CN101236906A - Acceptor activation method for nitrogen adulterated ZnO - Google Patents
Acceptor activation method for nitrogen adulterated ZnO Download PDFInfo
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- CN101236906A CN101236906A CNA2008100101030A CN200810010103A CN101236906A CN 101236906 A CN101236906 A CN 101236906A CN A2008100101030 A CNA2008100101030 A CN A2008100101030A CN 200810010103 A CN200810010103 A CN 200810010103A CN 101236906 A CN101236906 A CN 101236906A
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- nitrogen
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 25
- 230000004913 activation Effects 0.000 title claims abstract description 8
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000000137 annealing Methods 0.000 claims abstract description 25
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000010408 film Substances 0.000 claims description 17
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 7
- ZWWCURLKEXEFQT-UHFFFAOYSA-N dinitrogen pentaoxide Chemical compound [O-][N+](=O)O[N+]([O-])=O ZWWCURLKEXEFQT-UHFFFAOYSA-N 0.000 claims description 4
- WFPZPJSADLPSON-UHFFFAOYSA-N dinitrogen tetraoxide Chemical compound [O-][N+](=O)[N+]([O-])=O WFPZPJSADLPSON-UHFFFAOYSA-N 0.000 claims description 4
- 238000000407 epitaxy Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000007858 starting material Substances 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims description 3
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 claims description 2
- LZDSILRDTDCIQT-UHFFFAOYSA-N dinitrogen trioxide Chemical compound [O-][N+](=O)N=O LZDSILRDTDCIQT-UHFFFAOYSA-N 0.000 claims description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 239000001272 nitrous oxide Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 239000004065 semiconductor Substances 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 3
- 238000003795 desorption Methods 0.000 abstract description 3
- 238000005229 chemical vapour deposition Methods 0.000 abstract 1
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides an activation method for a nitrogen-doped ZnO acceptor, belonging to the semiconductor material field and particularly taking the radio frequency plasma metal-organic chemical vapor deposition (MOCVD) technique as the late-annealing technique of the nitrogen-doped ZnO. The invention aims to overcome the defect that the nitrogen-doped p type ZnO is hard to acquire and provides a method that by utilizing the radio frequency plasma annealing technique, the nitrogen-doped ZnO undergoes the high temperature annealing in the nitrogen oxide plasma, thereby obtaining the highly efficient and stable p type ZnO doping; because nitrogen and oxygen which are high in activity are formed in the atmosphere, the escape of the nitrogen in the nitrogen-doped ZnO can be prevented, and simultaneously the desorption of the oxygen in the ZnO can also be prevented, and simultaneously the nitrogen acceptor in the nitrogen-doped ZnO is activated, thereby realizing the preparation of the p type ZnO and further realizing the preparation of an pn junction LED device of the ZnO.
Description
Technical field
The present invention relates to the doping techniques of p type ZnO, the method for nitrogen doped p type ZnO thin film belongs to semi-conducting material material field, and particularly a kind of radio frequency plasma body technology that adopts activates the method that N is led as the nitrogen adulterated ZnO post annealed.
Background technology
ZnO is an another novel wide bandgap semiconductor materials after GaN, has the exciton bind energy higher than the GaN material, can realize relevant with exciton efficiently emission under the higher temperature even in room temperature.But in order to be implemented in the application on the photoelectric device, the p type doping problem of ZnO is the focus that people study always.Owing to have a lot of intrinsic defects among the ZnO, as Zn gap, O room etc., make unadulterated ZnO become n N-type semiconductor N material, and the strong self compensation effect of these defectives generations, so be difficult to carry out efficient, stable p-type ZnO doping.
And nitrogen to be considered in ZnO be a shallow acceptor energy level, when in ZnO, carrying out the doping of nitrogen, because nitrogen solid solubility in ZnO is lower, can only under lower temperature, mix, but because intrinsic alms giver defective is more in the low-temperature epitaxy ZnO material, the doped p type ZnO that makes direct nitrogen mix is difficult to obtain higher quality.Northeastern Japan university adopts the laser molecular beam method, utilize the underlayer temperature modulation technique to obtain p type ZnO film than good quality, but this technology exists growth course complexity, growth apparatus industrialization to transplant problems such as difficulty.
