CN108128799B - Preparation method of ultrathin zinc oxide spherical shell - Google Patents
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- CN108128799B CN108128799B CN201711447796.5A CN201711447796A CN108128799B CN 108128799 B CN108128799 B CN 108128799B CN 201711447796 A CN201711447796 A CN 201711447796A CN 108128799 B CN108128799 B CN 108128799B
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- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
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- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
Abstract
The invention discloses a preparation method of an ultrathin zinc oxide spherical shell, which comprises the following steps: 1) preparing zinc oxide @ zinc microspheres with core-shell structures by using a laser ablation method; 2) placing the prepared zinc oxide @ zinc microspheres in a tubular furnace, vacuumizing the tubular furnace until the vacuum degree reaches below 100Pa, and introducing protective gas to adjust the air pressure in the tubular furnace so as to stabilize the air pressure at 100 Pa; 3) and setting parameters of the tube furnace as raising the temperature for 5-15 h to 300-600 ℃, and then annealing for 1-3 h to obtain the ultrathin zinc oxide spherical shell. The method is a template-free method, does not need a template, can obtain the ultrathin zinc oxide spherical shell only by controlling the thermal annealing process, and is simple and easy to operate; the method can prepare the ultrathin zinc oxide spherical shell with perfect appearance and smooth surface, the diameter of the prepared zinc oxide spherical shell is in micron size grade, and the shell wall thickness of the spherical shell is below 10 nm; in addition, the method can also prepare the zinc oxide spherical shell with obvious laser luminescence characteristics.
Description
Technical Field
The invention relates to a preparation method of an ultrathin zinc oxide spherical shell, in particular to a method for preparing an ultrathin zinc oxide spherical shell by thermal annealing, belonging to the field of preparation of photoelectric nano materials.
Background
The zinc oxide has a forbidden band width of 3.37eV and an exciton binding energy of 60meV at room temperature, and thus has good light emitting characteristics in the ultraviolet region, as well as photocatalytic and sensing characteristics. The zinc oxide hollow microsphere has the characteristics of controllable shape and size, good monodispersity, high specific surface area and small density, and is widely applied to various fields of catalysis, medical treatment, photoelectric devices and the like. In the existing research, the zinc oxide microspheres with hollow structures are widely used in various fields, such as solar energy, photocatalysis, gas sensing and the like. In addition, zinc oxide is also a promising material in the field of biomedicine, and for example, zinc oxide has been widely used in the research fields of bacteriostasis, drug development, synthesis and the like. Therefore, the ultrathin zinc oxide microspheres have great research significance and prospect in various fields of optics, catalysis, sensing and biomedicine.
The template method is one of the common methods for preparing inorganic hollow microsphere shells, and various materials with different forms can be prepared by controlling the growth direction and the form of the material by using the template. The zinc oxide hollow sphere prepared by the template method is complex in preparation method, and is easy to introduce impurities, so that the structure and the performance of a sample are influenced. The hydrothermal method is also successfully used for preparing the zinc oxide spherical shell, but the prepared zinc oxide hollow microsphere has rough surface, poor crystallization property and no obvious laser phenomenon.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problems of complex preparation method, poor product structure performance, no laser phenomenon and the like existing in the preparation of the zinc oxide spherical shell by the existing template method and hydrothermal method, the preparation method of the ultrathin zinc oxide spherical shell is provided.
The technical scheme is as follows: the invention relates to a preparation method of an ultrathin zinc oxide spherical shell, which comprises the following steps:
1) preparing zinc oxide @ zinc microspheres with core-shell structures by using a laser ablation method;
2) placing the prepared zinc oxide @ zinc microspheres in a tubular furnace, vacuumizing the tubular furnace until the vacuum degree reaches below 100Pa, and introducing protective gas to adjust the air pressure in the tubular furnace so as to stabilize the air pressure at 100 Pa;
3) and setting parameters of the tube furnace as raising the temperature for 5-15 h to 300-600 ℃, and then annealing for 1-3 h to obtain the ultrathin zinc oxide spherical shell.
In the step 1), the preparation of the zinc oxide @ zinc microspheres by the laser ablation method preferably comprises the following steps:
1a) starting a laser, adjusting the position of a lens, and focusing a laser beam on the surface of the metal zinc target;
1b) dropping deionized water or absolute ethyl alcohol on the substrate until the substrate is fully paved;
1c) adjusting the laser output power to be 150-300 mW, and ablating the metal zinc target material in the air at normal temperature for 2-10 min;
1d) and (3) drying the substrate at 60 ℃ under vacuum to obtain the zinc oxide @ zinc microspheres on the substrate.
