CN101888061B - ZnO/ZnMgO multi-quantum trap ultraviolet laser diode and preparation method thereof - Google Patents

ZnO/ZnMgO multi-quantum trap ultraviolet laser diode and preparation method thereof Download PDF

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CN101888061B
CN101888061B CN2010102140268A CN201010214026A CN101888061B CN 101888061 B CN101888061 B CN 101888061B CN 2010102140268 A CN2010102140268 A CN 2010102140268A CN 201010214026 A CN201010214026 A CN 201010214026A CN 101888061 B CN101888061 B CN 101888061B
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zno
quantum well
multiple quantum
laser diode
electrode
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CN101888061A (en
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方国家
龙浩
黄晖辉
李颂战
莫小明
王皓宁
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Changshu Zijin Intellectual Property Service Co ltd
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Wuhan University WHU
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Abstract

The invention discloses a ZnO/ZnMgO multi-quantum trap ultraviolet laser diode and a preparation method thereof. The substrate of the ultraviolet laser diode is n-shaped GaN growing on a sapphire, a ZnO/Zn1-xMgxO multi-quantum trap active layer formed by alternately depositing ZnoO and Zn1-xMgxO, a p-shaped NiO thin film layer and a second electrode are sequentially arranged on the substrate from bottom to top, and a first electrode and the ZnO/Zn1-xMgxO multi-quantum trap active layer are deposited on an n-shaped GaN film layer in parallel. The preparation method of the ZnO/ZnMgO multi-quantum trap ultraviolet laser diode comprises the following steps of: firstly preparing the ZnO/Zn1-xMgxO multi-quantum trap active layer on the substrate by using a radio-frequency magnetic-control sputtering process; then sputtering the p-shaped NiO thin film layer on the n-shaped ZnO thin film layer; and finally making the first electrode and the second electrode. The ZnO/ZnMgO multi-quantum trap ultraviolet laser diode has the characteristic of favorable electro-ultraviolet free lasing light emitting, the light-emitting peak wavelength is about 373 nm, and the width of single lasing light rays is less than 0.5 nm. The ZnO/ZnMgO multi-quantum trap ultraviolet laser diode has the advantages of simple preparation process, low cost and easy realization of industrialization.

Description

ZnO/ZnMgO multi-quantum trap ultraviolet laser diode and preparation method thereof
Technical field
The present invention relates to a kind of laser diode and preparation method thereof, belong to 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, opto-electronic device such as photosensitive.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, simultaneously with low cost and environmental friendliness.Thereby ZnO is considered to the desirable substitution material of GaN, in the application aspect short-wave long light-emitting diode, laser and the relative photo electric device thereof great potential arranged.
But existing zno-based ultraviolet light-emitting diode ubiquity luminous intensity is not high; Be difficult to realize electricity cause ultraviolet freely swash penetrate luminous; It is as seen luminous that some device is attended by stronger deep energy level; The excessive device heating that causes of threshold current influences problems such as device stability and luminescent properties, thereby has limited its practicability.
The energy gap of ZnO:Mg alloy can be along with the Mg component different adjusted, can realize energy band engineering; And low-doped ZnO:Mg alloy and the lattice mismatch of ZnO are little, can be applicable to the ZnO/MgZnO quantum well structure, utilize this structure will improve the recombination probability of charge carrier in the ZnO trap to a great extent, realize high efficiency electricity cause ultraviolet freely swash penetrate luminous.The international and domestic report that does not also have ZnO/ZnMgO multi-quantum trap ultraviolet laser diode and preparation method thereof.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of ZnO/ZnMgO multi-quantum trap ultraviolet laser diode and preparation method thereof.
ZnO/ZnMgO multi-quantum trap ultraviolet laser diode of the present invention, substrate are the n type GaN that is grown on the sapphire; Have successively by ZnO and Mg from bottom to top at substrate 1-xZn xThe ZnO/Zn that the O alternating deposit forms 1-xMg xO multiple quantum well active layer, p type NiO thin layer and first electrode; Also have second electrode and ZnO/Zn 1-xMg xThe O multiple quantum well active layer is deposited on the n type GaN rete side by side, wherein ZnO/Zn 1-xMg x0.1≤x of O multiple quantum well active layer≤0.3.
Described ZnO/Zn 1-xMg xThe O multiple quantum well active layer is by the ZnO film in 3~10 cycles and Zn 1-xMg xThe structure that the O film alternately forms.
Described first electrode is Au, Pt, Pt/Ni or Au/Ni.
Described second electrode is In, Al, Ga or Ag.