MOCVD equipment is the preferred unit of present semiconductor light emitting epitaxial wafer preparation, has advantages such as the material growth quality is good, output big, production cost is lower.Utilize the MOCVD technology can realize the preparation of nitrogen doped p type ZnO, but the relatively poor problem of p type ZnO film electrical properties that ubiquity obtains.This mainly is because because high growth temperature ZnO growth quality is good, but nitrogen solid solubility in ZnO is lower.And nitrogen is easy to mix during low-temperature epitaxy, but has but introduced the intrinsic intrinsic defect of ZnO.In order to improve p type quality, often to carry out high annealing to the nitrogen adulterated ZnO of under cryogenic conditions, growing, make the nitrogen that originally enters among the ZnO can in its body, overflow again like this, simultaneously because the oxygen desorption effect of ZnO also can reduce the crystal mass of ZnO.Therefore, there is self-repugnance in this traditional annealing treating process.Obtaining high-quality nitrogen doped p type ZnO has become a big focus and a difficult point of ZnO research work at present.
Summary of the invention
Purpose of the present invention overcomes the shortcoming that present high-quality nitrogen doped p type ZnO is difficult to obtain, a kind of auxiliary method for annealing of radio frequency plasma that utilizes is provided, the ZnO that nitrogen is mixed carries out high annealing in the nitrogen oxide plasma environment, thereby obtains high-quality p type ZnO doping method.At first thereby annealing can activate among the ZnO more nitrogen and play the effect that generation is led in a large number under the high temperature.Secondly owing to form the nitrogen and the oxygen of high activity in atmosphere, promptly the nitrogen among the ZnO that can compensate is overflowed, and has also suppressed the desorption of oxygen among the ZnO simultaneously.So just realize the preparation of high-quality nitrogen doped p type ZnO, can prepare the p-n junction LED device of ZnO based on this high-quality nitrogen doped p type ZnO.
Technical scheme of the present invention is:
The equipment that p type ZnO film of the present invention growth is used is that described or application number is the special-purpose growth of the described ZnO film of 200410011164.0 a patents radio frequency plasma low-pressure MOCVD equipment as 02100436.6 patent.The high-temperature annealing activation processing step of nitrogen doped p type ZnO film is as follows.
(1) the ZnO film original position of the nitrogen doping of low-temperature epitaxy is placed on the interior growth tray of reative cell.
(2) reach 10Pa when following when reative cell vacuum degree, can start the turbomolecular pump of reative cell.The vacuum degree of reative cell reaches 3 * 10
-3During Pa, stop molecular pump, prepare annealing.
(3) feed nitrogen oxide gas, when vacuum degree is 10Pa～80Pa, open the radio frequency plasma power supply, setting power is 100～450W, the discharge of beginning plasma starter.
(4) heated substrate tablet tray is warmed up to a certain temperature spot in 500～800 ℃, and substrate slice was heat-treated 10～60 minutes.
(5) after annealing is finished, when slowly cooling to below 400 ℃, close radio-frequency power supply, close gas valve, can take out sample after continuing slowly to drop to room temperature.
The ZnO annealing that the present invention mixes to variable concentrations N realizes the processing of the p type ZnO film of different levels of doping by regulating stripped power, annealing temperature and annealing times such as nitrogen oxide gas source amount, radio frequency.
Nitrogen oxide in the explanation can be nitrous oxide (N
2O), nitric oxide (NO), nitrogen dioxide (NO
2), nitrogen trioxide (N
2O
3), dinitrogen tetroxide (N
2O
4) and dinitrogen pentoxide (N
2O
5) in one or more.
Plasma device in the explanation can combine with film growth apparatus, also can be independent plasma annealing device.The structural representation of plasma annealing device is seen Fig. 1.
