CN111525011A - Pt modified ZnO microwire heterojunction light emitting diode and preparation method thereof - Google Patents
Pt modified ZnO microwire heterojunction light emitting diode and preparation method thereof Download PDFInfo
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- CN111525011A CN111525011A CN202010059157.7A CN202010059157A CN111525011A CN 111525011 A CN111525011 A CN 111525011A CN 202010059157 A CN202010059157 A CN 202010059157A CN 111525011 A CN111525011 A CN 111525011A
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- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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- H—ELECTRICITY
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- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
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- H01L33/36—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the electrodes
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Abstract
The invention discloses a Pt modified ZnO micron line heterojunction light-emitting diode and a preparation method thereof, wherein the diode comprises a p-GaN substrate, PtNPs @ ZnO, a Ga composite micron line, a gasket and quartz glass, wherein the gasket and the p-GaN substrate are arranged side by side; the preparation method of the diode comprises the following steps: (S1) preparing a Pt @ ZnO: Ga metal modified semiconductor composite structure; (S2) preparing PtNPs @ ZnO: Ga composite micron line; (S3) preparing PtNPs @ n-ZnO: Ga/p-GaN heterostructure; (S4) preparing an alloy electrode on a p-GaN substrate, and preparing a metal particle electrode at one end of the PtNPs @ ZnO: Ga composite micron line; (S5) finally, pressing a piece of quartz glass on the whole structure to obtain the Pt modified ZnO microwire heterojunction light-emitting diode. The diode has high ultraviolet luminous efficiency, is a micron-sized photoelectric device, is convenient to use and prepare, and can flexibly adjust the luminous wavelength.
Description
Technical Field
The invention relates to a light-emitting diode and a preparation method thereof, in particular to a Pt modified ZnO microwire heterojunction light-emitting diode and a preparation method thereof.
Background
As an important component of semiconductor photoelectric devices, light emitting diodes play an important role in the production and life of people, wherein the development of ultraviolet light emitting diodes not only has important academic significance in basic research, but also has important application requirements in the fields of ultraviolet detection, national defense, photoelectric technology and the like. The II-VI family direct band gap semiconductor zinc oxide (ZnO) is of a hexagonal wurtzite structure, the forbidden band width is 3.37eV, the exciton binding energy is as high as 60meV, and the material is a high-quality material for realizing efficient ultraviolet exciton light emission and laser at room temperature. However, ZnO crystals exhibit n-type conductivity due to the presence of intrinsic defects such as O vacancies and Zn interstitial atoms, whereas p-type ZnO materials are difficult to obtain, so that the application range of ZnO is greatly limited. Therefore, other p-type materials are currently used as hole injection layers in ZnO-based light emitting diodes instead of p-type ZnO. p-GaN is used as an inorganic semiconductor material, is resistant to high temperature and is not easy to be broken down by electrons, and has an energy level structure matched with ZnO, so that p-GaN and ZnO are commonly used to form a p-n junction at present to manufacture a ZnO heterojunction light-emitting diode. However, when p-GaN and ZnO form a p-n junction, ZnO is often a nanowire or nanowire array, which is difficult to prepare and high in cost, and cannot form a diode which can be produced in a large scale and applied to practice, and the p-n junction formed by the pure ZnO nanowire or the nanowire array has low luminous efficiency in an ultraviolet band.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a micron-sized Pt modified ZnO micron-line heterojunction light-emitting diode which is simple in preparation steps, practical and high in luminous efficiency in an ultraviolet band, and the invention also aims to provide a preparation method of the light-emitting diode.
The technical scheme is as follows: the Pt modified ZnO micron line heterojunction light-emitting diode comprises a p-GaN substrate, PtNPs @ ZnO and Ga composite micron lines, a gasket and quartz glass, wherein the gasket is equal in thickness to the p-GaN substrate and is arranged side by side, the PtNPs @ ZnO and Ga composite micron lines are tightly attached to the p-GaN substrate and the gasket, a metal particle electrode is attached to one end of the gasket, an alloy electrode is plated on one end, which is not in contact with the PtNPs @ ZnO and Ga composite micron lines, of the p-GaN substrate, and the quartz glass is pressed on the PtNPs @ ZnO and Ga composite micron lines on the p-GaN substrate.
