CN111613968B - Method for realizing ZnO micron line EHP laser - Google Patents
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- H01S5/00—Semiconductor lasers
- H01S5/30—Structure or shape of the active region; Materials used for the active region
- H01S5/32—Structure or shape of the active region; Materials used for the active region comprising PN junctions, e.g. hetero- or double- heterostructures
- H01S5/327—Structure or shape of the active region; Materials used for the active region comprising PN junctions, e.g. hetero- or double- heterostructures in AIIBVI compounds, e.g. ZnCdSe-laser
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Abstract
The invention discloses a method for realizing ZnO microwire EHP laser, which comprises the following steps: step 1: sputtering an Ag quasi-particle film on the ZnO/Ga micron line, and converting the Ag quasi-particle film on the ZnO/Ga micron line into large-size AgNPs by using the joule heating effect to form a large-size AgNPs-coated ZnO/Ga micron line composite structure; step 2: exciting EHP laser with a large-size AgNPs-coated ZnO/Ga micron line composite structure by using laser. The invention can effectively reduce the threshold value of single micron line optical pumping laser and realize the enhancement of laser output; and as the excitation power is increased, the laser peak position generates obvious red shift and is accompanied with the mode spacing broadening of the lasing peak. Based on the fact that single ZnO-Ga micron line is wrapped by large-size AgNPs, the EHP lasing phenomenon under femtosecond laser excitation is achieved. Provides technical support and experimental basis for the subsequent AgNPs mixed quadrupole resonance enhanced wide bandgap semiconductor photoelectric device.
Description
Technical Field
The invention belongs to the technical field of preparation of zinc oxide laser devices, and particularly relates to a preparation method of a large-size AgNPs modified zinc oxide composite structure microcavity.
Background
The ZnO material is used as a direct band gap and wide forbidden band semiconductor material, and plays an important role in the aspects of ultraviolet photoelectric functional materials and devices. ZnO materials (micron lines and nanorods) with micro-nano structures have high crystallization quality, possess optical resonant cavities, and are widely applied to ultraviolet lasers, detectors, light-emitting diodes and the like. The ZnO ultraviolet laser comprises three oscillation modes: random lasers, Fabry-Perot (F-P) lasers and Whispering Gallery (WGM) lasers. Among them, the WGM mode laser is an important mode laser because of its low lasing threshold, good optical gain, and small loss. At present, related reports exist for enhancing ZnO intrinsic ultraviolet luminescence by utilizing plasma resonance on local surface of metal nanoparticles such as Al, Au and the like, so that the optical gain of a ZnO microcavity is improved. The research on the localized surface plasmon resonance of metal nanostructures mainly focuses on near-field coupling and resonance enhancement between excitons and excitons, and the research on the mechanism of the process from low-order resonance (dipole resonance) to high-order resonance (hybrid quadrupole resonance, etc.) is still in the primary stage.
Disclosure of Invention
The invention aims to provide a method for enhancing zinc oxide ultraviolet luminescence by using large-size AgNPs and realizing EHP laser. Because the mixed quadrupole resonance of the large-size AgNPs effectively induces the generation of hot electrons and then injects the hot electrons into the micron line, the EHP laser under the excitation of the femtosecond laser is formed, and the technical support is provided for the AgNPs mixed quadrupole resonance enhanced wide-bandgap semiconductor photoelectric device.
In order to achieve the purpose, the preparation method for realizing the EHP laser by the large-size AgNPs modified ZnO micron line comprises the following steps:
a method for realizing ZnO micron line EHP laser comprises the following steps:
step 1: sputtering an Ag quasi-particle film on the ZnO/Ga micron line, and converting the Ag quasi-particle film on the ZnO/Ga micron line into large-size AgNPs by using the joule heating effect to form a large-size AgNPs-coated ZnO/Ga micron line composite structure;
step 2: exciting EHP laser with a large-size AgNPs-coated ZnO/Ga micron line composite structure by using laser.