The invention also discloses the preparation method of above-mentioned ZnO/ZnMgO multi-quantum trap ultraviolet laser diode, concrete steps are as follows: adopting the n type GaN that is grown on the sapphire is substrate, at first clean substrate, on n type GaN substrate, replace sputter ZnO film and Zn by rf magnetron sputtering technology then with semiconductor technology 1-xMg xThe O film forms ZnO/Zn 1-xMg xThe O multiple quantum well active layer; At ZnO/Zn 1-xMg xReactive sputtering p type NiO thin layer on the O multiple quantum well active layer; Plate first electrode by rf magnetron sputtering technology on p type NiO surface at last, plate second electrode at n type GaN edge.
By rf magnetron sputtering prepared ZnO/Zn 1-xMg xIn the process of O multiple quantum well active layer, the target of preparation ZnO film is the ZnO ceramic target, preparation Zn 1-xMg xThe target of O film is Mg and ZnO hybrid target, and background air pressure is not more than 10 during sputter -3Pa, underlayer temperature is 200~400 ℃, air pressure is 0.5~5Pa, relative partial pressure of oxygen O during deposition 2/ (O 2+ Ar) be 15~40%, sputtering power 60~150W, every layer of sputtering time be 1~3 minute.
Preparation Zn 1-xMg xThe target of O film is selected the mixed target of Mg metallic target and ZnO ceramic target for use, and wherein the area ratio of Mg metallic target and ZnO ceramic target is 1: 0.5~1.5.
At ZnO/Zn 1-xMg xIn the process of reactive sputtering p type NiO thin layer, adopt the Ni metallic target on the O multiple quantum well active layer, relatively partial pressure of oxygen O 2/ (O 2+ Ar) be 50~70%, the cavity background air pressure before the sputter is not more than 10 -3Pa, underlayer temperature are that 150~400 ℃, sputtering pressure are that 0.5~5Pa, sputtering power 80~200W, sputtering time are 20~60 minutes.
Beneficial effect of the present invention is:
1. use ZnO/Zn 1-xMg xThe O Multiple Quantum Well has improved the recombination probability of charge carrier in the ZnO trap greatly, has made full use of the advantage of ZnO semi-conducting material broad stopband and big exciton binding energy, has improved luminous efficiency.By rational designs and material preparation process optimization, realized ultraviolet freely swash penetrate luminous;
2. adopt the n type GaN that is grown on the Sapphire Substrate as substrate, as ZnO/Zn 1-xMg xThe electron injecting layer of O multiple quantum well active layer, this substrate and ZnO/Zn simultaneously 1-xMg xThe O Multiple Quantum Well has realized good lattice match, has improved ZnO/Zn 1-xMg xThe crystal mass of O Multiple Quantum Well has reduced non-radiative compoundly, has improved electricity greatly and has caused ultra-violet light-emitting intensity.
3. adopt p type NiO as hole injection layer, the relative ZnO of energy gap is bigger under its room temperature, has given full play to the super injection advantage of heterojunction; Simultaneously, there is Ni in the NiO film 2+The room, make film at room temperature present natural hole conduction, thereby avoided the influence of excessive doping crystal mass.
4. the present invention adopts rf magnetron sputtering systems produce multiple quantum well active layer, greatly reduces cost, helps realizing industrialization production.
Description of drawings
Fig. 1 is the structural representation of ZnO/ZnMgO multi-quantum trap ultraviolet laser diode of the present invention, 1-sapphire wherein, 2-GaN, 3-ZnO/Zn 1-xMg xThe O multiple quantum well active layer, 4-NiO thin layer, 5-first electrode, 6-second electrode;
Fig. 2 is the room temperature electroluminescent spectrogram of the ZnO/ZnMgO multi-quantum trap ultraviolet laser diode that makes of embodiment 1;
Fig. 3 is the room temperature electroluminescent spectrogram of the ZnO/ZnMgO multi-quantum trap ultraviolet laser diode that makes of embodiment 2;
Fig. 4 is the room temperature electroluminescent spectrogram of the ZnO/ZnMgO multi-quantum trap ultraviolet laser diode that makes of embodiment 3;
Fig. 5 is the room temperature electroluminescent spectrogram of the ZnO/ZnMgO multi-quantum trap ultraviolet laser diode that makes of embodiment 4.
Embodiment
With reference to Fig. 1, ZnO/ZnMgO multi-quantum trap ultraviolet laser diode of the present invention, substrate is for being grown in the n type GaN (2) on the sapphire (1); Have successively by ZnO and Mg from bottom to top at substrate 1-xZn xThe ZnO/Zn that the O alternating deposit forms 1-xMg xO multiple quantum well active layer (3), p type NiO thin layer (4) and first electrode (5) also have second electrode (6) and ZnO/Zn 1-xMg xO multiple quantum well active layer (3) is deposited on n type GaN (2) rete side by side, wherein ZnO/Zn 1-xMg x0.1<x≤0.3 of O multiple quantum well active layer (3).
