CN103166112A - Nitrogen-magnesium co-doping p-type zinc oxide film - Google Patents
Nitrogen-magnesium co-doping p-type zinc oxide film Download PDFInfo
- Publication number
- CN103166112A CN103166112A CN2013100660327A CN201310066032A CN103166112A CN 103166112 A CN103166112 A CN 103166112A CN 2013100660327 A CN2013100660327 A CN 2013100660327A CN 201310066032 A CN201310066032 A CN 201310066032A CN 103166112 A CN103166112 A CN 103166112A
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- China
- Prior art keywords
- oxide film
- nitrogen
- type zinc
- magnesium
- zinc oxide
- Prior art date
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 39
- SVFOMDDAWOLOME-UHFFFAOYSA-N [N].[Mg] Chemical compound [N].[Mg] SVFOMDDAWOLOME-UHFFFAOYSA-N 0.000 title claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011777 magnesium Substances 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims description 18
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 12
- 229960001296 zinc oxide Drugs 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 4
- 229910052594 sapphire Inorganic materials 0.000 claims description 3
- 239000010980 sapphire Substances 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 10
- 238000000137 annealing Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000002950 deficient Effects 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Abstract
The invention discloses a nitrogen-magnesium co-doping p-type zinc oxide film. The mole percentage composition of magnesium (Mg) in the p-type zinc oxide film is 5-11%, and the mole percentage composition of nitrogen is 0.8-1.7%. Under a normal temperature, a piezoelectric constant d33 of the p-type zinc oxide film is larger than 16p C/N, and the resistivity of the p-type zinc oxide film is larger than 1.2*1010 omega cm.
Description
Technical field
The invention belongs to field of semiconductor lasers, relate in particular to a kind of p-type zinc-oxide film that can be used for a kind of nitrogen magnesium codope of semiconductor 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 structural representation of the present invention;
Summary of the invention:
The objective of the invention is to overcome the existing deficiency of present p-type ZnO doping, a kind of p-type zinc-oxide film of nitrogen magnesium codope is provided.
In described p-type ZnO crystal film, the molar content of Mg is 5-11%, and the molar content of nitrogen is 0.8-1.7%.
The invention has the beneficial effects as follows through the p-type ZnO crystal film of growing after nitrogen magnesium codope at normal temperatures its piezoelectric constant d
33Greater than 16pC/N, its resistivity is greater than 1.2 * 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 5-11%, and the molar content of nitrogen is 0.8-1.7%.Through the p-type ZnO crystal film of growing after nitrogen magnesium codope at normal temperatures, its piezoelectric constant d
33Greater than 16pC/N, its resistivity greater than ρ greater than 1.2 * 10
10Ω cm.
The manufacture method that the below introduces the nitrogen magnesium 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 absolute ethyl 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 absolute ethyl alcohol;
Second step, the magnesium oxide powder that is 5-11% with the purity molar content that is 99.99% Zinc oxide powder, magnesium mixes, and then compacting forms target;
The 3rd step, the substrate 1 of completing first step technique is put into the magnetron sputtering reative cell, the molar content that passes into nitrogen to this magnetron sputtering reative cell is NO, the NO of 0.8-1.7%
2The after-applied radio-frequency power of mist, this radio-frequency power makes NO and NO
2Gas activation, and target as sputter is deposited on substrate, be the p-type ZnO crystal film 2 of the nitrogen magnesium codope of 300-400nm 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, that the substrate of completing for the 4th step is naturally cooling.
Wherein, the vacuum degree of rf magnetron sputtering reative cell is 10
-5Pascal.
Wherein, substrate 1 first heats and keeps 600 ℃ of temperature before rf magnetron sputtering.
Wherein, the radio-frequency power 120-200W of rf magnetron sputtering, the rf magnetron sputtering time is 2-3 hour.
Embodiment 2
In described p-type ZnO crystal film, the molar content of Mg is 9%, and the molar content of nitrogen is 1.2%.Through the p-type ZnO crystal film of growing after nitrogen magnesium codope at normal temperatures, its piezoelectric constant d
33Greater than 16pC/N, its resistivity greater than ρ greater than 1.2 * 10
10Ω cm.