The diameter of the zinc oxide @ zinc microspheres is micron-sized by adopting the laser ablation method, the diameters of the finally prepared zinc oxide @ zinc microspheres are different due to different solutions dripped on the substrate, and the size of the zinc oxide @ zinc microspheres obtained in deionized water is larger.
The substrate used in step 1b) may be a silicon wafer or a quartz wafer. In the step 1c), the laser output power is preferably 200-220 mW, and is preferably 210 mW; the ablation time is preferably 4-6 min, and is preferably 5 min; at the moment, the zinc oxide @ zinc microspheres with smooth surfaces and better laser characteristics can be prepared; the zinc oxide @ zinc microspheres with laser characteristics cannot be prepared under the condition of too low or too high laser output power.
In the step 2), after the tube furnace is vacuumized, introducing inert gas (such as argon, helium and the like) or nitrogen into the tube furnace to keep the low-oxygen environment in the tube furnace; vacuumizing and introducing protective gas to reduce the content of oxygen, wherein the content of oxygen with extremely low concentration can slowly oxidize the sample under the protection of inert gas or nitrogen, so that the structure of the sample is prevented from being changed; preferably, nitrogen is introduced for protection in the step.
In the step 3), the parameters of the tubular furnace are preferably set to be heated for 10-15 hours to 500-600 ℃, and then annealing is carried out for 2-3 hours, so that the zinc oxide spherical shell with complete appearance, smooth surface and obvious laser phenomenon can be obtained; the thermal annealing condition is preferably that after the temperature is raised for 10 hours to 500 ℃, the zinc oxide spherical shell with high quality appearance and obvious laser phenomenon can be prepared after annealing for 2 hours, and the energy consumption of the thermal annealing condition is the lowest. The structure and the performance of the prepared zinc oxide spherical shell are directly influenced by the temperature rise time, the thermal annealing temperature and the annealing time, and particularly, the slow temperature rise time can prevent the sample from being damaged due to too fast reaction while ensuring slow oxidation because the shell wall of the sample is thin; the annealing temperature of 500-600 ℃ can lead the zinc oxide to generate a recrystallization process, the annealing time of about 2 hours can lead the sample to gradually form better structure and crystallinity, and the generation of the laser performance of the zinc oxide spherical shell has an inseparable relationship with the excellent performance of the structure.
Has the advantages that: compared with the prior art, the invention has the remarkable advantages that: (1) the preparation method of the zinc oxide spherical shell is a template-free method, saves the preparation process of a template compared with the common template method, can obtain the ultrathin zinc oxide spherical shell only by thermal annealing, and is simple and easy to operate; (2) the method can prepare the ultrathin zinc oxide spherical shell with perfect appearance and smooth surface, the diameter of the prepared zinc oxide spherical shell is in micron size level, and the shell wall thickness of the spherical shell is below 10 nm; (3) the method can prepare the zinc oxide spherical shell with obvious laser luminescence property.
Drawings
FIG. 1 is a scanning electron micrograph of the zinc oxide @ zinc microspheres prepared in example 1;
FIG. 2 is a laser spectrum of the zinc oxide @ zinc microspheres prepared in example 1 at different excitation powers;
FIG. 3 is a scanning electron micrograph of the spherical zinc oxide shell prepared in example 2;
FIG. 4 is a scanning electron micrograph of the spherical zinc oxide shell obtained in example 3;
FIG. 5 shows the photoluminescence laser spectrum of the zinc oxide spherical shell obtained in example 3.
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings.
The invention relates to a preparation method of an ultrathin zinc oxide spherical shell, which mainly comprises two steps of preparing zinc oxide @ zinc microspheres by utilizing a laser ablation technology, and then carrying out thermal annealing treatment on the zinc oxide @ zinc microspheres to prepare micron-sized ultrathin zinc oxide spherical shells; the method is simple and easy to operate, and the zinc oxide spherical shell with obvious laser luminescence property can be obtained by controlling the annealing process.
The process of preparing the zinc oxide @ zinc microspheres by the laser ablation method is generally carried out by adopting a pulse laser deposition system, the pulse laser deposition system comprises a pulse laser, a lens, a metal zinc target material, a storage table and a substrate, a gas phase ablation method can be adopted, the target material is directly ablated by laser in the air, the metal target material can generate metal plasma due to high-energy ablation of the laser, and then the metal plasma is agglomerated and oxidized in a liquid environment on the substrate, and finally the zinc oxide @ zinc composite microspheres can be formed on the substrate.
