CN101505035A - P-zinc oxide/N- nickel oxide heterogeneous PN junction ultraviolet laser diode and method for production - Google Patents
P-zinc oxide/N- nickel oxide heterogeneous PN junction ultraviolet laser diode and method for production Download PDFInfo
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Abstract
The invention discloses an n -zinc oxide/ p- nickel oxide heterogeneous pn junction ultraviolet laser diode and a preparation method thereof. The heterogeneous pn junction diode at least comprises a pn junction, a substrate and an ohm contacting electrode, wherein the pn junction is the heterogeneous pn junction by plating a p-type nickel oxide film on an n-type zinc oxide film; and the substrate is a sapphire plated with n-type GaN. The preparation method comprises the following steps: firstly preparing the n-type ZnO film layer on the substrate by the radio frequency magnetron sputtering technology; then sputtering a p-type NiO film layer on the n-type ZnO film layer to form the heterogeneity pn junction; finally manufacturing a pn junction electrode by a sputtering method or a thermal evaporation method; sputtering gold electrodes or platinum electrodes or nickel platinum electrodes or ITO electrodes on the NiO surface; plating indium electrodes or aluminum electrodes or gold electrodes on the GaN or the edge of ZnO; and making the electrodes form ohm contact after annealing alloying. The heterogeneous pn junction diode has the advantages of better electro-ultraviolet lasing luminescence characteristic, peak luminous wavelength of about 375 nm, simple preparation process and low cost.
Description
Technical field
The present invention relates to nickel oxide heterogeneous pn junction ultraviolet laser diode of a kind of n-zinc oxide/p-and preparation method thereof, belong to nano material and field of optoelectronic devices.
Background technology
Zinc oxide (ZnO) is a kind of novel II-VI family direct band gap semiconductor material with wide forbidden band.The energy gap of ZnO is 3.37eV in room temperature, and emission wavelength is equivalent to black light wavelength (370nm), is suitable for very much making short-wave long light-emitting and light-sensitive device.ZnO is still similar to GaN on energy gap in lattice structure, cell parameter, and have than higher fusing point of GaN and bigger exciton bind energy, have the threshold value of lower luminescence generated by light and stimulated radiation and good electromechanical coupling characteristics, thermal stability and chemical stability again.Thereby great potential is arranged in the application aspect royal purple light-emitting diode, laser and the relative photo electric device thereof.ZnO is considered to the desirable substitution material of GaN.Along with since some unique characteristics of nano material are found, the low-dimensional nano structure of ZnO also expects to have physics and the chemical property that polycrystal film and body monocrystalline are not had.(the Sheng Chu that has reported, Mario Olmedo, Zheng Yang, Jieying Kong, and Jianlin Liu, Electrically pumped ultraviolet ZnO diode lasers on Si, APPLIED PHYSICSLETTERS 93,181106_2008_) ZnO homojunction ultraviolet swashs and to penetrate diode and need do the multi-layer quantum well structure, and lower, the less stable of used p-ZnO mobility.The ultraviolet laser diode that development structure is simple, with low cost, the gain of light is high has important use and is worth.
Summary of the invention
For improving the performance of traditional ultraviolet light-emitting diode, the invention provides nickel oxide heterogeneous pn junction ultraviolet laser diode of a kind of n-zinc oxide/p-and preparation method thereof.This n-zinc oxide (n-ZnO)/p-nickel oxide (p-NiO) diode of heterogenous pn junction has lower forward cut-in voltage and big forward current density, and rectification characteristic and luminescent properties preferably, and institute's emission wavelength is at 375 ± 3nm, and live width is below 1nm.
Technical scheme provided by the invention is: the nickel oxide heterogeneous pn junction ultraviolet laser diode of a kind of n-zinc oxide/p-, comprise pn knot, substrate and Ohm contact electrode at least, and the pn knot is the heterogenous pn junction that is coated with p type nickel oxide film on n type zinc-oxide film; Substrate is the n type gallium nitride that is grown on the sapphire.