Effect of the present invention and benefit provide a kind of process of MOCVD equipment growth nitrogen doped p type ZnO thin film of suitable suitability for industrialized production.After utilizing MOCVD to carry out the preparation of the ZnO film that nitrogen mixes, can original position carry out the activation of nitrogen, overcome the problem of nitrogen doped p type ZnO preparation difficulty, solve the technological problems of MOCVD method growing P-type ZnO film, and then can prepare electricity and inject p-n junction type ZnO photoelectric generator spare.
Description of drawings
Fig. 1 is a plasma annealing device schematic diagram.Among the figure: 1 vacuum cavity; 2 gas lines; 3 radio-frequency coils; 4 vacuum pump interfaces; 5 quartz ampoules; 6 sample trays; 7 heating plates; 8 samples.
Fig. 2 is the X ray spread out line pattern (XRD) of annealing back nitrogen adulterated ZnO.
Embodiment
Be described in detail specific embodiments of the invention below in conjunction with technical scheme and accompanying drawing.
The nitrogen adulterated ZnO film that (1) will prepare, the concentration of nitrogen are 1 * 10
19Cm
-3Be placed on the sample tray.
(2) reach 10Pa when following when reative cell vacuum degree, can start the turbomolecular pump of reative cell.The vacuum degree of reative cell reaches 3 * 10
-3During Pa, stop molecular pump, prepare annealing.
(3) feed NO
2, when vacuum degree is 10Pa～80Pa, open the radio frequency plasma power supply, setting power is 100～450W, the discharge of beginning plasma starter.
(4) heated substrate tablet tray is warmed up to a certain temperature spot in 500～800 ℃, and substrate slice was heat-treated 10～60 minutes.
(5) after annealing is finished, when slowly cooling to below 400 ℃, close radio-frequency power supply, close gas valve, can take out sample after continuing slowly to drop to room temperature.
The resistivity of the p type ZnO film of preparing is between 0.1 Ω .cm～1000 Ω .cm, and carrier concentration is 10
15～10
18Cm
-3Between.
The X-ray diffraction pattern (XRD) of the p type ZnO of the ZnO film that method for preparing goes out shows that the nitrogen doped p type ZnO film that the inventive method makes has good crystalline quality.
Embodiment 2
The step of this process and example 1 is identical substantially, and institute's difference is that the nitrogen oxide that adopts is NO.
This process is identical with the step of embodiment 1, and institute's difference is that the nitrogen oxide that adopts is N
2O.
Claims (3)
1. the acceptor activation method of the ZnO that mixes of a nitrogen is characterized in that step is as follows: thus utilize stripped equipment such as radio frequency to come the ZnO thin film doped method that the N acceptor impurity obtains high-quality p type ZnO film that activates of handling to N; The ZnO that N is mixed carries out The high temperature anneal in the plasma atmosphere of nitrogen oxide, thereby realizes the preparation of the ZnO that high-quality p type nitrogen mixes; The present invention realizes the preparation of the p type ZnO film of different levels of doping to the ZnO annealing of different nitrogen doped concentrations by regulating stripped power, annealing temperature and annealing times such as nitrogen oxide gas source amount, radio frequency;
(1) keep the ZnO film original position of the nitrogen doping of low-temperature epitaxy to be positioned on the substrate slice pallet;
(2) reach 10Pa when following when reative cell vacuum degree, can start the turbomolecular pump of reative cell; The vacuum degree of reative cell reaches 3 * 10
-3During pa, stop molecular pump, prepare annealing;
(3) feed nitrogen oxide gas, when vacuum degree is 10Pa～80Pa, open the radio frequency plasma power supply, setting power is 100～450W, the discharge of beginning plasma starter;
(4) heated substrate tablet tray is warmed up to a certain temperature spot in 500～800 ℃, and substrate slice was heat-treated 10～60 minutes;
(5) after annealing is finished, when slowly cooling to below 400 ℃, close radio-frequency power supply, close gas valve, can take out sample after continuing slowly to drop to room temperature.
