in the actual installation process. In some embodiments, the relative distance between the substrate fixed in the cavity and the gallium oxide target is 50-60 mm, and the control of the growth uniformity of the gallium oxide nanowires is facilitated and the synthesis quality of the gallium oxide nanorods is improved by adjusting the relative distance between the substrate and the gallium oxide target within the range. Further, a gallium oxide target in the cavity is located at an upstream position of the substrate to facilitate deposition of ablated particles of the gallium oxide target on the substrate to form gallium oxide nanorods.
And step S02, introducing oxygen and inert gas into the cavity, wherein the introduction speed of the oxygen is 1-10 sccm, the introduction speed of the inert gas is 3-30 sccm, and the pressure of the cavity is kept at 0.11-2.0 Pa to form the gallium oxide nanorod instead of other gallium oxide nanostructures.
Oxygen and inert gas are introduced into the cavity at a specific speed, and the deposition pressure is kept at 0.11-2.0 Pa, so that on one hand, the gallium oxide nano material is ensured to grow in an obvious rod-shaped structure orientation manner to synthesize a gallium oxide nano rod; on the other hand, the epitaxial growth rate of the gallium oxide nano material is not ensured to be too high, and the rodlike growth of gallium oxide is promoted, so that the high-quality gallium oxide nano rod is formed. Experimental tests show that the gallium oxide nano material deposited under 0.11-2.0 Pa has obvious rod-shaped structure oriented growth and good crystallization quality.
The growth process of the gallium oxide nanorod of the embodiment of the application conforms to a VLS mode, as shown in FIG. 2. Specifically, in a cavity of pulsed laser deposition equipment, under the conditions of oxygen-deficient environment and deposition pressure of 0.11-2.0 Pa, pulsed laser ablation gallium oxide target excites gaseous Ga and O atoms, and the Ga and O atoms reach a substrate to form Ga2O3Layer of excess Ga in Ga2O3The surfaces of the layers are condensed into Ga droplets, and the Ga droplets adsorb O atoms to combine into liquid GaOxThereby forming a plurality of Ga and GaOxThen, the alloy droplets adsorb Ga and O atoms continuously to form a supersaturated state, and Ga is continuously precipitated2O3Crystals, due to the induction and catalytic action of the alloy droplets, gradually forming Ga2O3And (4) nanorods.
In the step of starting the pulse laser to carry out pulse laser deposition, the laser energy and the pulse frequency influence the deposition rate, the laser deposition time influences the thickness of the epitaxial layer of the gallium oxide nanorod, and the synthesis quality of the gallium oxide nanorod can be further optimized by adjusting the laser energy, the pulse frequency and the deposition time.
In some embodiments, in the step of starting the pulsed laser for pulsed laser deposition, the laser energy is controlled to be 250-300 mJ, and the pulse frequency is controlled to be 2-3 Hz. The laser energy is the maximum stable output energy which can be reached by a pulse laser, the pulse frequency can ensure the continuity of the maximum stable error input energy, when the pulse frequency is too large, the laser energy output is unstable, the laser energy is attenuated, and when the pulse frequency is too small, the crystal growth speed and the crystallization quality are influenced; when the laser energy is too high, the size of particles sputtered in the deposition process is too large, and the uniformity and crystallinity of the material are affected; when the laser energy is too low, the number of particles reaching the substrate surface during deposition is too low and the deposition rate of the material is reduced.
In some embodiments, the pulsed laser deposition time is 0.5-2 hours. The short deposition time can lead to the unobvious rod-shaped epitaxial growth, and the long deposition time can lead to the phenomena of lodging, film aggregation or crystal quality reduction of a rod-shaped structure and the like.
The choice of pulsed laser can be selected as is conventional in the art, such as in some embodiments a krypton fluoride excimer laser (also known as a KrF excimer pulsed laser).
Further, the step of introducing oxygen and inert gas into the chamber further comprises: vacuumizing the cavity to a background vacuum degree, and then heating the substrate to a working temperature; wherein the background vacuum degree is less than or equal to 6 × 10-5(ii) a The working temperature is 550-650 ℃. The lower the background vacuum degree is, the higher the vacuum degree in the cavity is, the less impurity gas in the cavity is, the more favorable the preparation of the gallium oxide nanorod with high purity and small error is, meanwhile, the deposition rate and the quality of the gallium oxide nanorod are influenced by the working temperature, if the working temperature is higher than 650 ℃, the thermal motion of the material deposited on the surface of the substrate can be accelerated, so that the particles have higher kinetic energy to migrate on the surface of the substrate, and further the particles can cross a diffusion barrier on the surface of the substrate more easily to display a film-shaped growth mode; if the working temperature is less than 550 ℃, the temperature will be reducedSo that the thermal motion in the growth process of the material can not obtain enough energy, and the crystallinity of the material is reduced. The embodiment of the application is favorable for synthesizing the high-quality gallium oxide nanorod by adjusting the background vacuum degree and the working temperature within the size range. Preferably, the background vacuum is 1X 10-6~6×10-5When the background vacuum degree is controlled to be in the range, the preparation of the gallium oxide nano-rod with high quality is facilitated. Preferably, the operating temperature is 600 ℃.
