CN100582321C - Method for growing Na doping p type ZnO crystal thin film - Google Patents
Method for growing Na doping p type ZnO crystal thin film Download PDFInfo
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- CN100582321C CN100582321C CN200710156587A CN200710156587A CN100582321C CN 100582321 C CN100582321 C CN 100582321C CN 200710156587 A CN200710156587 A CN 200710156587A CN 200710156587 A CN200710156587 A CN 200710156587A CN 100582321 C CN100582321 C CN 100582321C
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Abstract
The invention discloses a method for growing p type ZnO crystal thin film by doping Na, which adopts the pulsed laser sedimentation, the method comprises the following steps: firstly, mixing pure zinc oxide powder and sodium carbonate powder by ball-milling, then pressing to shape and sintering, preparing target material of ZnO doped with Na2O, secondly, in a growing chamber of a pulsed laser sedimentation device, taking the ZnO doped with Na2O as the target material, taking pure O2 as the growing atmosphere, controlling the pressure intensity of the O2 between 15pa and 45pa, controlling the laser frequency between 1 Hz and 5 Hz, and growing the p type ZnO crystal thin film on a substrate. The method of the invention can realize real time doping, and the doping concentration can be controlled by adjusting the growing temperature and the molar percentage of Na in the target material. The p type ZnO crystal thin film prepared by adopting the method of the invention has good electricity performance, repeatability and stability.
Description
Technical field
The present invention relates to p type ZnO crystal growth for Thin Film method, the especially method of Na doping growing P type ZnO crystal film.
Background technology
ZnO is as wide bandgap semiconductor, its special advantages is arranged, and bandwidth at room temperature is 3.37eV, and exciton binding energy is 60meV, exciton binding energy 25meV and room temperature molecular thermalmotion much larger than GaN can 26meV, the therefore high-power semiconductor laser devices of very potential realization.But the essential step that ZnO moves towards the photoelectric device application realizes the stable p-type ZnO film exactly.ZnO is owing to various native defects, as Zn
i, Zn
oAnd involuntary doping defective, as H
i, show as the n type.In ZnO, mix the Madelung energy that acceptor impurity can improve system, cause intensive alms giver compensating action simultaneously.What the direction that to seek a kind of suitable p type ZnO doping source be scientist's effort was always in the world reported in the world can have V group element as p type ZnO doping material: N, P, As etc. and the element Li of I family.Yet aspect theory calculating, the element Na of I family as be subjected to main have than the shallow acceptor level of V group element and than Li more near the performance of Zn atomic radius.The PLD method has that underlayer temperature is lower, deposition parameter is easily controlled, easily keep advantages such as film is consistent with the target composition, the film quality of growth is better, but also carries out the growth of Na doped p type ZnO thin film in this way.The present invention utilizes pulsed laser deposition technique, is the method for laser target growing P-type ZnO crystal film with the target of mixing the Na element oxide.
Summary of the invention
The objective of the invention is to overcome the existing deficiency of present p type ZnO doping, the method for Na doping growing P type ZnO crystal film is provided.
The method of Na doping growing P type ZnO crystal film of the present invention, employing be pulsed laser deposition, its step is as follows:
1) compression moulding after ball milling mixes with pure zinc oxide and powdered sodium carbonate,, makes and mixes Na more than 2 hours at 1000-1500 ℃ of sintering again more than 2 hours 600-800 ℃ of presintering
2The ZnO target of O, the molar content of Na are 0.2-1.0%;
2) will put into the growth room of pulsed laser deposition device after the substrate surface cleaning, growth room's vacuum tightness is extracted at least 10
-3Pa, heated substrate then, making underlayer temperature is 500-700 ℃, to mix Na
2The ZnO of O is a target, with pure O
2Be growth atmosphere, control O
2Pressure 15-45pa, laser frequency is 1-5Hz, grows, cool off under the oxygen protective atmosphere growth back.
Above-mentioned substrate can be zinc oxide, silicon, sapphire, glass or quartz.The purity of said zinc oxide is more than 99.99%.
Molar content and temperature that the present invention mixes Na by adjusting can prepare the p type ZnO crystal film of different levels of doping, and the time of growth is by required thickness decision.
Advantage of the present invention:
1) can realize real-time doping, realize simultaneously that in the ZnO crystal thin film growth process p type mixes;
2) doping content is higher, because pulsed laser deposition technique can copy to the composition of target in the film of being grown fully, the concentration of dopant higher position that therefore needs only the target of preparation obtains very high doping content;
3) doping content can be controlled by the molar content of regulating Na in growth temperature and the target;
4) Zhi Bei p type film has good electric property, and is repeated and stable.
