CN109607596B - Nano composite material based on gallium oxide/cuprous oxide structure and preparation method thereof - Google Patents

Nano composite material based on gallium oxide/cuprous oxide structure and preparation method thereof Download PDF

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CN109607596B
CN109607596B CN201811561128.XA CN201811561128A CN109607596B CN 109607596 B CN109607596 B CN 109607596B CN 201811561128 A CN201811561128 A CN 201811561128A CN 109607596 B CN109607596 B CN 109607596B
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gallium oxide
oxide
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seed crystal
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CN109607596A (en
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于乃森
陈向丰
齐岩
赵海燕
苑青
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Dalian Minzu University
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    • 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
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
    • C01P2004/86—Thin layer coatings, i.e. the coating thickness being less than 0.1 time the particle radius

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Abstract

A nano composite material based on a gallium oxide/cuprous oxide structure is a composite material with a cuprous oxide nano layer coated on the outer surface of a gallium oxide nanorod, and a zinc oxide seed crystal transition layer is arranged between the gallium oxide nanorod and the cuprous oxide nano layer. Wherein the gallium oxide layer is a nano rod-shaped structure prepared from a low-temperature aqueous solution, and the nano cuprous oxide coating layer is prepared by a multi-step seed crystal coating growth method; the transition layer adopts crystal lattice and beta-Ga2O3And the seed crystal layer is well matched. The product of the invention realizes beta-Ga2O3/Cu2The product has absorption to ultraviolet and visible light and expands the absorption range of the product; meanwhile, the preparation method does not need a catalyst, and has the advantages of good repeatability, simple process operation and low manufacturing cost.