The steps of evacuating the chamber to a background vacuum level and heating the substrate to an operating temperature may be according to conventional techniques in the art.
Furthermore, the step of turning on the pulsed laser for pulsed laser deposition further comprises: the gallium oxide target is pretreated to remove pollutants and an oxide layer on the surface of the target, ensure the cleanness and purity of reactants for deposition and ensure that a substrate can excite a stable and uniform purple plasma plume during laser ablation. In some embodiments, the substrate is blocked by a baffle plate under the deposition pressure of 0.11-2.0 Pa, the KrF excimer laser (laser energy 300mJ, pulse frequency 2Hz) is turned on, and the target material is ablated and melted for 15 min.
In addition, after the step of pulse laser deposition is finished, the pulse laser is turned off, and the temperature in the cavity is naturally cooled to be below 100 ℃, so that the gallium oxide nanorod product can be conveniently taken out.
Based on the technical scheme, the embodiment of the application also provides a photosensitive material and a photoelectric detector.
Correspondingly, the gallium oxide nanorod is prepared by the preparation method.
The gallium oxide nanorod provided by the embodiment of the application has an obvious rod-like structure, is high in crystallinity, large in specific surface area and strong in light scattering capacity, and can be applied to preparation of a photoelectric detection device with good light responsivity.
Correspondingly, the photoelectric detector comprises a photosensitive material, and the photosensitive material comprises the gallium oxide nanorod.
The photosensitive material of the photoelectric detector provided by the embodiment of the application comprises the gallium oxide nanorod, and the photoelectric detector has high light responsivity.
The practice of the present invention is illustrated by the following examples.
Example 1
The embodiment prepares the gallium oxide nanorod, and the preparation method specifically comprises the following steps:
(1) c-Al is singly polished by adopting the traditional method2O3(0001) Cleaning and removing an oxidation layer on the surface of the substrate to obtain a substrate with a clean surface and used as a material growth substrate, and placing and fixing the substrate in a cavity for vacuum deposition;
(2) fixing a pre-pressed gallium oxide ceramic target material (with the purity of 99.999%) in a cavity, and closing a cavity door after adjusting the distance between the target material and a substrate to be 60 mm;
(3) opening the mechanical pump to vacuumize the cavity, starting the molecular pump when the pressure in the cavity reaches below 0.1Pa, and pumping the pressure in the cavity to 6 × 10-5Pa;
(4) Opening a heating source to heat the substrate until the temperature of the substrate reaches 600 ℃ and keeping the temperature;
(5) closing the molecular pump, opening the vent valve, and introducing the mixed gas of oxygen and argon, O2The introducing speed of the gas inlet pipe is 10sccm, the introducing speed of Ar is 30sccm, and the pressure in the cavity is kept between 1 Pa;
(6) on the basis of the step (5), a baffle is used for blocking the substrate, a KrF excimer laser (laser energy is 300mJ, pulse frequency is 2Hz) is opened to ablate and melt the target for 15min to remove pollutants and an oxide layer on the surface of the target, the cleanness and high purity of deposits are ensured, and the laser ablation substrate is ensured to excite a stable and uniform purple plasma plume;
(7) opening a baffle plate for blocking the substrate on the basis of the step (6), and removing the substrate on the c-Al2O3(0001) Performing pulsed laser deposition on the surface of the substrate, wherein the deposition time is 60 min;
(8) and after the deposition is finished, closing the laser and the deposition system equipment, and taking out the sample when the temperature in the cavity is naturally reduced to be below 100 ℃ to obtain the gallium oxide nanorod.
The preparation methods of the gallium oxide nanomaterials provided in examples 2-3 and comparative example 1 are substantially the same as those of example 1, except that: the pressure of the chamber in step (5) is different, as shown in table 1.
TABLE 1
Example 2 | Example 3 | Comparative example 1 | |
Pressure of the chamber | 0.11Pa | 2.0Pa | 4.0Pa |
The gallium oxide nano materials prepared in examples 1 to 3 and comparative example 1 were taken, and the material morphology thereof was observed by a Scanning Electron Microscope (SEM) and the sample information of the gallium oxide nano materials was analyzed by an X-ray diffractometer, respectively.