Description of drawings
Fig. 1 is x ray diffraction (XRD) collection of illustrative plates of Na doped p type ZnO crystal film;
Fig. 2 is that Na doped p type ZnO crystal film gets photoluminescence spectrum;
Fig. 3 is that Na doped p type ZnO crystal film gets the optical transmission spectrum.
Embodiment
Further specify the present invention below in conjunction with specific examples.
Embodiment 1
1) getting purity is 99.99% zinc oxide and powdered sodium carbonate, and the Na molar content is 0.5%, with ZnO and Na
2CO
3Mixed powder pour in the agate ball cup, be placed on and carry out ball milling on the ball mill, the time of ball milling is four hours.The purpose of ball milling has two: at first be for ZnO, Na
2CO
3Powder mixes is even, with the homogeneity of the target that guarantees to prepare.Secondly, be for ZnO and Na
2CO
3Powder fining is beneficial to ZnO and Na subsequently
2CO
3The moulding of mixed powder and sintering.
After ball milling finished, it was 3mm that powder compression is become thickness, and diameter is the disk of 4cm.Then 800 ℃ of presintering 2 hours,, guarantee Na 1250 ℃ of following sintering 3 hours
2CO
3Decomposition.
2) with the quartz be substrate, put into the growth room of pulsed laser deposition device after substrate surface is cleaned, growth room's vacuum tightness is extracted into 5 * 10
-3Pa, heated substrate then, making underlayer temperature is 600 ℃, to mix Na
2The ZnO of O is a target, and the distance of adjusting substrate and target is 5cm, with pure O
2Be growth atmosphere, control O
2Pressure 45pa, laser frequency is 5Hz, and laser work voltage is 27KV, grows, and the time of growth is 60min.Cool off under the oxygen protective atmosphere growth back, and obtaining thickness is the Na doped p type ZnO crystal film of 300nm.
The Na doped p type ZnO crystal film that makes at room temperature has excellent electric property, and resistivity is 27.7 Ω cm, and carrier concentration is 4.64 * 10
17Cm
2/ Vs, mobility is 0.76cm
-3And placing after two months, electric property does not have considerable change.
Fig. 1 has shown X-ray diffractogram (XRD) figure of film, have only the appearance at (0002) and (0004) peak of ZnO, and halfwidth is less, shows the crystal property that film is good.
Fig. 2 is the photoluminescence spectrum of above-mentioned film, is positioned at the good light electroluminescent properties that very strong band edge peak of 3.23eV and faint green light peak have proved the Na doping type film of preparation, for progressive preparation electroluminescent device lays the foundation.
Fig. 3 is the optical transmission spectrum of above-mentioned film.As seen from the figure, up to 90%, precipitous band edge ABSORPTION EDGE is arranged near 380nm, shown the good optical transmission performance in the transmissivity of visible region.
Embodiment 2
1) getting purity is 99.99% zinc oxide and powdered sodium carbonate, and the Na molar content is 1.0%, with ZnO and Na
2CO
3Mixed powder pour in the agate ball cup, be placed on and carry out ball milling on the ball mill, the time of ball milling is four hours.After ball milling finished, it was 3mm that powder compression is become thickness, and diameter is the disk of 4cm.Then 600 ℃ of presintering 2 hours, 1400 ℃ of following sintering 3 hours.
2) with glass be substrate, put into the growth room of pulsed laser deposition device after substrate surface is cleaned, growth room's vacuum tightness is extracted into 5 * 10
-3Pa, heated substrate then, making underlayer temperature is 550 ℃, to mix Na
2The ZnO of O is a target, and the distance of adjusting substrate and target is 5cm, with pure O
2Be growth atmosphere, control O
2Pressure 30pa, laser frequency is 3Hz, and laser work voltage is 27KV, grows, and the time of growth is 60min.Cool off under the oxygen protective atmosphere growth back, and obtaining thickness is the Na doped p type ZnO crystal film of 300nm.
The Na doped p type ZnO crystal film that makes at room temperature has excellent electric property, and resistivity is 63.8 Ω cm, and carrier concentration is 1.72 * 10
17Cm
2/ Vs, mobility is 0.57cm
-3And placing after two months, electric property does not have considerable change.