Further, step 1 comprises:
step 1.1: displacing a single ZnO/Ga micron wire with a polygonal section onto a quartz substrate to ensure that one surface of the ZnO/Ga micron wire is attached to the quartz substrate, and pressing indium electrodes at two ends of the ZnO/Ga micron wire;
step 1.2: directionally sputtering an Ag nano quasi-particle film in the middle of the ZnO-Ga micron line obtained in the step 1.1;
step 1.3: placing the ZnO and Ga microwires wrapped by the Ag nano quasi-particle film obtained in the step 1.2 under a microscope containing CCD imaging so that an image of a ZnO and Ga microwire composite structure can be clearly seen in computer software, and then applying voltage on indium electrodes at two ends until the ZnO and Ga microwires can be seen to emit light; at the luminescence center, the Ag nanoparticle film degenerates into isolated large-size AgNPs.
Furthermore, the ZnO-Ga micron line is prepared by adopting a chemical vapor deposition method, and the interface of the ZnO-Ga micron line is hexagonal.
Furthermore, the electron concentration of the ZnO-Ga micron line is 1018～1019/cm3The electron mobility is 10-95 cm2/V·s。
Furthermore, the thickness of the Ag quasi-particle film sputtered on the ZnO-Ga micron line is 30-50 nm.
Further, in the step 2, the excitation wavelength of the laser is 355nm, and the excitation power is 1-700 μm.
Further, the large-size AgNPs are 200 nm.
Further, in the step 1.2, the part, containing the indium electrodes, of the two sides of the ZnO-Ga microwire is shielded by a mask plate, and then the ZnO-Ga microwire is placed into a vacuum chamber of a magnetron sputtering instrument, the selected sputtering target is an Ag target with the purity of 99.9999%, the gas in the vacuum chamber is argon, the pressure of the chamber is 31-32 Pa, the sputtering current is 28-29 mA, and the sputtering time is 300-400 s.
Furthermore, in step 1.3, the applied voltage value is 0V-210V, and the current value is 0-1A.
The invention has the beneficial effects that: the large-size AgNPs (d-200 nm) and the mixed quadrupole resonance thereof are realized by regulating and controlling the sputtering time and the heat treatment of the Ag nano film. And (3) combining sputtering and Joule heating effects, and wrapping large-size AgNPs (AgNPs @ ZnO: Ga micron lines) in the central area of the ZnO: Ga micron lines with hexagonal sections. The radiation loss of the mixed quadrupole resonance is very weak, and the efficiency of hot electrons generated by the resonance is greatly improved. The optical pumping test is carried out on a single AgNPs @ ZnO Ga micron line, and the experimental result shows that the threshold of optical pumping lasing of the single micron line can be effectively reduced and the enhancement of laser output can be realized based on the hot electron injection induced by the resonance of the mixed quadrupole of the large-size AgNPs; and as the excitation power is increased, the laser peak position generates obvious red shift and is accompanied with the mode spacing broadening of the lasing peak. Therefore, based on the fact that single ZnO-Ga micron line is wrapped by large-size AgNPs, the EHP lasing phenomenon under femtosecond laser excitation is achieved. Provides technical support and experimental basis for the subsequent AgNPs mixed quadrupole resonance enhanced wide bandgap semiconductor photoelectric device.
Drawings
FIG. 1 is a schematic structural view of the present invention sputtering Ag quasiparticle film on a ZnO-Ga microwire MSM structure.
FIG. 2 is a scanning electron microscope image of a single ZnO/Ga micron line sputtered Ag quasi-particle film of the present invention.
FIG. 3 is an electroluminescent photograph of a single ZnO to Ga microwire after sputtering Ag quasiparticle film according to the present invention.
FIG. 4 is a scanning electron microscope image of AgNPs on a single ZnO-Ga micron line.
