CN103151707A - Method for manufacturing laser diode - Google Patents
Method for manufacturing laser diode Download PDFInfo
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- CN103151707A CN103151707A CN2013100653817A CN201310065381A CN103151707A CN 103151707 A CN103151707 A CN 103151707A CN 2013100653817 A CN2013100653817 A CN 2013100653817A CN 201310065381 A CN201310065381 A CN 201310065381A CN 103151707 A CN103151707 A CN 103151707A
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- magnetron sputtering
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Abstract
The invention discloses a method for manufacturing a laser diode, which sequentially comprises the following steps of forming a nickel oxide film on a sapphire substrate; forming a p-type ZnO crystal film co-doped with magnesium and arsenic on the upper surface of the nickel oxide film; and sputtering a metal material on the lower surface of the substrate and the upper surface of the p-type ZnO crystal film co-doped with the magnesium and arsenic, so that a bottom electrode and an upper electrode are formed respectively.
Description
Technical field
The invention belongs to semiconductor applications, relate in particular to a kind of manufacture method of laser diode.
Background technology
Zinc oxide (ZnO) is in lattice structure, cell parameter 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 luminescence generated by light and stimulated radiation and good electromechanical coupling characteristics, thermal stability and chemical stability.Thereby in the application aspect royal purple light-emitting diode, laser and relative photo electric device 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 codope.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 dopant 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 that the present invention proposes the laser diode that manufacture method makes;
Summary of the invention:
The present invention is directed to the problem that prior art exists, proposed a kind of manufacture method that adopts the laser diode of magnesium arsenic codoped p type zinc-oxide film, it in turn includes the following steps:
The first step, choose sapphire as substrate, this substrate is placed in the ultrasonic oscillator with absolute ethyl alcohol cleans, to remove the grease of substrate surface, and then it is placed in the ultrasonic oscillator with deionized water cleans, to remove remaining absolute ethyl alcohol;
Second step is put into the magnetron sputtering reative cell with described substrate, forms the nickel oxide film of 300-600nm thickness on described substrate by rf magnetron sputtering technique;
In the 3rd 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; Then will complete the substrate of second step gained and put into the magnetron sputtering reative cell, utilize radio frequency magnetron sputtering method, target as sputter being deposited on the upper surface of described nickel oxide film in inert gas environment, is the p-type ZnO crystal film of the magnesium arsenic codope of 200-400nm thereby form thickness;
The 4th step, the substrate 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, and is naturally cooling after annealing;
In the 5th step, at splash-proofing sputtering metal material on the lower surface of described substrate and on the upper surface of the p-type ZnO crystal film of described magnesium arsenic codope, thereby form respectively hearth electrode and top electrode.
Wherein, in described magnesium arsenic codoped p type zinc-oxide film, the molar content of Mg is 8-13%, and the molar content of arsenic is 0.5-1.5%; And, at normal temperatures, the piezoelectric constant d of the p-type ZnO crystal film of magnesium arsenic codope
33Greater than 18pC/N, its resistivity is greater than 10
10Ω 〃 cm.
Embodiment:
The present invention is described in detail below by embodiment.
Referring to Fig. 1, adopt the manufacture method of the laser diode of magnesium arsenic codoped p type zinc-oxide film in turn include the following steps:
The first step, choose sapphire as substrate 2, this substrate 2 is placed in the ultrasonic oscillator with absolute ethyl alcohol cleans, to remove the grease on substrate 2 surfaces, and then it is placed in the ultrasonic oscillator with deionized water cleans, to remove remaining absolute ethyl alcohol;
Second step is put into the magnetron sputtering reative cell with described substrate 2, forms the nickel oxide film 3 of 300-600nm thickness on described substrate by rf magnetron sputtering technique;
In the 3rd 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; Then will complete the substrate 2 of second step gained and put into the magnetron sputtering reative cell, utilize radio frequency magnetron sputtering method, target as sputter being deposited on the upper surface of described nickel oxide film 3 in inert gas environment, is the p-type ZnO crystal film 4 of the magnesium arsenic codope of 200-400nm thereby form thickness;
The 4th step, the substrate 2 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, and is naturally cooling after annealing;
In the 5th step, at splash-proofing sputtering metal material on the lower surface of described substrate 2 and on the upper surface of the p-type ZnO crystal film 4 of described magnesium arsenic codope, thereby form respectively hearth electrode 1 and top electrode 5.
Wherein, in described magnesium arsenic codoped p type zinc-oxide film 4, the molar content of Mg is 8-13%, and the molar content of arsenic is 0.5-1.5%; And, at normal temperatures, the piezoelectric constant d of the p-type ZnO crystal film 4 of magnesium arsenic codope
33Greater than 18pC/N, its resistivity is greater than 10
10Ω 〃 cm.
Wherein, during second step and the 3rd went on foot, the vacuum degree of rf magnetron sputtering reative cell was all 10
-5Pascal;
Wherein, in second step, the radio-frequency power 120-200W of rf magnetron sputtering, the rf magnetron sputtering time is 1.5 hours.
Wherein, in the 3rd step, the radio-frequency power 100-150W of rf magnetron sputtering, the rf magnetron sputtering time is 2.5 hours.
Wherein, can adopt the various metals material to consist of the material of hearth electrode 1 and top electrode 5, for example gold, silver or copper, also can adopt the metallic compound material to consist of described hearth electrode 1 and top electrode 5, for example ITO.