As shown in FIG. 3, when the pressure of the chamber during deposition is 0.11 to 2.0Pa, the sample shows a significant quadrangular prism-shaped gallium oxide nanorod structure, the density of the nanorods gradually decreases with the increase of the gas pressure, and when the pressure of the chamber during deposition reaches 4.0Pa, as shown in FIG. 3(d), the surface of the sample is flat, which indicates that no significant rod-shaped structure oriented growth exists under the condition, which indicates that the optimal deposition pressure for forming gallium oxide nanorods in the method provided by the embodiment is 0.11 to 2.0 Pa.
As shown in figure 4 of the drawings,when the pressure of the cavity is 0.11-2.0 Pa during deposition, monoclinic beta-Ga is observed2O3Is/are as followsThe diffraction peak of the crystal face family shows that the crystallization quality of the nanorod is highest under the atmospheric pressure condition by the fact that the diffraction peak intensity is strongest and the full width at half maximum when the pressure of a cavity is 1.0Pa during deposition. When the pressure of the cavity reaches 4.0Pa during deposition, the beta-Ga2O3The diffraction peak of (a) disappears, and the shape analysis of SEM shows that amorphous gallium oxide is generated under the atmospheric pressure.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. The preparation method of the gallium oxide nanorod is characterized by comprising the following steps of:
providing a substrate and a gallium oxide target material, and fixing the substrate and the gallium oxide target material in a cavity capable of being vacuumized;
and introducing oxygen and inert gas into the cavity at the oxygen introduction speed of 1-10 sccm and the inert gas introduction speed of 3-30 sccm, keeping the pressure of the cavity at 0.11-2.0 Pa, and then starting a pulse laser to perform pulse laser deposition to form the gallium oxide nanorod.
2. The method of claim 1, wherein the step of introducing oxygen and an inert gas into the chamber is preceded by the step of: vacuumizing the cavity to a background vacuum degree, and then heating the substrate to a working temperature;
wherein the background vacuum is less than or equal to 6 x 10-5;
The working temperature is 550-650 ℃.
3. The method according to claim 1, wherein the step of starting the pulsed laser for pulsed laser deposition is performed by controlling the laser energy to be 250 to 300mJ and the pulse frequency to be 2 to 3 Hz.
4. The method according to claim 1, wherein the pulsed laser deposition time is 0.5 to 2 hours.
5. The method according to claim 1, wherein the substrate fixed in the chamber and the gallium oxide target material are at a relative distance of 50 to 60 mm.
6. The method according to any one of claims 1 to 5, wherein the inert gas is at least one selected from the group consisting of argon, helium, neon, krypton, xenon, and radon.
7. The method according to any one of claims 1 to 5, wherein the purity of the gallium oxide target material is 99.99% to 99.999%.
8. The method of any one of claims 1 to 5, wherein the substrate is selected from a sapphire substrate.
9. Gallium oxide nanorods, characterized in that they are obtained by the preparation process according to any one of claims 1 to 8.
10. A photodetector device comprising a photosensitive material, said photosensitive material comprising gallium oxide nanorods according to claim 9.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010868714.XA CN112111711B (en) | 2020-08-25 | 2020-08-25 | Gallium oxide nanorod, preparation method thereof and photoelectric detector |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010868714.XA CN112111711B (en) | 2020-08-25 | 2020-08-25 | Gallium oxide nanorod, preparation method thereof and photoelectric detector |
Publications (2)
Publication Number | Publication Date |
---|---|
CN112111711A true CN112111711A (en) | 2020-12-22 |
CN112111711B CN112111711B (en) | 2022-10-04 |
Family
ID=73805552
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010868714.XA Active CN112111711B (en) | 2020-08-25 | 2020-08-25 | Gallium oxide nanorod, preparation method thereof and photoelectric detector |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112111711B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114990505A (en) * | 2022-04-08 | 2022-09-02 | 集美大学 | Gallium oxide film based on optical waveguide effect and preparation method thereof |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080292808A1 (en) * | 2007-05-25 | 2008-11-27 | Imra America, Inc. | Method of producing compound nanorods and thin films |
CN101981678A (en) * | 2008-03-27 | 2011-02-23 | Imra美国公司 | A method for fabricating thin films |