EXAMPLE 1 preparation of Zinc oxide @ Zinc microspheres
Starting a pulse laser, adjusting the position of a lens, and focusing a laser beam on the surface of the zinc target material; then, a substrate silicon wafer is placed at a position which is 5mm away from the target material in the transverse direction and 1cm away from the laser focusing point in the longitudinal direction, and a plurality of drops of deionized water are dripped on the silicon wafer until the substrate is fully paved; regulating the laser output power to 210mW, and the ablation time to 5 min; the silicon wafer is dried at 60 ℃ to obtain the zinc oxide @ zinc microspheres, the structure of which is shown in figure 1, and the zinc oxide @ zinc microspheres are hollow core-shell type composite microspheres with zinc particles wrapped by zinc oxide spherical shells, have smooth surface spherical morphology and have the diameter of about 3 mu m.
The laser performance of the prepared zinc oxide @ zinc microsphere is tested, and the obtained laser spectrum is shown in figure 2, so that the zinc oxide @ zinc microsphere has obvious laser characteristics.
EXAMPLE 2 preparation of Zinc oxide spherical Shell
The quartz tube with openings at both ends was cleaned with alcohol and then dried, and the core-shell zinc oxide @ zinc composite microsphere prepared in example 1 and the substrate were placed in the quartz tube. Placing the sample in a special quartz glass tube of a split-type tube furnace, placing the sample in the central position of the tube furnace, and closing the cover of the tube furnace; starting a vacuum pump to pump the air pressure in the tube furnace to 100Pa, introducing nitrogen with the flow of 80sccm, and adjusting the air pressure in the tube to be stabilized at about 100 Pa; starting a controller of the split-type tube furnace, setting the temperature rise time as 5h, and annealing at 500 ℃ for 1h to obtain the zinc oxide spherical shell as shown in figure 3, wherein the wall of the spherical shell is thinner and the thickness is below 10 nm; however, part of the surface of the spherical shell is damaged because the wall of the sample shell is thin and the temperature rise speed is too high, so that the oxidation reaction process is rapid and the spherical shell is damaged.
EXAMPLE 3 preparation of Zinc oxide spherical Shell
The quartz tube with openings at both ends was cleaned with alcohol and then dried, and the core-shell zinc oxide @ zinc composite microsphere prepared in example 1 and the substrate were placed in the quartz tube. Placing the sample in a special quartz glass tube of a split-type tube furnace, placing the sample in the central position of the tube furnace, and closing the cover of the tube furnace; starting a vacuum pump to pump the air pressure in the tube furnace to 100Pa, introducing nitrogen with the flow of 80sccm, and adjusting the air pressure in the tube to be stabilized at about 100 Pa; starting a controller of the split-type tube furnace, setting the temperature rise time as 10 hours, and annealing at 500 ℃ for 2 hours to obtain a zinc oxide spherical shell with complete appearance and smooth surface, as shown in figure 4; the zinc oxide spherical shell has obvious laser phenomenon, and the laser spectrum of the zinc oxide spherical shell is shown in figure 5.
EXAMPLE 4 preparation of Zinc oxide spherical Shell
The quartz tube with openings at both ends was cleaned with alcohol and then dried, and the core-shell zinc oxide @ zinc composite microsphere prepared in example 1 and the substrate were placed in the quartz tube. Placing the sample in a special quartz glass tube of a split-type tube furnace, placing the sample in the central position of the tube furnace, and closing the cover of the tube furnace; and starting a vacuum pump to pump the air pressure in the tube furnace to 100Pa, introducing nitrogen with the flow rate of 80sccm, and adjusting the air pressure in the tube to be stabilized at about 100 Pa. Starting a controller of the split-type tube furnace, setting the temperature rise time as 10 hours, and annealing at 500 ℃ for 1 hour to obtain the zinc oxide spherical shell with irregular appearance without laser phenomenon. This is because the annealing time is short, and annealing in a short time is not sufficient to form zinc oxide into a structure having good crystallinity, and it is difficult to form laser characteristics.