2. the acceptor activation method of the ZnO that mixes according to the described a kind of nitrogen of claim 1 is characterized in that said nitrogen oxide is nitrous oxide (N
2O), nitric oxide (NO), nitrogen dioxide (NO
2), nitrogen trioxide (N
2O
3), dinitrogen tetroxide (N
2O
4) and dinitrogen pentoxide (N
2O
5) one or more mixtures.
3. the acceptor activation method of the ZnO that a kind of nitrogen according to claim 1 mixes, it is characterized in that adopting RF plasma generator with the nitrogen oxide ionization after, the ZnO that nitrogen is mixed at high temperature handles.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810010103A CN100590820C (en) | 2008-01-13 | 2008-01-13 | Acceptor activation method for nitrogen adulterated ZnO |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810010103A CN100590820C (en) | 2008-01-13 | 2008-01-13 | Acceptor activation method for nitrogen adulterated ZnO |
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| Publication Number | Publication Date |
|---|---|
| CN101236906A true CN101236906A (en) | 2008-08-06 |
| CN100590820C CN100590820C (en) | 2010-02-17 |
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104221126A (en) * | 2012-01-04 | 2014-12-17 | 道达尔销售服务公司 | Method for the low-temperature production of radial-junction semiconductor nanostructures, radial junction device, and solar cell including radial-junction nanostructures |
| CN104822219A (en) * | 2015-05-18 | 2015-08-05 | 京东方科技集团股份有限公司 | Plasma generator, annealing equipment, coating crystallization equipment, and annealing process |
| CN105261708A (en) * | 2015-09-21 | 2016-01-20 | 长安大学 | ZnO/polyvinylcarbazole-polytetrafluoroethylene (PVK-TFB) hybridized light emitting diode (LED) and preparation method thereof |
| CN108538714A (en) * | 2018-04-19 | 2018-09-14 | 中国电子科技集团公司第十三研究所 | The preparation method of III group nitride material of p-type |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004025712A2 (en) * | 2002-09-16 | 2004-03-25 | Massachusetts Institute Of Technology | Method for p-type doping wide band gap oxide semiconductors |
| KR100470155B1 (en) * | 2003-03-07 | 2005-02-04 | 광주과학기술원 | Manufacturing method of zinc oxide semiconductor |
| CN100375253C (en) * | 2005-07-19 | 2008-03-12 | 大连理工大学 | Metallorganics chemical vapour deposition (CVD) preparing method for p-type ZnO thin film |
-
2008
- 2008-01-13 CN CN200810010103A patent/CN100590820C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104221126A (en) * | 2012-01-04 | 2014-12-17 | 道达尔销售服务公司 | Method for the low-temperature production of radial-junction semiconductor nanostructures, radial junction device, and solar cell including radial-junction nanostructures |
| CN104221126B (en) * | 2012-01-04 | 2017-05-31 | 道达尔销售服务公司 | The low-temperature preparation method of radial junction nanometer semiconductor structure, radial direction junction device and the solar cell including radial junction nanostructured |
| CN104822219A (en) * | 2015-05-18 | 2015-08-05 | 京东方科技集团股份有限公司 | Plasma generator, annealing equipment, coating crystallization equipment, and annealing process |
| US9865435B2 (en) | 2015-05-18 | 2018-01-09 | Boe Technology Group Co., Ltd. | Plasma generator, annealing device, deposition crystallization apparatus and annealing process |
| CN105261708A (en) * | 2015-09-21 | 2016-01-20 | 长安大学 | ZnO/polyvinylcarbazole-polytetrafluoroethylene (PVK-TFB) hybridized light emitting diode (LED) and preparation method thereof |
| CN105261708B (en) * | 2015-09-21 | 2017-03-01 | 长安大学 | A kind of ZnO/PVK TFB hydridization LED and preparation method thereof |
| CN108538714A (en) * | 2018-04-19 | 2018-09-14 | 中国电子科技集团公司第十三研究所 | The preparation method of III group nitride material of p-type |
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| Publication number | Publication date |
|---|---|
| CN100590820C (en) | 2010-02-17 |
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