CN103147042B - Manufacturing method of magnesium/arsenium-codoped p-type zinc oxide film - Google Patents
Manufacturing method of magnesium/arsenium-codoped p-type zinc oxide film Download PDFInfo
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- CN103147042B CN103147042B CN201310067218.4A CN201310067218A CN103147042B CN 103147042 B CN103147042 B CN 103147042B CN 201310067218 A CN201310067218 A CN 201310067218A CN 103147042 B CN103147042 B CN 103147042B
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Abstract
The invention discloses a manufacturing method of a magnesium/arsenium-codoped p-type zinc oxide film, which comprises the following steps: placing sapphire used as a substrate in an ultrasonic oscillator containing anhydrous ethanol, cleaning to remove grease on the surface of the substrate, then placing the substrate in an ultrasonic oscillator containing deionized water, and cleaning to remove the residual anhydrous ethanol; mixing zinc oxide powder having a purity of 99.99%, magnesium oxide powder having a magnesium mol content of 8-13% and arsenium oxide powder having an arsenium mol content of 0.5-1.5%, and then pressing to form a target material; placing the substrate into a magnetron sputtering reaction chamber, and depositing the target material on the substrate through sputtering in an inert gas environment based on a radio-frequency magnetron sputtering method, thus forming a magnesium/arsenium-codoped p-type ZnO crystal film having a thickness of 200-400nm on the substrate; and naturally cooling the substrate after the previous step.
Description
Technical field
The invention belongs to field of semiconductor lasers, relate in particular to a kind of manufacture method that can be used for the magnesium arsenic codoped p type zinc-oxide film of semiconductor laser diode.
Background technology
Zinc oxide (ZnO) is in crystalline network, unit cell parameters or all similar to GaN in energy gap, and there is the fusing point higher than GaN and larger exciton bind energy, there is again threshold value and good electromechanical coupling characteristics, thermostability and the chemical stability of lower photoluminescence and stimulated radiation.Thus the application in royal purple light-emitting diode, laser apparatus and relative photo electrical part thereof has huge potentiality.At room temperature, the energy gap of zinc oxide (ZnO) is 3.37eV, and free exciton combines can up to 60meV, much larger than exciton binding energy 25meV and the hot ionization energy 26meV of room temperature of GaN, therefore easilier under room temperature or higher temperature, realizes exciton gain.But the key that ZnO moves towards photoelectric device application realizes the reliable and stable and p-type ZnO film of low-resistance.Owing to there is many intrinsic Shi zhiming (as Zn in ZnO
i, V
odeng) and the impurity such as H of involuntary doping, be usually expressed as N-shaped.The existence of these Shi zhiming can produce strong self-compensation mechanism to the acceptor impurity mixed, so be difficult to the P type doping realizing ZnO.ZnO homojunction ultraviolet swashs penetrates diode and needs to do multi-layer quantum well structure, and p-ZnO mobility used is lower, less stable.The ultraviolet laser diode that development structure is simple, with low cost, the gain of light is high has important using value.
At present, the report being obtained p-type zinc-oxide film by the mode of codoped is had in the industry.Such as, magnesium and antimony is mixed to form Mg-Sb codoped p type ZnO film in zinc oxide, wherein magnesium (Mg) can increase the energy gap of ZnO effectively as the doping agent of ZnO, so the intrinsic shallow donor energy level in ZnO just can away from conduction band limit, thus increase its ionization energy, reduce the N-shaped conductive characteristic of ZnO.But due to the auto-compensation of intrinsic shallow donor defect existed in ZnO, make Sb be difficult to be used to doping preparation p-type ZnO material.
