CN103147042A - 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 PDF

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Publication number
CN103147042A
CN103147042A CN2013100672184A CN201310067218A CN103147042A CN 103147042 A CN103147042 A CN 103147042A CN 2013100672184 A CN2013100672184 A CN 2013100672184A CN 201310067218 A CN201310067218 A CN 201310067218A CN 103147042 A CN103147042 A CN 103147042A
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substrate
magnesium
codoped
magnetron sputtering
arsenic
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CN103147042B (en
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钱时昌
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LIYANG HUAJING ELECTRONIC MATERIAL CO Ltd
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LIYANG HUAJING ELECTRONIC MATERIAL CO Ltd
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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

A kind of manufacture method of magnesium arsenic codoped p type zinc-oxide film
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 on energy gap, and have than the higher fusing point of GaN and larger exciton bind energy, have again the threshold value of lower photoluminescence and stimulated radiation and good electromechanical coupling characteristics, thermostability and chemical stability.Thereby in the application aspect royal purple light-emitting diode, laser apparatus and relative photo electrical part thereof, huge potentiality are arranged.At room temperature, the energy gap of zinc oxide (ZnO) is 3.37eV, and free exciton is in conjunction with can be up to 60meV, much larger than exciton binding energy 25meV and the hot ionization energy 26meV of room temperature of GaN, therefore easilier realizes the exciton gain under room temperature or higher temperature.But the key that ZnO moves towards the photoelectric device application is to realize the p-type ZnO film of reliable and stable and low-resistance.ZnO is owing to existing many intrinsic alms giver's defectives (as Zn i, V oDeng) and the impurity such as H of involuntary doping, be usually expressed as N-shaped.The existence of these alms giver's defectives can produce strong self compensation effect to the acceptor impurity that mixes, so be difficult to realize the P type doping of ZnO.ZnO homojunction ultraviolet swashs penetrates diode and need to do the 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, have in the industry the report that obtains the p-type zinc-oxide film by the mode of codoped.For example, mix magnesium and antimony and 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's energy level in ZnO just can be away from the conduction band limit, thereby increased its ionization energy, weakened the N-shaped conductive characteristic of ZnO.But due to the auto-compensation of the intrinsic shallow donor's defective that exists in ZnO, make Sb be difficult to be used to doping preparation p-type ZnO material.
Description of drawings
Fig. 1 is the structural representation of the prepared magnesium arsenic of the manufacture method codoped p type zinc-oxide film that proposes of the present invention;
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 cleans, to remove the grease on substrate 1 surface, and then it is placed in the ultrasonic oscillator with deionized water cleans, to remove remaining dehydrated alcohol;
Second step, the arsenic oxide arsenoxide powder that is 0.5-1.5% with the purity molar content that is 99.99% Zinc oxide powder, magnesium the molar content that is the magnesium oxide powder of 8-13% and arsenic mixes, and then compacting forms target;
The 3rd step, the substrate 1 of completing the first step technique is put into the magnetron sputtering reaction chamber, utilizing radio frequency magnetron sputtering method, in inert gas environment, target as sputter is deposited on substrate, is the p-type ZnO crystal film 2 of the magnesium arsenic codoped of 200-400nm thereby form thickness on substrate 1;
The 4th step, the substrate 1 of completing for the 3rd step is carried out thermal annealing, annealing atmosphere is oxygen, and annealing temperature is 700 ℃, and annealing time is 40 minutes;
In the 5th step, the substrate naturally cooling in the 4th step will be completed.
Wherein, the vacuum tightness of rf magnetron sputtering reaction chamber is 10 -5Pascal.
Wherein, substrate 1 first heats and keeps 600 ℃ of temperature before rf magnetron sputtering.
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 33Greater than 18pC/N, its resistivity is greater than 10 10Ω cm.
Embodiment:
The present invention is described in detail below by embodiment.
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%.Through the p-type ZnO crystal film of growing after magnesium arsenic codoped at normal temperatures, its piezoelectric constant d 33Greater than 18pC/N, its resistivity greater than ρ greater than 10 10Ω cm.
The manufacture method that the below introduces the magnesium arsenic growing p-type ZnO crystal film by codoping of the present invention's proposition describes.
The first step, choose sapphire as substrate 1, this substrate 1 is placed in the ultrasonic oscillator with dehydrated alcohol cleans, to remove the grease on substrate 1 surface, and then it is placed in the ultrasonic oscillator with deionized water cleans, to remove remaining dehydrated alcohol;
Second step, the arsenic oxide arsenoxide powder that is 0.5-1.5% with the purity molar content that is 99.99% Zinc oxide powder, magnesium the molar content that is the magnesium oxide powder of 8-13% and arsenic mixes, and then compacting forms target;
The 3rd step, the substrate 1 of completing the first step technique is put into the magnetron sputtering reaction chamber, utilizing radio frequency magnetron sputtering method, in inert gas environment, target as sputter is deposited on substrate, is the p-type ZnO crystal film 2 of the magnesium arsenic codoped of 200-400nm thereby form thickness on substrate 1;
The 4th step, the substrate 1 of completing for the 3rd step is carried out thermal annealing, annealing atmosphere is oxygen, and annealing temperature is 700 ℃, and annealing time is 40 minutes.
In the 5th step, the substrate naturally cooling in the 4th step will be completed.
Wherein, the vacuum tightness of rf magnetron sputtering reaction chamber is 10 -5Pascal.
Wherein, substrate 1 first heats and keeps 600 ℃ of temperature before rf magnetron sputtering.
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%.Through the p-type ZnO crystal film of growing after magnesium arsenic codoped at normal temperatures, its piezoelectric constant d 33Greater than 18pC/N, its resistivity greater than ρ greater than 10 10Ω cm.
The manufacture method that the below introduces the magnesium arsenic growing p-type ZnO crystal film by codoping of the present invention's proposition describes.
The first step, choose sapphire as substrate 1, this substrate 1 is placed in the ultrasonic oscillator with dehydrated alcohol cleans, to remove the grease on substrate 1 surface, and then it is placed in the ultrasonic oscillator with deionized water cleans, to remove remaining dehydrated alcohol;
Second step is that 0.8% arsenic oxide arsenoxide powder mixes with the purity molar content that is 99.99% Zinc oxide powder, magnesium the molar content that is 11% magnesium oxide powder and arsenic, and then compacting forms target;
The 3rd step, the substrate 1 of completing the first step technique is put into the magnetron sputtering reaction chamber, utilizing radio frequency magnetron sputtering method, in inert gas environment, target as sputter is deposited on substrate, is the p-type ZnO crystal film 2 of the magnesium arsenic codoped of 300nm thereby form thickness on substrate 1;
The 4th step, the substrate 1 of completing for the 3rd step is carried out thermal annealing, annealing atmosphere is oxygen, and annealing temperature is 700 ℃, and annealing time is 40 minutes.
In the 5th step, the substrate naturally cooling in the 4th step will be completed.
Wherein, the vacuum tightness of rf magnetron sputtering reaction chamber is 10 -5Pascal.
Wherein, substrate 1 first heats and keeps 600 ℃ of temperature before rf magnetron sputtering.
Above embodiment is described in detail the present invention, but above-mentioned embodiment is not in order to limit scope of the present invention, and protection scope of the present invention is defined by the appended claims.