Wherein the thickness of the p-GaN substrate is 2-10 μm, and the hole concentration is 1017-1019/cm3Hole mobility of 5-100cm2the/V.s, PtNPs @ ZnO and Ga composite micron line is prepared by modifying Pt nano particles on the surface of ZnO and Ga micron line, and the electron concentration of the ZnO and Ga micron line is 1017-1019/cm3Electron mobility of 5-100cm2The Ga doping concentration is less than 1%, the average diameter of Pt nano particles is 30-300nm, the distribution interval is 50-200nm, the alloy electrode is Ni/Au alloy, the thickness of Ni is 20-30 nm, and the thickness of Au is 40-50 nm.
The preparation method of the Pt modified ZnO microwire heterojunction light-emitting diode comprises the following steps:
(S1) preparing a Pt quasi-particle nano film on a ZnO: Ga micron line to form a Pt @ ZnO: Ga metal modified semiconductor composite structure;
(S2) electrifying the composite structure of the Pt @ ZnO: Ga metal modified semiconductor to heat the composite structure to 480-520 ℃, and converting the Pt quasi-particle nano-film into isolated Pt nano-particles by utilizing the Joule heating effect to obtain a PtNPs @ ZnO: Ga composite micron line;
(S3) pressing the PtNPs @ ZnO: Ga composite micron line on a p-GaN substrate and a gasket to obtain a PtNPs @ n-ZnO: Ga/p-GaN heterostructure;
(S4) preparing an alloy electrode at a position where the p-GaN substrate does not contact the PtNPs @ ZnO: Ga composite microwire in the PtNPs @ n-ZnO: Ga/p-GaN heterostructure, and preparing a metal particle electrode at one end of the PtNPs @ ZnO: Ga composite microwire on the gasket;
(S5) pressing a piece of quartz glass on the surface of the prepared electrode PtNPs @ n-ZnO: Ga/p-GaN heterostructure to obtain the Pt modified ZnO microwire heterojunction light-emitting diode.
In step S1, a Pt quasi-particle nano-film is prepared by a magnetron sputtering method, in step S3, a p-GaN substrate is adhered to a base, in step S2, the average diameter of Pt nanoparticles can be regulated by heating, so that the light-emitting wavelength of the Pt modified ZnO micron-line heterojunction light-emitting diode can be regulated within the wavelength range of 375-396nm, and in step S4, an alloy electrode is prepared by an electron beam evaporation method.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages: 1. the luminous efficiency of Ga micron line of ZnO is enhanced through Pt nano particle modification, the Pt modified ZnO micron line heterojunction light-emitting diode has high ultraviolet luminous efficiency, an ultraviolet luminous peak is arranged at 391nm, and the half-peak width is 38.2 nm; 2. the Pt modified ZnO micron line heterojunction light-emitting diode is a micron-sized photoelectric device, and is convenient to use and prepare; 3. the light emitting wavelength of the light emitting diode can be adjusted by adjusting the diameter of the Pt particles.
Drawings
FIG. 1 is a schematic structural view of the present invention;
FIG. 2 is a scanning electron microscope image of the PtNPs @ ZnO: Ga composite microwire in example 1;
FIG. 3 is a graph of I-V characteristics of example 1;
FIG. 4 is a graph showing the luminous effect of example 1;
FIG. 5 is a graph of the electroluminescence spectrum of example 1;
FIG. 6 is an electroluminescence spectrum of example 2.