Embodiment 3
1) getting purity is 99.99% zinc oxide and powdered sodium carbonate, and the Na molar content is 0.2%, with ZnO and Na
2CO
3Mixed powder pour in the agate ball cup, be placed on and carry out ball milling on the ball mill, the time of ball milling is four hours.After ball milling finished, it was 3mm that powder compression is become thickness, and diameter is the disk of 4cm.Then 600 ℃ of presintering 2 hours, 1400 ℃ of following sintering 3 hours.
2) with glass be substrate, put into the growth room of pulsed laser deposition device after substrate surface is cleaned, growth room's vacuum tightness is extracted into 5 * 10
-3Pa, heated substrate then, making underlayer temperature is 700 ℃, to mix Na
2The ZnO of O is a target, and the distance of adjusting substrate and target is 5cm, with pure O
2Be growth atmosphere, control O
2Pressure 30pa, laser frequency is 3Hz, and laser work voltage is 27KV, grows, and the time of growth is 60min.Cool off under the oxygen protective atmosphere growth back, and obtaining thickness is the Na doped p type ZnO crystal film of 300nm.
The Na doped p type ZnO crystal film that makes at room temperature has excellent electric property, and resistivity is 49 Ω cm, and carrier concentration is 1.52 * 10
17Cm
2/ Vs, mobility is 0.84cm
-3And placing after two months, electric property does not have considerable change.
Claims (3)
1.Na the method for doping growing P type ZnO crystal film is characterized in that step is as follows:
1) compression moulding after ball milling mixes with pure zinc oxide and powdered sodium carbonate,, makes and mixes Na more than 2 hours at 1000-1500 ℃ of sintering again more than 2 hours 600-800 ℃ of presintering
2The ZnO target of O, the molar content of Na are 0.2-1.0%;
2) will put into the growth room of pulsed laser deposition device after the substrate surface cleaning, growth room's vacuum tightness is extracted at least 10
-3Pa, heated substrate then, making underlayer temperature is 500-700 ℃, to mix Na
2The ZnO of O is a target, with pure O
2Be growth atmosphere, control O
2Pressure 15-45Pa, laser frequency is 1-5Hz, grows, cool off under the oxygen protective atmosphere growth back.
2. the method for Na doping growing P type ZnO crystal film according to claim 1 is characterized in that said substrate is zinc oxide, silicon, sapphire, glass or quartz.
3. the method for Na doping growing P type ZnO crystal film according to claim 1, the purity that it is characterized in that zinc oxide is more than 99.99%.
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481817B (en) * | 2008-12-31 | 2010-08-25 | 浙江大学 | Growth method of nonpolar ZnO crystal film |
| CN101671842B (en) * | 2009-10-26 | 2011-07-20 | 浙江大学 | Method for growing Na-N co-doping p-type ZnO crystal film by annealing |
| CN101831701B (en) * | 2010-04-13 | 2012-12-12 | 浙江大学 | Method for growing n-type transparent conducting ZnO crystal thin film by F doping |
| US8722456B2 (en) * | 2010-09-25 | 2014-05-13 | Hangzhou Bluelight Opto-electronic Material Co., Ltd. | Method for preparing p-type ZnO-based material |
| CN102373425B (en) * | 2011-11-03 | 2013-04-24 | 浙江大学 | Method for preparing Na-doped p-type NnO film |
| CN102496578A (en) * | 2011-12-07 | 2012-06-13 | 中国科学院长春光学精密机械与物理研究所 | Method for preparing p-type zinc oxide (ZnO) based thin film in lithium-nitrogen (Li-N) double-acceptor co-doping mode |
| CN106400114B (en) * | 2016-09-09 | 2018-10-23 | 昆明理工大学 | A kind of non-polarized preferred orientation zno-based polycrystalline preparation of sections method |
| CN107188218B (en) * | 2017-06-26 | 2019-05-14 | 华南理工大学 | A kind of natrium doping p-type zinc-oxide nano bar material and the preparation method and application thereof |
| CN108570643A (en) * | 2018-05-18 | 2018-09-25 | 华南师范大学 | A kind of preparation method of Er doping ZnO transparent conductive thin film |
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Non-Patent Citations (2)
| Title |
|---|
| Fabrication of p-type Li-doped ZnO films by pulsedlaserdeposition. Bin Xiao, Zhizhen Ye, Yinzhu Zhang, Yujia Zeng, LipingZhu,Binghui Zhao.Applied Surface Science,Vol.253 . 2006 |
| Fabrication of p-type Li-doped ZnO films by pulsedlaserdeposition. Bin Xiao, Zhizhen Ye, Yinzhu Zhang, Yujia Zeng, LipingZhu,Binghui Zhao.Applied Surface Science,Vol.253 . 2006 * |
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