Accompanying drawing explanation
Fig. 1 is the structural representation of the magnesium arsenic codoped p type zinc-oxide film obtained by manufacture method that the present invention proposes;
Summary of the invention:
The manufacture method that the present invention proposes in turn includes the following steps:
The first step, choose sapphire as substrate 1, this substrate 1 is placed in the ultrasonic oscillator with dehydrated alcohol and cleans, to remove the grease on substrate 1 surface, and then be placed into there is deionized water ultrasonic oscillator in clean, to remove remaining dehydrated alcohol;
Purity is the Zinc oxide powder of 99.99% by second step, the arsenic oxide arsenoxide powder of the molar content of magnesium to be the magnesium oxide powder of 8-13% and the molar content of arsenic be 0.5-1.5% mixes, and then compacting forms target;
3rd step, the substrate 1 completing the first step technique is put into magnetron sputtering reaction chamber, utilize radio frequency magnetron sputtering method, in inert gas environment, target as sputter is deposited on substrate, thus form the p-type ZnO crystal film 2 that thickness is the magnesium arsenic codoped of 200-400nm on substrate 1;
4th step, carry out thermal annealing to the substrate 1 completing the 3rd step, annealing atmosphere is oxygen, and annealing temperature is 700 DEG C, and annealing time is 40 minutes;
5th step, will complete the substrate naturally cooling of the 4th step.
Wherein, the vacuum tightness of rf magnetron sputtering reaction chamber is 10
-5pascal.
Wherein, substrate 1, before rf magnetron sputtering, first carries out heating and keeps temperature 600 DEG C.
Wherein, the radio frequency power 100W of rf magnetron sputtering, the rf magnetron sputtering time is 2.5 hours.
Wherein, in the p-type ZnO crystal film of described magnesium arsenic codoped, the molar content of Mg is 8-13%, and the molar content of arsenic is 0.5-1.5%;
Wherein, at normal temperatures, the piezoelectric constant d of the p-type ZnO crystal film of magnesium arsenic codoped
33be greater than 18pC/N, its resistivity is greater than 10
10Ω cm.
Embodiment:
Below by embodiment, the present invention is described in detail.
Embodiment 1
In described p-type ZnO crystal film, the molar content of Mg is 8-13%, and the molar content of arsenic is 0.5-1.5%.The p-type ZnO crystal film grown after magnesium arsenic codoped at normal temperatures, its piezoelectric constant d
33be greater than 18pC/N, its resistivity is greater than ρ and is greater than 10
10Ω cm.
The manufacture method introducing the magnesium arsenic growing p-type ZnO crystal film by codoping that the present invention proposes below is described.
The first step, choose sapphire as substrate 1, this substrate 1 is placed in the ultrasonic oscillator with dehydrated alcohol and cleans, to remove the grease on substrate 1 surface, and then be placed into there is deionized water ultrasonic oscillator in clean, to remove remaining dehydrated alcohol;
Purity is the Zinc oxide powder of 99.99% by second step, the arsenic oxide arsenoxide powder of the molar content of magnesium to be the magnesium oxide powder of 8-13% and the molar content of arsenic be 0.5-1.5% mixes, and then compacting forms target;
3rd step, the substrate 1 completing the first step technique is put into magnetron sputtering reaction chamber, utilize radio frequency magnetron sputtering method, in inert gas environment, target as sputter is deposited on substrate, thus form the p-type ZnO crystal film 2 that thickness is the magnesium arsenic codoped of 200-400nm on substrate 1;
4th step, carry out thermal annealing to the substrate 1 completing the 3rd step, annealing atmosphere is oxygen, and annealing temperature is 700 DEG C, and annealing time is 40 minutes.
5th step, will complete the substrate naturally cooling of the 4th step.
Wherein, the vacuum tightness of rf magnetron sputtering reaction chamber is 10
-5pascal.
Wherein, substrate 1, before rf magnetron sputtering, first carries out heating and keeps temperature 600 DEG C.
Wherein, the radio frequency power 100W of rf magnetron sputtering, the rf magnetron sputtering time is 2.5 hours.
Embodiment 2
In described p-type ZnO crystal film, the molar content of Mg is 11%, and the molar content of arsenic is 0.8%.The p-type ZnO crystal film grown after magnesium arsenic codoped at normal temperatures, its piezoelectric constant d
33be greater than 18pC/N, its resistivity is greater than ρ and is greater than 10
10Ω cm.
The manufacture method introducing the magnesium arsenic growing p-type ZnO crystal film by codoping that the present invention proposes below is described.