Claims (4)

1. the manufacture method of a 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 cleans, to remove the grease on substrate 1 surface, and then it is placed in the ultrasonic oscillator with deionized water cleans, to remove remaining dehydrated alcohol;
Second step, the arsenic oxide arsenoxide powder that is 0.5-1.5% with the purity molar content that is 99.99% Zinc oxide powder, magnesium the molar content that is the magnesium oxide powder of 8-13% and arsenic mixes, and then compacting forms target;
The 3rd step, the substrate 1 of completing the first step technique is put into the magnetron sputtering reaction chamber, utilizing radio frequency magnetron sputtering method, in inert gas environment, target as sputter is deposited on substrate, is the p-type ZnO crystal film 2 of the magnesium arsenic codoped of 200-400nm thereby form thickness on substrate 1;
The 4th step, the substrate 1 of completing for the 3rd step is carried out thermal annealing, annealing atmosphere is oxygen, and annealing temperature is 700 ℃, and annealing time is 40 minutes;
In the 5th step, the substrate naturally cooling in the 4th step will be completed.
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 first heats and keeps 600 ℃ of temperature before rf magnetron sputtering.
4. the manufacture method of one of as any in claim 1-3 described magnesium arsenic codoped p type zinc-oxide film, it is characterized in that: wherein, in the p-type ZnO crystal film of described magnesium arsenic codoped, the molar content of Mg is 8-13%, the molar content of arsenic is 0.5-1.5%, at normal temperatures, the piezoelectric constant d of the p-type ZnO crystal film of magnesium arsenic codoped 33Greater than about 18pC/N, its resistivity is greater than approximately 10 10Ω cm.
CN201310067218.4A 2013-03-01 2013-03-01 Manufacturing method of magnesium/arsenium-codoped p-type zinc oxide film Expired - Fee Related CN103147042B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
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CN108364855A (en) * 2018-02-10 2018-08-03 广东美的制冷设备有限公司 Zinc oxide semiconductor material and preparation method thereof, semiconductor devices and air conditioner

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CN103151707A (en) * 2013-02-28 2013-06-12 溧阳市宏达电机有限公司 Method for manufacturing laser diode

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US20110089418A1 (en) * 2009-10-20 2011-04-21 Stanley Electric Co., Ltd. Zinc oxide based compound semiconductor device
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
CN103151707A (en) * 2013-02-28 2013-06-12 溧阳市宏达电机有限公司 Method for manufacturing laser diode

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姚斌等: "氮掺夹p型MgxZn1-xO薄膜的制备及其表征", 《吉林师范大学学报（自然科学版）》 *
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108364855A (en) * 2018-02-10 2018-08-03 广东美的制冷设备有限公司 Zinc oxide semiconductor material and preparation method thereof, semiconductor devices and air conditioner
CN108364855B (en) * 2018-02-10 2021-09-14 广东美的制冷设备有限公司 Zinc oxide semiconductor material, preparation method thereof, semiconductor device and air conditioner

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