Detailed Description
Example 1
Taking a ZnO-Ga micron line with the length of 0.6cm, sputtering a layer of compact Pt quasi-particle film on the surface of the micron line by using a plasma magnetron sputtering instrument to obtain a Pt @ ZnO-Ga metal modified semiconductor composite structure, wherein the thickness of the Pt quasi-particle film is 80nm, the sputtering target material is a Pt target material with the specification of 50.8 × 1.0.0 mm, the purity of 99.99 percent, the working gas is argon, the pressure of a cavity is 32Pa, the sputtering current is 29mA, the sputtering time is 300s, and the electron concentration of the ZnO-Ga micron line is 1019/cm3Electron mobility of 50cm2V.s, the Ga doping concentration is less than 1 percent; adding Pt @ ZnO to Ga metalThe composite structure of the modified semiconductor is placed on a quartz substrate, indium particles are pressed at two ends of the composite structure, the current is adjusted to 12.56mA to enable the composite structure to emit weak light, the surface temperature of a micron line is raised to 500 ℃, a Pt quasi-particle nano film on the cross section of the micron line is converted into isolated nano particles through joule heating effect, the micron line is taken down, the indium particles are removed, and PtNPs @ ZnO Ga composite micron line 2 is obtained, a scanning electron microscope image is shown in figure 2, Pt particles are distributed on a Ga micron line, the particle size of the Pt particles is 90nm, and gaps among the Pt particles are 110 nm;
placing a p-GaN substrate 1 with the size of 1.8 × 1.0.0 cm in a high-temperature tube furnace for annealing at 900 ℃ for 2h, then cleaning the annealed p-GaN substrate 1 and a base 5 by trichloroethylene, acetone, ethanol and deionized water in sequence, and drying by using nitrogen, wherein the thickness of the p-GaN substrate 1 is 2.5 mu m, and the hole concentration is 1019/cm3Hole mobility of 50cm2V.s, adhering the p-GaN substrate 1 on a base 5 by utilizing PMMA, wherein the base 5 is a quartz plate with the size of 2.5 × 1.6.6 cm;
transferring the PtNPs @ ZnO and Ga composite microwire 2 to the surfaces of a p-GaN substrate 1 and a gasket 6 under an optical microscope, wherein the gasket 6 is a plastic sheet with the thickness of 2.5 mu m, one surface, without Pt nanoparticles, of the PtNPs @ ZnO and Ga composite microwire 2 is tightly attached to the surface of the p-GaN, the PtNPs @ ZnO and Ga composite microwire 2 is covered by a mask, an alloy electrode 4 is vapor-plated on one end of the p-GaN by using electron beams, the first layer is a Ni electrode with the thickness of 30nm, the second layer is an Au electrode with the thickness of 50nm, and the alloy electrode 4 is in ohmic contact;
pressing a metal particle electrode 3 at one end of the PtNPs @ ZnO: Ga composite micron line 2 on a gasket 6 by adopting In electrode particles, cleaning quartz glass 7 with the size of 1.0 multiplied by 2.5cm by trichloroethylene, acetone, ethanol and deionized water, drying by using nitrogen, then putting the quartz glass into a vacuum drying oven to dry for 2 hours at 180 ℃, taking out and pressing the quartz glass on the PtNPs @ ZnO: Ga micron line 2 to enable the quartz glass to just cover the PtNPs @ ZnO: Ga composite micron line 2 on a p-GaN substrate 1, and finally forming the PtNPs @ n-ZnO: Ga/p-GaN heterojunction light-emitting diode, wherein the structure of the PtNPs @ ZnO: Ga/p-GaN heterojunction light-emitting diode is shown In figure 1.
Electrical tests are carried out on the PtNPs @ n-ZnO: Ga/p-GaN heterojunction light-emitting diode, an I-V curve chart is shown in figure 3, the starting voltage is 3.2V, and the reverse breakdown voltage is-9.1V; when the diode is subjected to photoelectric performance test, an electroluminescence spectrum is shown in fig. 5, when an excitation voltage is 45V, an ultraviolet light emission peak exists at 391nm, the light emission intensity is 45000a.u., and it can be seen from a light emission photograph taken in fig. 4 that the light emission brightness can be controlled by adjusting different voltages.