The first step, choose sapphire as substrate 1, this substrate 1 is placed in the ultrasonic oscillator with dehydrated alcohol and cleans, to remove the grease on substrate 1 surface, and then be placed into there is deionized water ultrasonic oscillator in clean, to remove remaining dehydrated alcohol;
Purity is the Zinc oxide powder of 99.99% by second step, the molar content of magnesium to be the magnesium oxide powder of 11% and the molar content of arsenic be 0.8% arsenic oxide arsenoxide powder mix, then compacting forms target;
3rd step, the substrate 1 completing the first step technique is put into magnetron sputtering reaction chamber, utilize radio frequency magnetron sputtering method, in inert gas environment, target as sputter is deposited on substrate, thus form the p-type ZnO crystal film 2 that thickness is the magnesium arsenic codoped of 300nm on substrate 1;
4th step, carry out thermal annealing to the substrate 1 completing the 3rd step, annealing atmosphere is oxygen, and annealing temperature is 700 DEG C, and annealing time is 40 minutes.
5th step, will complete the substrate naturally cooling of the 4th step.
Wherein, the vacuum tightness of rf magnetron sputtering reaction chamber is 10
-5pascal.
Wherein, substrate 1, before rf magnetron sputtering, first carries out heating and keeps temperature 600 DEG C.
Above embodiment is to invention has been detailed introduction, but above-mentioned embodiment is not intended to limit scope of the present invention, and protection scope of the present invention is defined by the appended claims.
Claims (3)
1. a manufacture method for magnesium arsenic codoped p type zinc-oxide film, in turn includes the following steps:
The first step, choose sapphire as substrate 1, this substrate 1 is placed in the ultrasonic oscillator with dehydrated alcohol and cleans, to remove the grease on substrate 1 surface, and then be placed into there is deionized water ultrasonic oscillator in clean, to remove remaining dehydrated alcohol;
Purity is the Zinc oxide powder of 99.99% by second step, the arsenic oxide arsenoxide powder of the molar content of magnesium to be the magnesium oxide powder of 8-13% and the molar content of arsenic be 0.5-1.5% mixes, and then compacting forms target;
3rd step, the substrate 1 completing the first step technique is put into magnetron sputtering reaction chamber, utilize radio frequency magnetron sputtering method, in inert gas environment, target as sputter is deposited on substrate, thus form the p-type ZnO crystal film 2 that thickness is the magnesium arsenic codoped of 200-400nm on substrate 1;
4th step, carry out thermal annealing to the substrate 1 completing the 3rd step, annealing atmosphere is oxygen, and annealing temperature is 700 DEG C, and annealing time is 40 minutes;
5th step, will complete the substrate naturally cooling of the 4th step;
Wherein, in the p-type ZnO crystal film of described magnesium arsenic codoped, the molar content of Mg is 11%, and the molar content of arsenic is 0.8%, at normal temperatures, and the piezoelectric constant d of the p-type ZnO crystal film of magnesium arsenic codoped
33be greater than 18pC/N, its resistivity is greater than 10
10Ω cm.
2. the manufacture method of magnesium arsenic codoped p type zinc-oxide film as claimed in claim 1, it is characterized in that: wherein, the vacuum tightness of rf magnetron sputtering reaction chamber is 10
-5pascal, the radio frequency power 100W of rf magnetron sputtering, the rf magnetron sputtering time is 2.5 hours.
3. the manufacture method of magnesium arsenic codoped p type zinc-oxide film as claimed in claim 1 or 2, is characterized in that:
Wherein, substrate 1, before rf magnetron sputtering, first carries out heating and keeps temperature 600 DEG C.
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| CN102650033A (en) * | 2011-02-24 | 2012-08-29 | 海洋王照明科技股份有限公司 | Phosphor-doped zinc stannate transparent conductive film, and preparation method and application thereof |
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| US8546797B2 (en) * | 2009-10-20 | 2013-10-01 | Stanley Electric Co., Ltd. | Zinc oxide based compound semiconductor device |
| CN103151707B (en) * | 2013-02-28 | 2015-08-05 | 溧阳市宏达电机有限公司 | A kind of manufacture method of laser diode |
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| CN102650033A (en) * | 2011-02-24 | 2012-08-29 | 海洋王照明科技股份有限公司 | Phosphor-doped zinc stannate transparent conductive film, and preparation method and application thereof |
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