And this heterogenous pn junction ultraviolet laser diode sends the Ultra-Violet Laser of wavelength in 375 ± 3 nanometers under electricity causes incentive action, live width is less than 1 nanometer.Ultra-Violet Laser is Fabry-Perot (Fabry-Perot) resonance Ultra-Violet Laser.
The present invention also provides the preparation method of the nickel oxide heterogeneous pn junction ultraviolet laser diode of this n-zinc oxide/p-, and its concrete steps are at first to prepare n type ZnO film layer with rf magnetron sputtering technology on substrate, and substrate is the n type gallium nitride that is grown on the sapphire; Sputter p type NiO thin layer forms heterogenous pn junction on n type ZnO film layer then; Adopt sputtering method or thermal evaporation to make the pn junction electrode at last; Wherein, NiO surface sputtering gold electrode or platinum electrode or nickel platinum electrode or ITO electrode plate indium electrode or aluminium electrode or gold electrode at GaN or at the ZnO edge; Electrode forms ohmic contact by the after annealing alloying.
Wherein the concrete steps that prepare n type ZnO film layer with rf magnetron sputtering technology on substrate are at first to clean substrate with semiconductor technology; Make with rf magnetron sputtering technology then, the rf magnetron sputtering process conditions are: target is the ZnO ceramic target, and the base vacuum degree is greater than 10 during sputter
-3Pa, underlayer temperature is 100～400 ℃, air pressure is 0.5～5Pa, relative partial pressure of oxygen O during deposition
2/ (O
2+ Ar)=15～40%, sputtering power 80～150W, sputtering time be 15～40 minutes.
Sputter p type NiO thin layer formation heterogenous pn junction is to adopt the Ni metallic target on n type ZnO film layer, at relative partial pressure of oxygen O
2/ (O
2+ Ar)=50～70%, the cavity base vacuum degree before the sputter is greater than 5 * 10
-4Pa, sputtering pressure are 0.5～1.5Pa, under the condition of sputtering power 100～250W, and sputter plating NiO film on n type ZnO, the plated film time is 30～80min, underlayer temperature is 150～400 ℃.
As shown from the above technical solution, the present invention utilizes the ZnO nano thin-film, has been compounded to form heterogenous pn junction structure with the p-NiO film.By to the control of conditions such as ZnO film growth, NiO film preparation, the optimization of pn junction structure etc., improved the heterogenous pn junction performance, it is improved in ultra-violet light-emitting, performance aspect photosensitive. give full play to the advantage of growing high-quality ZnO film on the GaN substrate, improve the luminescent properties of ZnO heterojunction.This diode of heterogenous pn junction has preferably electricity and causes ultraviolet and swash and penetrate the characteristics of luminescence, and peak luminous wavelength is about 375nm, and preparation technology is simple, with low cost.
Description of drawings
Fig. 1 is the structural representation of the embodiment of the invention 1, embodiment 3 and embodiment 4;
Fig. 2 is the luminescent spectrum figure of embodiment 1;
Fig. 3 is that embodiment 2 is structural representations;
Fig. 4 is the luminescent spectrum figure of embodiment 2;
Fig. 5 is the luminescent spectrum figure of embodiment 3;
Fig. 6 is the luminescent spectrum figure of embodiment 4;
Embodiment
The nickel oxide heterogeneous pn junction ultraviolet laser diode of n-zinc oxide/p-of the present invention comprises pn knot, substrate and Ohm contact electrode at least, and wherein the pn knot is the heterogenous pn junction that is coated with p type nickel oxide film on n type zinc-oxide film; Substrate is the n type gallium nitride that is grown on the sapphire.