Description

Nano composite material based on gallium oxide/cuprous oxide structure and preparation method thereof
Technical Field
The invention relates to a semiconductor material and a preparation method thereof, in particular to a gallium oxide semiconductor material and a preparation method thereof.
Background
Gallium oxide is an important novel wide bandgap semiconductor material, and has a bandgap of 4.9eV, and has received increasing attention due to its high bandgap, high breakdown voltage, and excellent ultraviolet transmittance. beta-Ga2O3An intrinsic n-type oxide semiconductor due to the presence of oxygen vacancy defects, and beta-Ga2O3As a new semiconductor nanomaterial, it also has unique physicochemical properties not possessed by bulk materials. Has great potential and value in the application aspects of luminescence, sensors, solar cells, photocatalysis, and the like. The p-type Ga which is stable at present2O3It is still difficult to prepare.
Disclosure of Invention
The invention aims to provide a nano composite material based on a gallium oxide/cuprous oxide structure and a preparation method thereof. The composite material of the invention is: the gallium oxide layer is covered with a nano cuprous oxide bag by taking a gallium oxide/zinc oxide seed crystal layer as a transition layerCoating; wherein the gallium oxide layer is a nano rod-shaped structure prepared from a low-temperature aqueous solution, and the nano cuprous oxide coating layer is prepared by a multi-step seed crystal coating growth method; the transition layer adopts crystal lattice and beta-Ga2O3And the seed crystal layer is well matched. The preparation method of the invention firstly adopts beta-Ga2O3Growing ZnO nano seed crystal layer on the surface, and finally, carrying out corrosive growth on the ZnO nano seed crystal layer to obtain nano Cu2And (4) an O coating layer.
The invention specifically comprises the following contents:
the material is a composite material with a cuprous oxide nano-layer coated on the outer surface of a gallium oxide nanorod, a gallium oxide/zinc oxide seed crystal transition layer is arranged between the gallium oxide nanorod and the cuprous oxide nano-layer and serves as a template, and then Cu is carried out2The O nano material grows, so that the composite material is sequentially beta-Ga from inside to outside2O3Nanorod core layer, ZnO seed crystal transition layer and Cu2And (4) an O nano coating layer.
Secondly, the preparation method of the invention comprises the following steps:
drying, heating for 15-30 minutes at 150-200 ℃, adopting a low-temperature aqueous solution method, taking 10-30 mol/L gallium nitrate and 10-30 mol/L hexamethylenetetramine as reaction raw materials, reacting for 3-8 hours at 70-90 ℃ at a volume ratio of 1:1, and preparing a gallium oxide precursor GaOOH.
Secondly, placing the precursor GaOOH grown in the step one in a heating furnace, heating for 2-5 hours at 600-800 ℃, and naturally cooling to obtain beta-Ga2O3A nanorod material.
Dissolving zinc acetate in ethanol to prepare ZnO seed crystal transition growth layer solution with the concentration of 3-7 g/L; and (4) placing the powder obtained in the step two in a ZnO seed crystal transition growth layer solution, performing ultrasonic treatment for 5 minutes under the conditions of ultrasonic frequency of 40kHz and output power of 400W, naturally soaking for 12-24 hours, filtering, placing the powder in an oven, and naturally cooling to room temperature. Repeating the soaking, filtering and heating processes for three times to obtain the structure of the gallium oxide/zinc oxide seed crystal transition layer attached to the gallium oxide nano rod.
Dissolving copper acetate in ethanol, and quickly and uniformly stirring to prepare a mixed solution with the concentration of 2-5 g/L; and soaking the gallium oxide nanorod with the ZnO transition seed crystal layer after the heat treatment in the step three into the mixed solution, and reacting for 12-24 hours at 70 ℃. And after the reaction is finished, taking out the product, washing the product with deionized water, and drying the product. And then placing the mixture in a heating furnace for heating for 15-30 minutes at the temperature of 150-200 ℃, naturally cooling the mixture and placing the mixture at room temperature, and repeating the growth and heating processes for three times. And preparing the gallium oxide/cuprous oxide nano composite structure.
The design idea of the invention is as follows: cuprous oxide is a natural p-type semiconductor material with excellent performance, has the advantages of no toxicity, rich raw materials and the like, has the forbidden bandwidth of about 2.1eV, is in the optimal energy gap range of photovoltaic power generation, is matched with the maximum value of a solar spectrum, has higher absorption rate in a visible light range, and has higher theoretical photoelectric conversion efficiency. Thus Cu2O is an ideal material in the field of solar cells. It is known that a highly active photocatalyst must have both high crystallinity and large specific surface area. The former can reduce the recombination rate of photo-generated electron holes at defect points, while the latter can enhance the adsorption capacity of reactants on the surfaces of the nanoparticles and further react with the photo-generated electron holes. Further, the realization of optically enhanced structures by nano-cladding of narrow bandgap semiconductors with wide bandgap semiconductors may play an important role in future photonic devices.
Compared with the prior art, the invention has the following advantages:
1. the product of the invention realizes beta-Ga2O3/Cu2The product has the absorption for ultraviolet light and visible light, and the absorption range is expanded.
2. The preparation method of the invention does not need a catalyst, has good repeatability, simple process operation and low manufacturing cost.
Drawings
FIG. 1 shows β -Ga in an embodiment of the present invention2O3Scanning electron microscope image of the nano rod;