Embodiment 1:
1. substrate cleans: adopting the n type GaN that is grown on the sapphire is substrate, is cut into 15mm * 15mm size, adopts acetone, alcohol, deionized water to distinguish ultrasonic cleaning 3 minutes, dries up with nitrogen gun at last.
2.ZnO/Zn 1-xMg xThe growth of O multiple quantum well active layer: the substrate after the surface clean is put into the growth room of rf magnetron sputtering system, and the growth room is evacuated to background air pressure 5 * 10 -4Pa, heated substrate to temperature is 250 ℃.Select the target of ZnO ceramic target as deposition ZnO potential well layer for use, the mixed target of selecting Mg metallic target and ZnO ceramic target for use is as deposition Zn 1-xMg xThe target of O barrier layer, wherein the area ratio of Mg metallic target and ZnO ceramic target is 2: 3, the Zn of this condition preparation 1-xMg xX=0.1 in the O layer.Before plated film, pre-sputter 10min is to remove the impurity of target material surface.Use the method for rf magnetron sputtering on n type GaN, alternately to deposit ZnO film layer and Zn then 0.9Mg 0.1The O thin layer, the ZnO/Zn in 10 cycles of formation 0.9Mg 0.1The O mqw active layer.250 ℃ of deposition substrate temperature; Air pressure 0.5Pa during deposition; Relative partial pressure of oxygen O 2/ (O 2+ Ar) be 40%, power 60W; Sputtering time 1min/ layer.
3.p the preparation of type NiO: the method for using reactive sputtering is at ZnO/Zn 0.9Mg 0.1Deposition NiO film on the O mqw active layer.Before plated film, pre-sputter 5min is to remove the impurity of target material surface.Target is selected highly purified metal Ni target, background air pressure 5 * 10 for use -4Pa, deposition substrate temperature: 150 ℃; Deposition pressure: 0.5Pa, partial pressure of oxygen O relatively 2/ (O 2+ Ar) be 50%; Power: 120W, sputtering time: 30min.
4. the preparation of electrode: adopt the method for rf magnetron sputtering to prepare the Au electrode down as first electrode 100 ℃ of NiO film surfaces, sedimentation time is 15s.The n type GaN of substrate surface goes up plating In as second electrode.
The electroluminescent spectrum figure that records the ZnO/ZnMgO multi-quantum trap ultraviolet laser diode that present embodiment 1 makes under the room temperature 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 15mm * 15mm size, adopts acetone, alcohol, deionized water to distinguish ultrasonic cleaning 3 minutes, dries up with nitrogen gun at last.
2.ZnO/Zn 1-xMg xThe growth of O multiple quantum well active layer: the substrate after the surface clean is put into the growth room of rf magnetron sputtering system, and the growth room is evacuated to background air pressure 1 * 10 -3Pa, heated substrate to temperature is 200 ℃.Select the target of ZnO ceramic target as deposition ZnO potential well layer for use, the mixed target of selecting Mg metallic target and ZnO ceramic target for use is as deposition Zn 1-xMg xThe target of O barrier layer, wherein the area ratio of Mg metallic target and ZnO ceramic target is 1: 1, the Zn of this condition preparation 1-xMg xX=0.18 in the O layer.Before plated film, pre-sputter 10min is to remove the impurity of target material surface.Use the method for rf magnetron sputtering on n type GaN, alternately to deposit ZnO film layer and Zn then 0.82Mg 0.18The O thin layer, the ZnO/Zn in 3 cycles of formation 0.82Mg 0.18The O mqw active layer.200 ℃ of deposition substrate temperature; Air pressure 5.0Pa during deposition; Relative partial pressure of oxygen O 2/ (O 2+ Ar) be 20%, power 150W; Sputtering time 3.0min/ layer.
3.p the preparation of type NiO: the method for using reactive sputtering is at ZnO/Zn 0.82Mg 0.18Deposition NiO film on the O mqw active layer.Before plated film, pre-sputter 5min is to remove the impurity of target material surface.Target is selected highly purified metal Ni target, background air pressure 5 * 10 for use -4Pa, deposition substrate temperature: 400 ℃; Deposition pressure: 5.0Pa, partial pressure of oxygen O relatively 2/ (O 2+ Ar) be 70%; Power: 200W, sputtering time: 60min.