Its concrete preparation process is as follows:
(1) adopt the cleaning method in the semiconductor technology to clean substrate (substrate) and oven dry;
(2) growing ZnO thin-film layer: used conditional parameter is when carrying out rf magnetron sputtering: target is the ZnO ceramic target.The base vacuum degree is better than 10 during sputter
-3Pa, underlayer temperature is 100～400 ℃, air pressure is 0.5～5Pa, relative partial pressure of oxygen O during deposition
2/ (O
2+ Ar)=15～40%, sputtering power scope 80～150W, sputtering time be 15 minutes～40 minutes (as document Guojia Fang, et al., Influence of post-deposition annealing on theproperties of transparent conductive nanocrystalline AZO (ZnO:Al) thin films preparedby RF magnetron sputtering with highly conductive ceramic target, Thin Solid Films, 2002,418 (2): 156-162);
(3) preparation of p-NiO: adopting diameter is the Ni metallic target of 50mm.Report (I.Hotovy, J.Huran, J. according to people such as I.Hotovy
Et al., Deposition and properties of nickel oxide filmsproduced by DC reactive magnetron sputtering, Vacuum, 1998,51 (2): 157.), the NiO film of reactive magnetron sputtering preparation, the O in mixed atmosphere
2When ratio raise, the resistivity of film can rise thereupon, and light transmittance then can descend thereupon, to make the NiO film and had higher electric conductivity and light transmission simultaneously, the relative partial pressure of oxygen O that we adopt in order to make
2/ (O
2+ Ar)=50～70% this optimized amount.Cavity base vacuum degree before the sputter is greater than 5 * 10
-4Pa, sputtering pressure are 0.5～1.5Pa, sputtering power 100～250W.Before plated film, pre-sputter 10min is to remove the impurity of target material surface.Growing plating NiO film on the substrate of having got well ZnO film.The plated film time is 30～80min, underlayer temperature be 150～400 ℃ (as document Lei Ai,
Guojia Fang *LongyanYuan, Nishuang Liu, Mingjun Wang, Chun Li, Qilin Zhang, Jun Li, Xingzhong Zhao, Influence ofsubstrate temperature on electrical and optical properties of p-type semitransparent conductivenickel oxide thin films deposited by radio frequency sputtering, Appl.Surf.Sci., 254 (2008) 2401-2405).
(4) preparation of electrode: adopt surface and ZnO or the GaN edge making electrode of methods such as sputtering method or thermal evaporation (as: Tang Weizhong work, thin-film material preparation principle, technology and application, metallurgical industry publishing house 1998 front pages) at NiO.NiO surface sputtering platinum or gold electrode or Ni/Pt electrode or ito transparent electrode, ZnO or GaN edge plate indium or gold or aluminium electrode.Electrode forms ohmic contact by the after annealing alloying.
(5) test
Adopt the characteristics of luminescence of a constant pressure source and PL spectrum testing system measuring diode.
Above-mentioned substrate is the sapphire 1 that is coated with n type GaN2.
Embodiment 1:
1. substrate cleans: adopting the n type GaN that is grown on the sapphire is substrate, is cut into 25mm * 30mm size, adopts acetone, alcohol, deionized water ultrasonic cleaning 3min respectively, dries up with nitrogen gun at last.
2.n the growth of type layer ZnO: use the method for rf magnetron sputtering on GaN1, to deposit ZnO film 2.Target is selected the ZnO ceramic target for use, and base vacuum is 1*10
-3Pa, deposition substrate temperature: 300 ℃; Air pressure during deposition: 0.5Pa; Relative partial pressure of oxygen O
2/ (O
2+ Ar)=15%, power 150W; Sputtering time: 15min.
3.p-NiO preparation: use the method for reactive sputtering on the ZnO nano thin-film, to deposit NiO film 3.Target is selected highly purified metal Ni target, base vacuum 4*10 for use
-4Pa, deposition substrate temperature: 150 ℃; Deposition pressure: 1.5Pa, partial pressure of oxygen O relatively
2/ (O
2+ Ar)=50%; Power: 100W, sputtering time: 80min.
4. the preparation of electrode: adopt the method for rf magnetron sputtering to prepare Au electrode 4 under NiO film surface normal temperature, sedimentation time is 20s.Plating In is as n type electrode 5 on the GaN film of substrate surface.The structure chart that obtains at last as shown in Figure 1.
5. test: the luminescent spectrum that records this diode of heterogenous pn junction is as shown in Figure 2.