FIG. 2 shows β -Ga in an embodiment of the present invention2O3/Cu2O nanometer composite structure scanning electron microscope appearance picture;
FIG. 3 shows β -Ga in an embodiment of the present invention2O3/Cu2A transmission electron microscope image of the O nano composite structure;
FIG. 4 shows β -Ga in an embodiment of the present invention2O3/Cu2An element distribution diagram at an O nano composite structure interface;
FIG. 5 shows β -Ga in an embodiment of the present invention2O3Nanorod absorption spectrogram;
FIG. 6 shows β -Ga in an embodiment of the present invention2O3/Cu2Absorption spectrum of O nano composite structure.
The description of the above figures is as follows:
as can be seen from FIG. 1, synthesized beta-Ga2O3The size of the nano rod is between 500 and 800 nm.
As can be seen from FIG. 2, synthesized β -Ga2O3Nanorod all-coated Cu2And uniformly coating the O nano material.
As can be seen from FIG. 3, Cu of the clad layer2The size of the O nano material is about 50 nm.
As can be seen from FIG. 4, the nano-beta-Ga prepared by the embodiment of the invention2O3/Cu2The O nano composite structure mainly comprises Ga and Cu elements.
As can be seen from FIG. 5, beta-Ga produced in the examples of the present invention2O3The nano-rods have obvious absorption in the ultraviolet region.
As can be seen from FIG. 6, the nano-beta-Ga prepared by the embodiment of the invention2O3/Cu2The O nanocomposite structure absorbs significantly in both the ultraviolet and visible regions.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
The test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
By using a low-temperature aqueous solution method, 0.76g of gallium nitrate and 0.42g of hexamethylene tetramine are firstly weighed and dissolved in a 100ml aqueous solution system to be used as a precursor reaction source, and the reaction temperature is 90 ℃ for 5 hours to prepare a gallium oxide precursor GaOOH. Placing the grown precursor GaOOH in an annealing furnace, heating at 800 ℃ for 2 hours, and naturally cooling to obtain beta-Ga2O3A nanorod material. Dissolving 0.66g of zinc acetate in 100ml of ethanol to prepare a ZnO seed crystal transition growth layer solution; beta-Ga to be obtained2O3Putting the nanorod powder into the prepared ZnO seed crystal transition growth layer solution, performing ultrasonic treatment for 5 minutes under the conditions of ultrasonic frequency of 40kHz and output power of 400W, naturally soaking for 24 hours after dispersion, filtering, putting the powder into an oven for drying, heating for 30 minutes at 200 ℃, and naturally cooling to room temperature. And then repeating the processes of soaking, filtering and heating for three times to obtain a structure in which the gallium oxide/zinc oxide seed crystal transition layer is attached to the gallium oxide nano-rod. Dissolving 0.45g of copper acetate in 100mL of ethanol, and quickly and uniformly stirring to prepare a mixed solution; immersing the sample on which the transition seed crystal grows after the heat treatment into the mixed reaction solution, and reacting for 24 hours at 70 ℃. And after the reaction is finished, taking out the product, washing the product with deionized water, and drying the product. Then the mixture is placed in a heating furnace for heating at the temperature of 200 ℃ for 15 minutes, then the mixture is naturally cooled to room temperature, and then the growth and heating processes are repeated three times. And preparing the gallium oxide/cuprous oxide nano composite structure.
The results of the corresponding characterization tests performed on the samples are as follows: the synthesized beta-Ga can be seen through the tests of a scanning electron microscope and a transmission electron microscope2O3The nano-rod has a size of 500-800nm and a Cu-coated surface2Uniformly coating the O nano material; cu of coating layer2The size of the O nano material is about 50 nm; absorption spectrum tests show that the nano beta-Ga is synthesized2O3/Cu2The O nanocomposite structure absorbs significantly in both the ultraviolet and visible regions.
Example 2
Using low-temperature aqueous processes, first called0.51g of gallium nitrate and 0.28g of hexamethylenetetramine are dissolved in a 100ml water solution system to be used as a precursor reaction source, the reaction temperature is 70 ℃, and the reaction is carried out for 7 hours to prepare a gallium oxide precursor GaOOH. Putting the grown precursor GaOOH into an annealing furnace, heating at 600 ℃ for 5 hours, and naturally cooling to obtain beta-Ga2O3A nanorod material. Dissolving 0.15g of zinc acetate in 100ml of ethanol to prepare a ZnO seed crystal transition growth layer solution; beta-Ga to be obtained2O3And putting the nanorod powder into the prepared ZnO seed crystal transition growth layer solution, performing ultrasonic treatment for 5 minutes under the conditions of ultrasonic frequency of 40kHz and output power of 400W, naturally soaking for 12 hours after dispersion, filtering, putting the powder into an oven for drying, heating for 15 minutes at 150 ℃, and naturally cooling to room temperature. And then repeating the processes of soaking, filtering and heating for three times to obtain a structure in which the gallium oxide/zinc oxide seed crystal transition layer is attached to the gallium oxide nano-rod. Dissolving 0.2g of copper acetate in 100mL of ethanol, and quickly and uniformly stirring to prepare a mixed solution; immersing the sample on which the transition seed crystal grows after the heat treatment into the mixed reaction solution, and reacting for 12 hours at 70 ℃. And after the reaction is finished, taking out the product, washing the product with deionized water, and drying the product. Then the mixture is placed in a heating furnace for heating at 150 ℃ for 30 minutes, then the mixture is naturally cooled to room temperature, and the growth and heating processes are repeated three times. And preparing the gallium oxide/cuprous oxide nano composite structure.