4. the preparation of electrode: adopt the method for rf magnetron sputtering to prepare the Pt electrode down as first electrode 100 ℃ of NiO film surfaces, sedimentation time is 15s.The n type GaN of substrate surface goes up plating Ag as second electrode.The electroluminescent spectrum figure that records the ZnO/ZnMgO multi-quantum trap ultraviolet laser diode that present embodiment 2 makes under the room temperature as shown in Figure 3.
Embodiment 3:
1. substrate cleans: adopting the n type GaN that is grown on the sapphire is substrate, is cut into 15mm * 15mm size, adopts acetone, alcohol, deionized water ultrasonic cleaning 3min respectively, dries up with nitrogen gun at last.
2.ZnO/Zn 1-xMg xThe growth of O multiple quantum well active layer: the substrate after the surface clean is put into the growth room of rf magnetron sputtering system, and the growth room is evacuated to background air pressure 1 * 10 -3Pa, heated substrate to temperature is 300 ℃.Select the target of ZnO ceramic target as deposition ZnO potential well layer for use, the mixed target of selecting Mg metallic target and ZnO ceramic target for use is as deposition Zn 1-xMg xThe target of O barrier layer, wherein the area ratio of Mg metallic target and ZnO ceramic target is 1: 1, the Zn of this condition preparation 1-xMg xX=0.18 in the O layer.Before plated film, pre-sputter 10min is to remove the impurity of target material surface.Use the method for rf magnetron sputtering on n type GaN, alternately to deposit ZnO film layer and Zn then 0.82Mg 0.18The O thin layer, the ZnO/Zn in 5 cycles of formation 0.82Mg 0.18The O mqw active layer.300 ℃ of deposition substrate temperature; Air pressure 1.0Pa during deposition; Relative partial pressure of oxygen O 2/ (O 2+ Ar) be 15%, power 100W; Sputtering time 1.5min/ layer.
3.p the preparation of type NiO: the method for using reactive sputtering is at ZnO/Zn 0.82Mg 0.18Deposition NiO film on the O mqw active layer.Before plated film, pre-sputter 5min is to remove the impurity of target material surface.Target is selected highly purified metal Ni target, background air pressure 5 * 10 for use -4Pa, deposition substrate temperature: 300 ℃; Deposition pressure: 2.0Pa, partial pressure of oxygen O relatively 2/ (O 2+ Ar) be 50%; Power: 80W, sputtering time: 30min.
4. the preparation of electrode: adopt the method for rf magnetron sputtering to prepare the Au/Ni electrode down as first electrode 100 ℃ of NiO film surfaces, sedimentation time is 20s.The n type GaN of substrate surface goes up plating Al as second electrode.
The electroluminescent spectrum figure that records the ZnO/ZnMgO multi-quantum trap ultraviolet laser diode that present embodiment 3 makes under the room temperature as shown in Figure 4.
Embodiment 4:
1. substrate cleans: adopting the n type GaN that is grown on the sapphire is substrate, is cut into 15mm * 15mm size, adopts acetone, alcohol, deionized water ultrasonic cleaning 3min respectively, dries up with nitrogen gun at last.
2.ZnO/Zn 1-xMg xThe growth of O multiple quantum well active layer: the substrate after the surface clean is put into the growth room of rf magnetron sputtering system, and the growth room is evacuated to air pressure 1 * 10 -3Pa, heated substrate to temperature is 400 ℃.Select the target of ZnO ceramic target as deposition ZnO potential well layer for use, the mixed target of selecting Mg metallic target and ZnO ceramic target for use is as deposition Zn 1-xMg xThe target of O barrier layer, wherein the area ratio of Mg metallic target and ZnO ceramic target is 2: 1, the Zn of this condition preparation 1-xMg xX=0.3 in the O layer.Before plated film, pre-sputter 10min is to remove the impurity of target material surface.Use the method for rf magnetron sputtering on n type GaN, alternately to deposit ZnO film layer and Zn then 0.7Mg 0.3The O thin layer, the ZnO/Zn in 8 cycles of formation 0.7Mg 0.3The O mqw active layer.400 ℃ of deposition substrate temperature; Air pressure 0.8Pa during deposition; Relative partial pressure of oxygen O 2/ (O 2+ Ar) be 15%, power 120W; Sputtering time 1.5min/ layer.
3.p the preparation of type NiO: the method for using reactive sputtering is at ZnO/Zn 0.7Mg 0.3Deposition NiO film on the O mqw active layer.Before plated film, pre-sputter 5min is to remove the impurity of target material surface.Target is selected highly purified metal Ni target, base vacuum 1 * 10 for use -3Pa, deposition substrate temperature: 300 ℃; Deposition pressure: 1.5Pa, partial pressure of oxygen O relatively 2/ (O 2+ Ar) be 50%; Power: 120W, sputtering time: 20min.