Embodiment 2:
1. substrate cleans: adopting the n type GaN that is grown on the sapphire is substrate, is cut into 25mm * 30mm size, adopts acetone, alcohol, deionized water ultrasonic cleaning 3min respectively, dries up with nitrogen gun at last.
2.n the growth of type layer: use the method for rf magnetron sputtering on GaN1, to deposit ZnO film 2.Target is selected the ZnO ceramic target for use, and base vacuum is 8*10
-4Pa, deposition substrate temperature: 100 ℃; Air pressure during deposition: 5.0Pa; Relative partial pressure of oxygen O
2/ (O
2+ Ar)=40%, power 80W; Sputtering time: 40min.
3.p-NiO preparation: the method for using reactive sputtering is deposition NiO film 3 on the long sheet glass that the ZnO nano rod arranged.Target is selected highly purified metal Ni target for use, and base vacuum is 5*10
-4Pa, deposition substrate temperature: 400 ℃; Deposition pressure: 0.5Pa, partial pressure of oxygen O relatively
2/ (O
2+ Ar)=70%; Power: 250W, sputtering time: 30min.
4. the preparation of electrode: adopt the method for rf magnetron sputtering to prepare Pt electrode 4 under NiO film surface normal temperature, sedimentation time is 20s.Plating Al is as n type electrode 5 on the ZnO film.The structure chart that obtains at last as shown in Figure 3.
5. test: the luminescent spectrum that records this diode of heterogenous pn junction is as shown in Figure 4.
Embodiment 3:
1. substrate cleans: adopting the n type GaN that is grown on the sapphire is substrate, is cut into 25mm * 30mm size, adopts acetone, alcohol, deionized water ultrasonic cleaning 3min respectively, dries up with nitrogen gun at last.
2.n the growth of type layer: use the method for rf magnetron sputtering on GaN1, to deposit ZnO film 2.Target is selected the ZnO ceramic target for use, and base vacuum is 1*10
-3Pa, deposition substrate temperature: 300 ℃; Air pressure during deposition: 1.0Pa; Relative partial pressure of oxygen O
2/ (O
2+ Ar)=20%, power 100W; Sputtering time: 30min.
3.p-NiO preparation: use the method for reactive sputtering on ZnO film, to deposit NiO film 3.Target is selected highly purified metal Ni target for use, and base vacuum is 10
-3Pa, deposition substrate temperature: 300 ℃; Deposition pressure: 1.0Pa, partial pressure of oxygen O relatively
2/ (O
2+ Ar)=60%; Power: 150W, sputtering time: 40min.
6. the preparation of electrode; Adopt the method for rf magnetron sputtering to prepare ITO electrode 4 under NiO film surface normal temperature, sedimentation time is 20s.Plating Au is as n type electrode 5 on the GaN film.The structure chart that obtains at last as shown in Figure 1.
7. test: the luminescent spectrum that records this diode of heterogenous pn junction is as shown in Figure 5.
Embodiment 4:
1. substrate cleans: adopting the n type GaN that is grown on the sapphire is substrate, is cut into 25mm * 30mm size, adopts acetone, alcohol, deionized water ultrasonic cleaning 3min respectively, dries up with nitrogen gun at last.
2.n the growth of type layer: use the method for rf magnetron sputtering on GaN1, to deposit ZnO film 2.Target is selected the ZnO ceramic target for use, and base vacuum is 9*10
-4Pa, deposition substrate temperature: 300 ℃; Air pressure during deposition: 1.0Pa; Relative partial pressure of oxygen O
2/ (O
2+ Ar)=30%, power 120W; Sputtering time: 25min.
3.p-NiO preparation: use the method for reactive sputtering on ZnO film 2, to deposit NiO film 3.Target is selected highly purified metal Ni target for use, and base vacuum is 3*10
-4Pa, deposition substrate temperature: 300 ℃; Deposition pressure: 1.0Pa, partial pressure of oxygen O relatively
2/ (O
2+ Ar)=20%; Power: 100W, sputtering time: 50min.