Claims (3)

1. A nanometer composite material based on gallium oxide/cuprous oxide structure is characterized in that: the composite material is characterized in that the outer surface of a gallium oxide nanorod is coated with a cuprous oxide nano layer, a gallium oxide/zinc oxide seed crystal transition layer is arranged between the gallium oxide nanorod and the cuprous oxide nano layer, and the preparation method comprises the following steps:
firstly, a low-temperature aqueous solution method is adopted, 10-30 mol/L gallium nitrate and 10-30 mol/L hexamethylenetetramine are used as reaction raw materials, the volume ratio of the raw materials is 1:1, and a gallium oxide precursor GaOOH is prepared by reacting for 3-8 hours at the temperature of 70-90 ℃;
secondly, placing the precursor GaOOH grown in the step one in a heating furnace, heating for 2-5 hours at 600-800 ℃, and naturally cooling to obtain beta-Ga2O3A nanorod material;
dissolving zinc acetate in ethanol to prepare ZnO seed crystal transition growth layer solution with the concentration of 3-7 g/L; placing the powder obtained in the second step in a ZnO seed crystal transition growth layer solution, performing ultrasonic treatment for 5 minutes under the conditions of ultrasonic frequency of 40kHz and output power of 400W, then naturally soaking for 12-24 hours, filtering, then placing the powder in an oven for drying, heating for 15-30 minutes at 150-200 ℃, then naturally cooling to room temperature, repeating the soaking, filtering and heating processes for three times, and obtaining a structure of a gallium oxide/zinc oxide seed crystal transition layer attached to a gallium oxide nanorod;
dissolving copper acetate in ethanol, and quickly and uniformly stirring to prepare a mixed solution with the concentration of 2-5 g/L; immersing the gallium oxide nanorod with the ZnO transition seed crystal layer grown after the heat treatment in the step three into the mixed solution, reacting for 12-24 hours at 70 ℃, taking out after the reaction is finished, washing with deionized water, drying, heating for 15-30 minutes in a heating furnace at 150-200 ℃, naturally cooling, standing at room temperature, and repeating the growing and heating processes for three times.
2. The gallium oxide/cuprous oxide structure based nanocomposite of claim 1, wherein: the composite material is sequentially beta-Ga from inside to outside2O3Nanorod core layer, ZnO seed crystal transition layer and Cu2And (4) an O nano coating layer.
3. The gallium oxide/cuprous oxide structure based nanocomposite of claim 1, wherein: the gallium oxide layer is a nano rod-shaped structure prepared from a low-temperature aqueous solution, and the nano cuprous oxide coating layer is prepared by a multi-step seed crystal coating growth method; the transition layer adopts crystal lattice and beta-Ga2O3And the seed crystal layer is well matched.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103894172A (en) * 2012-12-28 2014-07-02 索尼公司 ZnGa2O4-Ga2O3 heterojunction photocatalytic material, preparation method and application of material
CN106549079A (en) * 2016-09-30 2017-03-29 大连民族大学 A kind of ultraviolet light detector and preparation method thereof
CN107697945A (en) * 2017-10-23 2018-02-16 浙江理工大学 A kind of Ga2O3Mutually knot nanometer rods and preparation method thereof
CN108878512A (en) * 2018-06-29 2018-11-23 云南大学 A kind of metal oxide stack field-effect material and its application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103894172A (en) * 2012-12-28 2014-07-02 索尼公司 ZnGa2O4-Ga2O3 heterojunction photocatalytic material, preparation method and application of material
CN106549079A (en) * 2016-09-30 2017-03-29 大连民族大学 A kind of ultraviolet light detector and preparation method thereof
CN107697945A (en) * 2017-10-23 2018-02-16 浙江理工大学 A kind of Ga2O3Mutually knot nanometer rods and preparation method thereof
CN108878512A (en) * 2018-06-29 2018-11-23 云南大学 A kind of metal oxide stack field-effect material and its application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Ultrasensitive multiple networked Ga2O3-core/ZnO-shell nanorod gas sensors;Changhyun Jin等;《Sensors and Actuators B: Chemical》;20111106;第223-228页 *

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