FIG. 5 shows the photoluminescence spectrum of large-size AgNPs-modified ZnO-Ga microwire under femtosecond laser.
Detailed Description
The invention is further illustrated below with reference to examples and figures.
The invention comprises the following steps:
(1) cleaning the quartz substrate to ensure that the quartz substrate is completely clean;
(2) a single ZnO/Ga micron wire with a hexagonal section is displaced onto a quartz substrate, one surface of the hexagon is ensured to be attached to the quartz substrate, and indium electrodes are pressed at two ends of the ZnO/Ga micron wire;
(3) directionally sputtering an Ag nano quasi-particle film in the middle of the ZnO-Ga micron line obtained in the step (2);
(4) and (4) placing the ZnO and Ga microwires wrapped by the Ag nano quasi-particle film obtained in the step (3) under a microscope containing CCD imaging so that an image of a ZnO and Ga microwire composite structure can be clearly seen in computer software, and then applying voltage to indium electrodes at two ends until the ZnO and Ga microwires can be seen to emit light. At the luminescence center, the Ag nanoparticle film degenerates into isolated large-size AgNPs.
(5) And (4) placing the sample prepared in the step (4) under the light pumping laser, and lasing the EHP laser under a certain power.
The method for cleaning the quartz substrate in the step (1) comprises the following steps: respectively putting the quartz substrate into a trichloroethylene solution and an ultrasonic cleaning machine, and cleaning for 20 minutes; taking the quartz substrate out of the trichloroethylene solution, respectively putting the quartz substrate into acetone, ethanol and deionized water for ultrasonic cleaning for 20 minutes by the same method, putting the quartz substrate into an oven for drying for 1 hour, and then drying by using nitrogen. Wherein the quartz substrate size (L-W ═ 8.0 to 5.0 cm).
And (2) preparing the single ZnO-Ga micron line displacement quartz substrate: taking out a ZnO/Ga micron line with a hexagonal section from the corundum boat by using tweezers, horizontally placing the ZnO/Ga micron line on a quartz substrate, and operating the ZnO/Ga micron line under a microscope to ensure that one surface of the ZnO/Ga micron line is attached to the quartz substrate. And pressing indium grain electrodes at two ends of the ZnO: Ga micron line to ensure that the indium electrodes, the ZnO: Ga micron line and the quartz substrate are compactly attached together to form a metal-semiconductor-metal (MSM) structure. The electron concentration of the ZnO-Ga micron line is 1018～1019/cm3The electron mobility is 10-95 cm2/V·s。
And (3) shielding the indium-containing electrode parts on the two sides of the ZnO/Ga microwire in the step (2) by using a mask, and sputtering a layer of compact Ag nano quasi-particle film on the surface of the ZnO/Ga microwire by using a plasma sputtering instrument. The mask used for sputtering can be tightly attached to an object to be shielded, so that any area on the surface of the ZnO-Ga micron line can be shielded for sputtering; the sputtering target is an Ag target with the purity of 99.9999%, argon is used as a working gas, the pressure of a cavity is 31-32 Pa, the sputtering current is 28-29 mA, the sputtering time is 300-400 s, and the sputtering area is ZnO-Ga microwire without indium electrodes at two ends; the schematic structural diagram of the sputtered ZnO-Ga micron line is shown in 1, and the scanning electron microscope image is shown in 2.
And (4) putting the ZnO and Ga micron line wrapped by the Ag nano quasi-particle film obtained in the step (3) under a microscope, and focusing the ZnO and Ga micron line to form a clear image. A voltage is applied to the indium electrodes at both ends, and a source meter for applying the voltage can freely adjust the voltage and the current value. The voltage of the source table was slowly increased until the ZnO: Ga microwire emitted, and the photograph of the emission is shown in fig. 3. Due to joule heating effect, the Ag quasi-particle film at the luminescent center of the Ga micron line of ZnO becomes isolated Ag nano-particles, wherein large-size AgNPs (d-200 nm) can excite quadrupole resonance. The scanning electron micrograph thereof is shown in FIG. 4.