EXAMPLE 5 preparation of Zinc oxide spherical Shell
The quartz tube with openings at both ends was cleaned with alcohol and then dried, and the core-shell zinc oxide @ zinc composite microsphere prepared in example 1 and the substrate were placed in the quartz tube. Placing the sample in a special quartz glass tube of a split-type tube furnace, placing the sample in the central position of the tube furnace, and closing the cover of the tube furnace; and starting a vacuum pump to pump the air pressure in the tube furnace to 100Pa, introducing nitrogen with the flow rate of 80sccm, and adjusting the air pressure in the tube to be stabilized at about 100 Pa. And (3) starting a controller of the split-type tube furnace, setting the temperature rise time to be 15h, and annealing at 600 ℃ for 3h to obtain the zinc oxide spherical shell with the appearance and the laser characteristics similar to those of the sample prepared in the example 3.
Comparative example 1
The quartz tube with openings at both ends was cleaned with alcohol and then dried, and the core-shell zinc oxide @ zinc composite microsphere prepared in example 1 and the substrate were placed in the quartz tube. The sample was placed in a quartz glass tube dedicated to the split tube furnace, placed in the center of the tube furnace, and the lid of the tube furnace was closed. And (3) starting a controller of the split-type tube furnace, setting the temperature rise time as 10 hours, and annealing at 500 ℃ for 1 hour to obtain the zinc oxide compound with the sea urchin-shaped structure.
Comparative example 2
And cleaning the quartz tubes with openings at two ends by using alcohol, and drying. The core-shell structure zinc oxide @ zinc composite microsphere prepared by the laser ablation method and the substrate are placed in a quartz tube. The sample was placed in a quartz glass tube dedicated to the split tube furnace, placed in the center of the tube furnace, and the lid of the tube furnace was closed. Starting a controller of the split-type tube furnace, setting the temperature rise time as 5h, and annealing at 400 ℃ for 1h to obtain the zinc oxide compound with the star-shaped structure.
Comparative example 3
And cleaning the quartz tubes with openings at two ends by using alcohol, and drying. The core-shell structure zinc oxide @ zinc composite microsphere prepared by the laser ablation method and the substrate are placed in a quartz tube. The sample was placed in a quartz glass tube dedicated to the split tube furnace, placed in the center of the tube furnace, and the lid of the tube furnace was closed. And starting a controller of the split-type tube furnace, setting the temperature rise time to be 7.5h, and annealing at 300 ℃ for 1.5h to obtain the zinc oxide spherical shell, wherein the surface is rough and has no laser phenomenon.
According to comparative examples 1 to 3, the high-concentration oxygen content enables zinc in the sample to be rapidly dissolved at high temperature and oxidized to grow into zinc oxide with a linear structure, so that the original structure of the sample is changed; and the melting point of the zinc is about 410 ℃, so at the annealing temperature lower than the melting point, such as 300 ℃ in the comparative example 3, the zinc in the microspheres is not melted, but is oxidized into zinc oxide by oxygen in a gas environment, so that the surface appearance of the sample is not changed and is still microspherical.
Claims (4)
1. The preparation method of the ultrathin zinc oxide spherical shell is characterized by comprising the following steps:
1) preparing zinc oxide @ zinc microspheres with core-shell structures by using a laser ablation method;
1a) starting a laser, adjusting the position of a lens, and focusing a laser beam on the surface of the metal zinc target;
1b) dropping deionized water or absolute ethyl alcohol on the substrate until the substrate is fully paved;
1c) adjusting the laser output power to be 150-300 mW, and ablating the metal zinc target material in the air at normal temperature for 2-10 min;
1d) drying the substrate at 60 ℃ under vacuum to obtain zinc oxide @ zinc microspheres on the substrate;
2) placing the prepared zinc oxide @ zinc microspheres in a tubular furnace, vacuumizing the tubular furnace until the vacuum degree reaches 100Pa, and introducing protective gas to adjust the air pressure in the tubular furnace so as to stabilize the air pressure at 100 Pa;
3) setting parameters of a tubular furnace to raise the temperature for 10-15 h to 500-600 ℃, and then annealing for 2-3 h to obtain an ultrathin zinc oxide spherical shell; the shell wall thickness of the ultrathin zinc oxide spherical shell is less than 10 nm.
2. The method for preparing an ultrathin zinc oxide spherical shell according to claim 1, wherein in step 1b), the substrate is a silicon wafer or a quartz wafer.
3. The method for preparing the ultrathin zinc oxide spherical shell according to claim 1, wherein in the step 1c), the laser output power is 200-220 mW, and the ablation time is 4-6 min.
4. The method for preparing ultrathin zinc oxide spherical shells according to claim 1, wherein in step 2), the protective gas is an inert gas or nitrogen.
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