The manufacture method that the below introduces the nitrogen magnesium 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 absolute ethyl 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 absolute ethyl alcohol;
Second step is that 9% magnesium oxide powder compacting forms target with the purity molar content that is 99.99% Zinc oxide powder, magnesium;
In the 3rd step, the molar content that passes into nitrogen to this magnetron sputtering reative cell is 1.2% NO, NO
2The after-applied radio-frequency power of mist, this radio-frequency power makes NO and NO
2Gas activation, and target as sputter is deposited on substrate, be the p-type ZnO crystal film 2 of the nitrogen magnesium codope of 360nm 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, that the substrate of completing for the 4th step is naturally cooling.
Wherein, the vacuum degree of rf magnetron sputtering reative cell is 10
-5Pascal.
Wherein, substrate 1 first heats and keeps 600 ℃ of temperature before rf magnetron sputtering.
Wherein, the radio-frequency power 160W of rf magnetron sputtering, the rf magnetron sputtering time is 2.5 hours.
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 (2)
1. the p-type zinc-oxide film of a nitrogen magnesium codope is characterized in that:
In described p-type zinc-oxide film, the molar content of Mg is 5-11%, and the molar content of nitrogen is 0.8-1.7%; Wherein, described p-type zinc-oxide film at normal temperatures, its piezoelectric constant d
33Greater than 16pC/N, its resistivity is greater than 1.2 * 10
10Ω cm.
2. nitrogen magnesium codoped p type zinc-oxide film as claimed in claim 1 is characterized in that:
The p-type zinc-oxide film of described nitrogen magnesium codope forms by radio frequency magnetron sputtering method on Sapphire Substrate, and its thickness is about 300-400nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310066032.7A CN103166112B (en) | 2013-03-01 | 2013-03-01 | A kind of p-type zinc-oxide film of nitrogen magnesium codope |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310066032.7A CN103166112B (en) | 2013-03-01 | 2013-03-01 | A kind of p-type zinc-oxide film of nitrogen magnesium codope |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103166112A true CN103166112A (en) | 2013-06-19 |
| CN103166112B CN103166112B (en) | 2016-03-02 |
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|---|---|---|---|
| CN201310066032.7A Expired - Fee Related CN103166112B (en) | 2013-03-01 | 2013-03-01 | A kind of p-type zinc-oxide film of nitrogen magnesium codope |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104792824A (en) * | 2015-04-15 | 2015-07-22 | 西安工程大学 | Temperature difference potential current method for detection of ZnO ceramic point defect structure |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1542915A (en) * | 2003-11-04 | 2004-11-03 | 浙江大学 | p-Zn1-XMgXO crystal film and method for making same |
| CN101097979A (en) * | 2007-07-13 | 2008-01-02 | 浙江大学 | ZnO based LED and its preparing process |
| US20080191350A1 (en) * | 2007-02-13 | 2008-08-14 | Micron Technology, Inc. | Magnesium-doped zinc oxide structures and methods |
| JP2009295868A (en) * | 2008-06-06 | 2009-12-17 | Rohm Co Ltd | Oxide conductive film |
-
2013
- 2013-03-01 CN CN201310066032.7A patent/CN103166112B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1542915A (en) * | 2003-11-04 | 2004-11-03 | 浙江大学 | p-Zn1-XMgXO crystal film and method for making same |
| US20080191350A1 (en) * | 2007-02-13 | 2008-08-14 | Micron Technology, Inc. | Magnesium-doped zinc oxide structures and methods |
| CN101097979A (en) * | 2007-07-13 | 2008-01-02 | 浙江大学 | ZnO based LED and its preparing process |
| JP2009295868A (en) * | 2008-06-06 | 2009-12-17 | Rohm Co Ltd | Oxide conductive film |
Non-Patent Citations (2)
| Title |
|---|
| 姚斌等: "氮掺杂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）》 * |
| 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 (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104792824A (en) * | 2015-04-15 | 2015-07-22 | 西安工程大学 | Temperature difference potential current method for detection of ZnO ceramic point defect structure |
| CN104792824B (en) * | 2015-04-15 | 2017-10-31 | 西安工程大学 | Thermoelectric force current methods for the ceramic defects detections of ZnO |
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| Publication number | Publication date |
|---|---|
| CN103166112B (en) | 2016-03-02 |
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