And (5) placing the ZnO and Ga microwires wrapped by the large-size Ag nano particles obtained in the step (4) under optical pumping laser, wherein the focus of the laser is aligned to the ZnO and Ga microwires wrapped by the large-size Ag nano particles. The excitation wavelength of the optical pumping laser is 355nm, and the excitation power is 1-700 mu w. As the optical pumping power is increased, the central wavelength of the ZnO Ga ultraviolet laser has obvious red shift, and the EHP effect is shown as figure 5.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (6)
1. A method for realizing ZnO micron line EHP laser is characterized by comprising the following steps:
step 1: sputtering an Ag quasi-particle film on the ZnO/Ga micron line, and converting the Ag quasi-particle film on the ZnO/Ga micron line into large-size AgNPs by using the joule heating effect to form a large-size AgNPs-coated ZnO/Ga micron line composite structure;
step 2: exciting EHP laser with a large-size AgNPs-coated ZnO/Ga micron line composite structure by using laser;
the step 1 comprises the following steps:
step 1.1: a single ZnO/Ga micron wire with a hexagonal section is displaced onto a quartz substrate, one surface of the ZnO/Ga micron wire is ensured to be attached to the quartz substrate, and indium electrodes are pressed at two ends of the ZnO/Ga micron wire;
step 1.2: sputtering an Ag nano quasi-particle film on the ZnO-Ga micron line obtained in the step 1.1;
step 1.3: placing the ZnO and Ga microwires wrapped by the Ag nano quasi-particle film obtained in the step 1.2 under a microscope containing CCD imaging so that an image of a ZnO and Ga microwire composite structure can be clearly seen in computer software, and then applying voltage on indium electrodes at two ends until the ZnO and Ga microwires can be seen to emit light; at the luminescence center, the Ag nano quasi-particle film is degenerated into isolated large-size AgNPs;
the diameter of the large-size AgNPs is 200 nm;
in the step 1.2, the parts containing indium electrodes on two sides of the ZnO-Ga microwire are shielded by a mask plate, and then the ZnO-Ga microwire is placed into a vacuum chamber of a magnetron sputtering instrument, the selected sputtering target is an Ag target with the purity of 99.9999%, the gas in the vacuum chamber is argon, the pressure of the chamber is 31-32 Pa, the sputtering current is 28-29 mA, and the sputtering time is 300-400 s.
2. The method for realizing the EHP laser of the ZnO microwire as the claim 1, wherein the ZnO-Ga microwire is prepared by adopting a chemical vapor deposition method.
3. The method of claim 1, wherein the electron concentration of the ZnO to Ga micron line is 1018～1019/cm3The electron mobility is 10-95 cm2/V·s。
4. The method of claim 1, wherein the Ag quasiparticle film sputtered on the ZnO-Ga microwire has a thickness of 30-50 nm.
5. The method of claim 1, wherein in step 2, the laser has an excitation wavelength of 355nm and an excitation power of 1-700 μm.
6. The method of claim 1, wherein in step 1.3, the applied voltage is 0V-210V and the current is 0-1A.
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| CN110828620A (en) * | 2019-10-16 | 2020-02-21 | 南京航空航天大学 | Single ZnO micron line heterojunction-based near-infrared light-emitting diode and preparation method thereof |
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| CN101282022A (en) * | 2008-04-30 | 2008-10-08 | 苏州纳米技术与纳米仿生研究所 | Near-field optical enhancement type nanometer array light-through hole laser |
| WO2012015990A2 (en) * | 2010-07-27 | 2012-02-02 | The Regents Of The University Of California | Plasmon lasers at deep subwavelength scale |
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| CN110137315A (en) * | 2019-04-25 | 2019-08-16 | 南京航空航天大学 | Single ZnO:Ga micro wire hetero-junctions substantial point source device and preparation method |
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