Above execution mode is described in detail the present invention, but above-mentioned execution mode 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 laser diode, it in turn includes the following steps:
The first step, choose sapphire as substrate, this substrate is placed in the ultrasonic oscillator with absolute ethyl alcohol cleans, to remove the grease of substrate surface, and then it is placed in the ultrasonic oscillator with deionized water cleans, to remove remaining absolute ethyl alcohol;
Second step is put into the magnetron sputtering reative cell with described substrate, forms the nickel oxide film of 300-600nm thickness on described substrate by rf magnetron sputtering technique;
In the 3rd 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; Then will complete the substrate of second step gained and put into the magnetron sputtering reative cell, utilize radio frequency magnetron sputtering method, target as sputter being deposited on the upper surface of described nickel oxide film in inert gas environment, is the p-type ZnO crystal film of the magnesium arsenic codope of 200-400nm thereby form thickness;
The 4th step, the substrate 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, and is naturally cooling after annealing;
In the 5th step, at splash-proofing sputtering metal material on the lower surface of described substrate and on the upper surface of the p-type ZnO crystal film of described magnesium arsenic codope, thereby form respectively hearth electrode and top electrode.
2. the manufacture method of laser diode as claimed in claim 1 is characterized in that:
Wherein, in described magnesium arsenic codoped p type zinc-oxide film, the molar content of Mg is 8-13%, and the molar content of arsenic is 0.5-1.5%; And, at normal temperatures, the piezoelectric constant d of the p-type ZnO crystal film of magnesium arsenic codope
33Greater than 18pC/N, its resistivity is greater than 10
10Ω 〃 cm.
3. method for manufacturing laser diode as claimed in claim 1 or 2 is characterized in that:
Wherein, during second step and the 3rd went on foot, the vacuum degree of rf magnetron sputtering reative cell was all 10
-5Pascal; In second step, the radio-frequency power 120-200W of rf magnetron sputtering, the rf magnetron sputtering time is 1.5 hours; In the 3rd step, the radio-frequency power 100-150W of rf magnetron sputtering, the rf magnetron sputtering time is 2.5 hours.
4. one of as any in claim 1-3 described method for manufacturing laser diode is characterized in that:
Wherein, can adopt the various metals material to consist of the material of hearth electrode 1 and top electrode 5, for example gold, silver or copper, also can adopt the metallic compound material to consist of described hearth electrode 1 and top electrode 5, for example ITO.
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| CN201310065381.7A CN103151707B (en) | 2013-02-28 | 2013-02-28 | A kind of manufacture method of laser diode |
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| CN201310065381.7A CN103151707B (en) | 2013-02-28 | 2013-02-28 | A kind of manufacture method of laser diode |
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| CN103151707B CN103151707B (en) | 2015-08-05 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103147042A (en) * | 2013-03-01 | 2013-06-12 | 溧阳华晶电子材料有限公司 | Manufacturing method of magnesium/arsenium-codoped p-type zinc oxide film |
| CN103151708A (en) * | 2013-03-01 | 2013-06-12 | 溧阳华晶电子材料有限公司 | Magnesium-arsenic co-doped p type zinc oxide film |
| CN114525472A (en) * | 2022-02-22 | 2022-05-24 | 重庆工商大学 | Preparation method of nickel oxide film with nanostructure |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110089418A1 (en) * | 2009-10-20 | 2011-04-21 | Stanley Electric Co., Ltd. | Zinc oxide based compound semiconductor device |
-
2013
- 2013-02-28 CN CN201310065381.7A patent/CN103151707B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110089418A1 (en) * | 2009-10-20 | 2011-04-21 | Stanley Electric Co., Ltd. | Zinc oxide based compound semiconductor device |
Non-Patent Citations (2)
| Title |
|---|
| J.C.FAN ET AL.: "Shallow acceptor and hydrogen impurity in p-type arsenic-doped ZnMgO films grown by radio frequency magnetron sputtering", 《SEMICONDUCTOR SCIENCE AND TECHNOLOGY》 * |
| 赵龙: "p-ZnMgO:As薄膜的MOCVD生长及其发光器件制备研究", 《中国优秀硕士学位论文全文数据库 信息科技辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103147042A (en) * | 2013-03-01 | 2013-06-12 | 溧阳华晶电子材料有限公司 | Manufacturing method of magnesium/arsenium-codoped p-type zinc oxide film |
| CN103151708A (en) * | 2013-03-01 | 2013-06-12 | 溧阳华晶电子材料有限公司 | Magnesium-arsenic co-doped p type zinc oxide film |
| CN103151708B (en) * | 2013-03-01 | 2015-08-05 | 溧阳华晶电子材料有限公司 | A kind of magnesium arsenic codoped p type zinc-oxide film |
| CN114525472A (en) * | 2022-02-22 | 2022-05-24 | 重庆工商大学 | Preparation method of nickel oxide film with nanostructure |
| CN114525472B (en) * | 2022-02-22 | 2023-09-19 | 重庆工商大学 | Preparation method of nano-structured nickel oxide film |
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| CN103151707B (en) | 2015-08-05 |
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Effective date of registration: 20190104 Address after: 213300 Hongkou Road 218, Zhongguancun Science and Technology Industrial Park, Liyang City, Changzhou City, Jiangsu Province Patentee after: Liyang High-tech Venture Center Address before: 213300 No. 86 Beimen East Road, Liyang City, Changzhou City, Jiangsu Province Patentee before: Liyang Hongda Motors Co., Ltd. |
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