4. the preparation of electrode: adopt the method for rf magnetron sputtering to prepare the Pt/Ni electrode down as first electrode 100 ℃ of NiO film surfaces, sedimentation time is 15s.The n type GaN of substrate surface goes up plating Ga as second electrode.
The electroluminescent spectrum figure that records the ZnO/ZnMgO multi-quantum trap ultraviolet laser diode that present embodiment 4 makes under the room temperature as shown in Figure 5.
From embodiments of the invention as can be seen, the ZnO/ZnMgO multi-quantum trap ultraviolet laser diode of preparation has rectification characteristic and luminescent properties preferably, the ultraviolet that this ultraviolet laser diode sends wavelength 373 (± 3) nm freely swashs penetrates laser, single swash penetrate optical linewidth less than 0.5nm, threshold current density 4.7A/cm 2

Claims (7)

1. a ZnO/ZnMgO Multiple Quantum Well electricity causes ultraviolet and freely swashs and penetrate laser diode, and it is characterized in that: substrate is for being grown in the n type GaN (2) on the sapphire (1); Have successively by ZnO and Zn from bottom to top at substrate 1-xMg xThe ZnO/Zn that the O alternating deposit forms 1-xMg xO multiple quantum well active layer (3), p type NiO thin layer (4) and first electrode (5); Also have second electrode (6) and ZnO/Zn 1-xMg xO multiple quantum well active layer (3) is deposited on the n type GaN layer (2), wherein side by side
ZnO/Zn 1-xMg xIn the O multiple quantum well active layer (3), 0.1≤x≤0.3.
2. the ultraviolet that causes ZnO/ZnMgO Multiple Quantum Well electricity according to claim 1 freely swashs penetrates laser diode, it is characterized in that: described ZnO/Zn 1-xMg xO multiple quantum well active layer (3) is ZnO film and the Zn by 3~10 cycles 1-xMg xThe structure that the O film alternately forms.
3. the ultraviolet that causes ZnO/ZnMgO Multiple Quantum Well electricity according to claim 1 and 2 freely swashs penetrates laser diode, and it is characterized in that: described first electrode (5) is Au, Pt, Pt/Ni or Au/Ni.
4. the ultraviolet that causes ZnO/ZnMgO Multiple Quantum Well electricity according to claim 1 and 2 freely swashs penetrates laser diode, and it is characterized in that: described second electrode (6) is In, Al, Ga or Ag.
5. the described ZnO/ZnMgO Multiple Quantum Well of claim 1 electricity causes ultraviolet and freely swashs the preparation method who penetrates laser diode, it is characterized in that: adopting the n type GaN (2) that is grown on the sapphire is substrate, at first clean substrate, on n type GaN (2) substrate, replace sputter ZnO film and Zn by rf magnetron sputtering technology then with semiconductor technology 1-xMg xThe O film forms ZnO/Zn 1-xMg xO multiple quantum well active layer (3); At ZnO/Zn 1-xMg xO multiple quantum well active layer (3) goes up reactive sputtering p type NiO thin layer (4); Plate first electrode (5) by rf magnetron sputtering technology on p type NiO (4) surface at last, plate second electrode (6) at n type GaN (2) edge.
6. preparation method according to claim 5 is characterized in that: by rf magnetron sputtering prepared ZnO/Zn 1-xMg xIn the process of O multiple quantum well active layer (3), the target of preparation ZnO film is the ZnO ceramic target, preparation Zn 1-xMg xThe target of O film is Mg and ZnO hybrid target, and background air pressure is not more than 10 during sputter -3Pa, underlayer temperature is 200~400 ℃, air pressure is 0.5~5Pa, relative partial pressure of oxygen O during deposition 2/ (O 2+ Ar) be 15~40%, sputtering power 60~150W, every layer of sputtering time be 1~3 minute.
7. according to claim 5 or 6 described preparation methods, it is characterized in that: at ZnO/Zn 1-xMg xO multiple quantum well active layer (3) goes up in the process of reactive sputtering p type NiO thin layer (4), adopts the Ni metallic target, relatively partial pressure of oxygen O 2/ (O 2+ Ar) be 50~70%, the cavity background air pressure before the sputter is not more than 10 -3Pa, underlayer temperature are that 150~400 ℃, sputtering pressure are that 0.5~5Pa, sputtering power 80~200W, sputtering time are 20~60 minutes.
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