Example 2
Taking a ZnO-Ga micron line with the length of 0.6cm, sputtering a layer of compact Pt quasi-particle film on the surface of the micron line by using a plasma magnetron sputtering instrument to obtain a Pt @ ZnO-Ga metal modified semiconductor composite structure, wherein the thickness of the Pt quasi-particle film is 110nm, the sputtering target material is a Pt target material with the specification of 50.8 × 1.0.0 mm, the purity of 99.99 percent, the working gas is argon, the pressure of a cavity is 31Pa, the sputtering current is 28mA, the sputtering time is 450s, and the electron concentration of the ZnO-Ga micron line is 1019/cm3Electron mobility of 50cm2V.s, the Ga doping concentration is less than 1 percent; placing a composite structure of Pt @ ZnO and Ga metal modified semiconductor on a quartz substrate, pressing indium particles at two ends, adjusting current to 15.71mA to enable the composite structure to emit weak light, raising the surface temperature of a microwire to 490 ℃, converting a Pt quasi-particle nano film on the surface of the microwire into isolated nano particles through joule heating effect, taking down the microwire, and removing the indium particles to obtain PtNPs @ ZnO and Ga composite microwire 2, wherein the Pt particles are distributed on the ZnO and Ga microwire, the particle size of the Pt particles is 120nm, and the gap between the Pt particles is 150 nm;
placing a p-GaN substrate 1 with the size of 1.8 × 1.0.0 cm in a high-temperature tube furnace for annealing at 900 ℃ for 2h, then cleaning the annealed p-GaN substrate 1 and a base 5 by trichloroethylene, acetone, ethanol and deionized water in sequence, and drying by using nitrogen, wherein the thickness of the p-GaN substrate 1 is 2.5um, and the hole concentration is 1019/cm3Hole mobility of 50cm2V.s, adhering the p-GaN substrate 1 on a base 5 by utilizing PMMA, wherein the base 5 is a quartz plate with the size of 2.5 × 1.6.6 cm;
transferring the PtNPs @ ZnO and Ga composite microwire 2 to the surfaces of a p-GaN substrate 1 and a gasket 6 under an optical microscope, wherein the gasket 6 is a plastic sheet with the thickness of 2.5 mu m, one surface, without Pt nanoparticles, of the PtNPs @ ZnO and Ga composite microwire 2 is tightly attached to the surface of the p-GaN, the PtNPs @ ZnO and Ga composite microwire 2 is covered by a mask, an alloy electrode 4 is vapor-plated on one end of the p-GaN by using electron beams, the first layer is a Ni electrode with the thickness of 30nm, the second layer is an Au electrode with the thickness of 50nm, and the alloy electrode 4 is in ohmic contact;
pressing a metal particle electrode 3 at one end of the PtNPs @ ZnO: Ga composite micron line 2 on a gasket 6 by adopting In electrode particles, cleaning quartz glass 7 with the size of 1.0 multiplied by 2.5cm by trichloroethylene, acetone, ethanol and deionized water, drying by using nitrogen, then putting the quartz glass into a vacuum drying oven to dry for 2 hours at 180 ℃, taking out the quartz glass and pressing the quartz glass on the PtNPs @ ZnO: Ga micron line 2 to just cover the PtNPs @ ZnO: Ga composite micron line 2 on a p-GaN substrate 1, and finally forming the PtNPs @ n-ZnO: Ga/p-GaN heterojunction light-emitting diode.
The PtNPs @ n-ZnO: Ga/p-GaN heterojunction light-emitting diode is subjected to photoelectric performance test, the electroluminescence spectrum is shown in figure 6, when the excitation voltage is 61V, an ultraviolet light luminescence peak exists at 382nm, and the luminescence intensity is 38000a.u.
Claims (10)
- The Pt modified ZnO micron line heterojunction light-emitting diode is characterized by comprising a p-GaN substrate (1), PtNPs @ ZnO: Ga composite micron lines (2), a gasket (6) and quartz glass (7), wherein the gasket (6) and the p-GaN substrate (1) are equal in thickness and are arranged side by side, the PtNPs @ ZnO: Ga composite micron lines (2) cling to the p-GaN substrate (1), a metal particle electrode (3) is pasted at one end of the gasket (6), an alloy electrode (4) is plated at one end, which is not in contact with the PtNPs @ ZnO: Ga composite micron lines (2), of the p-GaN substrate (1), and the quartz glass (7) presses the PtNPs @ ZnO: Ga composite micron lines (2) on the p-GaN substrate (1).