4. the preparation of electrode: adopt the method for rf magnetron sputtering under NiO film surface normal temperature, to prepare Ni/Pt electrode 4,, the sedimentation time of Ni and Pt is respectively 10s, 20s.Plating Al is as n type electrode 5 on the GaN film.The structure chart that obtains at last as shown in Figure 1.
5. test: the luminescent spectrum that records this diode of heterogenous pn junction is as shown in Figure 6.
Claims (6)
1, the nickel oxide heterogeneous pn junction ultraviolet laser diode of a kind of n-zinc oxide/p-comprises pn knot, substrate and Ohm contact electrode at least, it is characterized in that: the pn knot is the heterogenous pn junction that is coated with p type nickel oxide film on n type zinc-oxide film; Substrate is the n type gallium nitride that is grown on the sapphire.
2, the nickel oxide heterogeneous pn junction ultraviolet laser diode of n-zinc oxide/p-according to claim 1, it is characterized in that: this heterogenous pn junction ultraviolet laser diode is under electricity causes incentive action, send the Ultra-Violet Laser of wavelength in 375 ± 3 nanometers, live width is less than 1 nanometer.
3, the nickel oxide heterogeneous pn junction ultraviolet laser diode of n-zinc oxide/p-according to claim 2 is characterized in that: Ultra-Violet Laser is a Fabry-Perot resonance Ultra-Violet Laser.
4, the preparation method of the nickel oxide heterogeneous pn junction ultraviolet laser diode of the described n-zinc-oxide film/p-of claim 1, it is characterized in that adopting following concrete steps: at first prepare n type ZnO film layer with rf magnetron sputtering technology on substrate, substrate is the n type gallium nitride that is grown on the sapphire; Sputter p type NiO thin layer forms heterogenous pn junction on n type ZnO film layer then; Adopt sputtering method or thermal evaporation to make the pn junction electrode at last; Wherein, NiO surface sputtering gold electrode or platinum electrode or nickel platinum electrode or ITO electrode plate indium electrode or aluminium electrode or gold electrode at GaN or at the ZnO edge; Electrode forms ohmic contact by the after annealing alloying.
5, preparation method according to claim 4 is characterized in that: the concrete steps that prepare n type ZnO film layer with rf magnetron sputtering technology on substrate are at first to clean substrate with semiconductor technology; Make with rf magnetron sputtering technology then, the rf magnetron sputtering process conditions are: target is the ZnO ceramic target, and the base vacuum degree is greater than 10 during sputter
-3Pa, underlayer temperature is 100～400 ℃, air pressure is 0.5～5Pa, relative partial pressure of oxygen O during deposition
2/ (O
2+ Ar)=15～40%, sputtering power 80～150W, sputtering time be 15～40 minutes.
6, preparation method according to claim 4 is characterized in that: sputter p type NiO thin layer formation heterogenous pn junction is to adopt the Ni metallic target on n type ZnO film layer, at relative partial pressure of oxygen O
2/ (O
2+ Ar)=50～70%, the cavity base vacuum degree before the sputter is greater than 5 * 10
-4Pa, sputtering pressure are 0.5～1.5Pa, under the condition of sputtering power 100～250W, and sputter plating NiO film on n type ZnO, the plated film time is 30～80min, underlayer temperature is 150～400 ℃.
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| CN106784156A (en) * | 2017-01-05 | 2017-05-31 | 上海芯石微电子有限公司 | One kind is based on NiO/ZnO nanorod heterojunction diodes and preparation method thereof |
| CN107460438A (en) * | 2017-07-04 | 2017-12-12 | 北京化工大学 | A kind of method that the super flat NiO films of large area are prepared based on vapour deposition process |
| CN111029475A (en) * | 2019-11-25 | 2020-04-17 | 深圳市华星光电半导体显示技术有限公司 | Display and preparation method thereof |
| CN111381077A (en) * | 2020-03-02 | 2020-07-07 | 五邑大学 | Method for manufacturing film body electrode and film |
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