CN103233202A (en) * | 2013-02-19 | 2013-08-07 | 广州金升阳科技有限公司 | Method for preparing CuInS2 nanorods by pulsed laser deposition |
CN104593733A (en) * | 2015-02-13 | 2015-05-06 | 哈尔滨工业大学 | Pulsed laser deposition preparation method for copper-doped zinc oxide nanorod |
US20180222766A1 (en) * | 2014-08-26 | 2018-08-09 | King Abdullah University Of Science And Technology | Synthesis of vertically aligned metal oxide nanostructures |
CN108821331A (en) * | 2018-09-06 | 2018-11-16 | 桂林电子科技大学 | A kind of preparation method and product of gallium oxide nanometer rods |
-
2020
- 2020-08-25 CN CN202010868714.XA patent/CN112111711B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080292808A1 (en) * | 2007-05-25 | 2008-11-27 | Imra America, Inc. | Method of producing compound nanorods and thin films |
CN101981678A (en) * | 2008-03-27 | 2011-02-23 | Imra美国公司 | A method for fabricating thin films |
CN103233202A (en) * | 2013-02-19 | 2013-08-07 | 广州金升阳科技有限公司 | Method for preparing CuInS2 nanorods by pulsed laser deposition |
US20180222766A1 (en) * | 2014-08-26 | 2018-08-09 | King Abdullah University Of Science And Technology | Synthesis of vertically aligned metal oxide nanostructures |
CN104593733A (en) * | 2015-02-13 | 2015-05-06 | 哈尔滨工业大学 | Pulsed laser deposition preparation method for copper-doped zinc oxide nanorod |
CN108821331A (en) * | 2018-09-06 | 2018-11-16 | 桂林电子科技大学 | A kind of preparation method and product of gallium oxide nanometer rods |
Non-Patent Citations (1)
Title |
---|
HONG YANG 等: ""Surface/structural characteristics and band alignments of thin Ga2O3 films grown on sapphire by pulse laser deposition"", 《APPLIED SURFACE SCIENCE》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114990505A (en) * | 2022-04-08 | 2022-09-02 | 集美大学 | Gallium oxide film based on optical waveguide effect and preparation method thereof |
CN114990505B (en) * | 2022-04-08 | 2023-08-22 | 集美大学 | Gallium oxide film based on optical waveguide effect and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN112111711B (en) | 2022-10-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Gomez et al. | Gallium-doped ZnO thin films deposited by chemical spray | |
CN112647130B (en) | Method for growing gallium oxide film by low-pressure chemical vapor deposition | |
CN112086344B (en) | Preparation method of aluminum gallium oxide/gallium oxide heterojunction film and application of aluminum gallium oxide/gallium oxide heterojunction film in vacuum ultraviolet detection | |
JP3531865B2 (en) | Ultra-flat transparent conductive film and manufacturing method thereof | |
CN112111711B (en) | Gallium oxide nanorod, preparation method thereof and photoelectric detector | |
Kumar et al. | Structural and optical properties of nanostructured Cu2O thin films for optoelectronic devices | |
Yusof et al. | Fabrication and characterization of copper doped zinc oxide by using Co-sputtering technique | |
CN112456452B (en) | Preparation method of germanium diselenide nano material | |
CN109706434B (en) | Solid solution nanowire and preparation method and application thereof | |
CN112103177A (en) | Preparation method of amorphous indium-aluminum-tin oxide semiconductor film | |
CN114657637B (en) | Zinc gallate thin film and preparation method thereof, ultraviolet detector and preparation method thereof | |
Hojabri et al. | Influence of Thermal Oxidation Temperatures on the Structural and Morphological Properties of MoO_3 Thin Films | |
Yu et al. | ZnO thin films produced by the RF magnetron sputtering | |
Ceylan et al. | Formation of ST12 phase Ge nanoparticles in ZnO thin films | |
US11982017B2 (en) | Transparent conductive oxide thin film and use thereof | |
CN112695380A (en) | Preparation method and application of novel transparent conductive oxide film | |
CN110993504A (en) | Ga based on SiC substrate2O3Preparation method of film and Ga based on SiC substrate2O3Film(s) | |
KR20070119939A (en) | 3d structural nano devices having zinc oxide type nano wires and devices using it | |
GÖNÜLLÜ | The Effect of Annealing Technique on ZnO Film Properties | |
CN115029683B (en) | Through low bond energy N 2 Preparation of high-quality steady-state beta-Ga by O thermal oxidation 2 O 3 Method for producing thin films | |
KR100594383B1 (en) | Method of manufacturing zinc oxide thin film doped with aluminum | |
Choi et al. | Formation Mechanism and Properties of Foam-Structured ZnO Films Prepared Using Catalyst-Free Carbothermal Method | |
CN110981215B (en) | Method for improving thermal stability of aluminum-doped zinc oxide conductive glass | |
CN115376886B (en) | Nitrogen-doped p-type gallium oxide film and preparation method and application thereof | |
Jin et al. | Preparation, structure and photoluminescence properties of SiO2–coated ZnS nanowires |
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 |