- 2. The Pt-modified ZnO microwire heterojunction light-emitting diode of claim 1, wherein the p-GaN substrate (1) has a thickness of 2-10 μm and a hole concentration of 1017-1019/cm3Hole mobility of 5-100cm2/V·s。
- 3. The Pt modified ZnO microwire heterojunction light emitting diode of claim 1, wherein the PtNPs @ ZnO: Ga composite microwire (2) is made of Pt nanoparticles modified on the surface of ZnO: Ga microwire.
- 4. The Pt-modified ZnO microwire heterojunction light-emitting diode of claim 3, wherein the electron concentration of the ZnO to Ga microwire is 1017-1019/cm3Electron mobility of 5-100cm2The Ga doping concentration is less than 1 percent.
- 5. The Pt modified ZnO microwire heterojunction light emitting diode of claim 3, wherein the Pt nanoparticles have an average diameter of 30-300nm and a distribution spacing of 50-200 nm.
- 6. The Pt modified ZnO microwire heterojunction light-emitting diode according to claim 1, wherein the alloy electrode (4) is a Ni/Au alloy, the Ni thickness is 20-30 nm, and the Au thickness is 40-50 nm.
- 7. The preparation method of the Pt modified ZnO microwire heterojunction light emitting diode of claim 1, which is characterized by comprising the following steps:(S1) preparing a Pt quasi-particle nano film on a ZnO: Ga micron line to form a Pt @ ZnO: Ga metal modified semiconductor composite structure;(S2) electrifying the Pt @ ZnO: Ga metal modified semiconductor composite structure to heat the composite structure to 480-520 ℃, and converting the Pt quasi-particle nano-film into isolated Pt nano-particles by utilizing the Joule heating effect to obtain a PtNPs @ ZnO: Ga composite micron line (2);(S3) pressing the PtNPs @ ZnO: Ga composite micron line (2) on the p-GaN substrate (1) and the gasket (6) to obtain a PtNPs @ n-ZnO: Ga/p-GaN heterostructure;(S4) preparing an alloy electrode (4) at a position where the p-GaN substrate (1) does not contact the PtNPs @ ZnO: Ga composite microwire (2) in the PtNPs @ n-ZnO: Ga/p-GaN heterostructure, and preparing a metal particle electrode (3) at one end of the PtNPs @ ZnO: Ga composite microwire (2) on a gasket (6);(S5) pressing a piece of quartz glass (7) on the surface of the prepared electrode PtNPs @ n-ZnO: Ga/p-GaN heterostructure to obtain the Pt modified ZnO microwire heterojunction light-emitting diode.
- 8. The method of claim 7, wherein in step S1, the Pt quasi-particle nano-film is prepared by magnetron sputtering, and in step S3, the p-GaN substrate (1) is adhered to the base (5).
- 9. The method as claimed in claim 7, wherein the Pt quasi-particle nano-film has a thickness of 50-150nm in step S1, and the light-emitting wavelength of the Pt-modified ZnO microwire heterojunction light-emitting diode can be adjusted by adjusting the thickness of the Pt quasi-particle nano-film within the wavelength range of 375-396 nm.
- 10. The method of claim 7, wherein the alloy electrode (4) is prepared by electron beam evaporation in step S4.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112234127A (en) * | 2020-10-16 | 2021-01-15 | 南京工程学院 | Single Rh @ ZnO micron line heterojunction ultraviolet-enhanced light-emitting diode and preparation method and application thereof |
| CN117393635A (en) * | 2023-10-17 | 2024-01-12 | 南京航空航天大学 | PtNPs@n-ZnO Ga/p-SiC heterojunction based self-driven ultraviolet photoelectric detector and preparation method thereof |
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