CN102162131A - Method for growing p-type ZnMgO crystal film by doping Ag - Google Patents
Method for growing p-type ZnMgO crystal film by doping Ag Download PDFInfo
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- CN102162131A CN102162131A CN 201110082020 CN201110082020A CN102162131A CN 102162131 A CN102162131 A CN 102162131A CN 201110082020 CN201110082020 CN 201110082020 CN 201110082020 A CN201110082020 A CN 201110082020A CN 102162131 A CN102162131 A CN 102162131A
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Abstract
The invention discloses a method for growing a p-type ZnMgO crystal film by doping Ag, wherein a pulse laser deposition method is adopted. A target material is a ceramic target prepared by carrying out ball milling, mixing, pressing, forming and sintering on ZnO powder, MgO powder and Ag2O powder, wherein the molar percentage content of Mg is 10 % and the molar percentage content of Ag is 0.6-1%; and then, the target material is placed in a growing chamber of a pulse laser deposition device, and the p-type ZnMgO crystal film is grown on a substrate by taking pure O2 as a growth atmosphere and controlling the O2 pressure to be 30-60Pa, the laser frequency to be 3-5Hz and the growth temperature to be 300-600 DEG C. The method disclosed by the invention can be used for realizing real-time doping, and the doping concentration is controlled by regulating the growth temperature and the molar percentage content of Ag in the target material. The p-type ZnMgO crystal film prepared with the method disclosed by the invention has the advantages of favorable electrical property, repeatability and stability.
Description
Technical field
The present invention relates to the growth method of p type ZnMgO crystal film, especially the method for Ag doped growing p type ZnMgO crystal film.
Background technology
ZnO is a kind of II-VI family wide bandgap semiconductor, its special advantages is arranged, energy gap at room temperature is 3.37 eV, the free exciton bound energy is up to 60 meV, exciton binding energy 25 meV and hot ionization energy 26 meV of room temperature much larger than GaN, therefore easier realization exciton gain under room temperature or higher temperature is a kind of material of very potential realization high-power semiconductor laser spare.But it is to realize the p type ZnO film of reliable and stable and low-resistance that ZnO moves towards the photoelectric device key in application.ZnO is owing to exist many intrinsic alms giver's defectives (as Zn
i, V
oDeng) and impurity such as involuntary adulterated H, be usually expressed as the n type.The existence of these alms giver's defectives can produce intensive self compensation effect to the acceptor impurity that mixes, so be difficult to realize that the p type of ZnO mixes.
In theory, realize that p type ZnO has following selection:
Family's element (Li, Na, K, Ag, Cu and Au) substitutes the position of Zn, and perhaps V group element (N, P, As, Sb) substitutes the position of O, can realize that the p type of ZnO changes.Draw by the first principle electronic structure calculation,
The doping process of B family element is easy to realize that element replaces the Zn position and forms acceptor impurity under excess oxygen, and this defective formation can be very low, and the defective formation that enters the gap can be very high, so IB family element easier replacement Zn position rather than formation interstitial atom in ZnO film.In addition, this excess oxygen growth can effectively suppress hole carrier is formed many intrinsic alms giver's defectives of compensation (as the oxygen room
V OWith gap Zn
i) formation.Theoretical Calculation shows also that with analyzing Ag has relative more shallow acceptor level (0.4 eV) in ZnO, comparing with other IB family elements (Cu, Au) is a kind of acceptor doping of ideal more element, and this is subjected to, and main ionization energy is comparable intends to be described as best doped element N.On the other hand,, can regulate energy gap, realize energy band engineering by in ZnO, mixing Mg.The ZnMgO alloy can apply to the ZnMgO/ZnO heterojunction, in the structures such as quantum well and superlattice.These structures are used in photoelectric device, among photodiode, ultraviolet detector, solar cell, can improve the performance and the efficient of device greatly.And p type ZnMgO layer is incorporated in the ZnMgO/ZnO quantum well heterojunction structure, then further optimised devices structure is widened its operation wavelength to ultraviolet band.Therefore, carrying out the adulterated research of ZnMgO film p type has very important significance.Pulsed laser deposition has deposition parameter and easily controls, easily keeps advantages such as film film quality consistent with the target composition, that can realize doping in real time and growth is good, but does not up to the present also carry out the growth of Ag doped growing p type ZnMgO crystal film in this way.
Summary of the invention
The objective of the invention is to overcome the present p type ZnMgO existing deficiency of mixing, Ag doped growing p type ZnMgO is provided the method for crystal film.
The method of Ag doped growing p type ZnMgO crystal film of the present invention, employing be pulsed laser deposition, its step is as follows:
1) the pure ZnO of weighing, pure MgO and pure Ag
2The O powder, wherein the molar content of Mg is 10%, and the molar content of Ag is 0.6 ~ 1%, and compression moulding after ball milling mixes more than 8 hours, makes target at 1200 ℃ of sintering then;
2) substrate after will cleaning is put into the growth room of pulsed laser deposition device, and the distance between target and the substrate is 5.5 cm, and growth room's back of the body end vacuum tightness is evacuated to 10
-4Pa, heated substrate then, making underlayer temperature is 300 ~ 600 ℃, with pure O
2Be growth atmosphere, control O
2Pressure 30 ~ 60 Pa, laser frequency is 3 ~ 5 Hz, grows, the film after the growth is cooled to room temperature under the oxygen atmosphere protection of 100 Pa.
Above-mentioned substrate can be silicon, sapphire, glass or quartz.Said oxygen purity is more than 99.99%.Pure zinc oxide, pure zirconia magnesium and pure zirconia silver powder purity be 99.99%.
The present invention can prepare the p type ZnMgO crystal film of different levels of doping by regulating molar content, underlayer temperature and the growth atmosphere pressure of Ag, 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 ZnMgO crystal film process of growth the p type mixes;
2) doping content can be controlled by the molar content of regulating Ag in growth temperature and the target;
3) Zhi Bei p type film has good electric property, and is repeated and stable.
Description of drawings
Fig. 1 is the pulsed laser deposition device synoptic diagram that the inventive method adopts, and among the figure: 1 is laser apparatus; 2 is the growth room; 3 is target; 4 is substrate;
Fig. 2 is x ray diffraction (XRD) collection of illustrative plates of the p type ZnMgO crystal film of embodiment 1;
Fig. 3 is light at room temperature photoluminescence (PL) spectrum of the p type ZnMgO crystal film of embodiment 1.
Embodiment
Further specify the present invention below in conjunction with specific examples.
1) get purity and be 99.99% zinc oxide, magnesium oxide and silver oxide powder, wherein the molar content of Mg is 10%, and the molar content of Ag is 1%,, with ZnO, MgO and Ag
2The mixed powder of O is poured in the agate ball cup, is placed on to carry out ball milling on the ball mill, and the time of ball milling is 24 hours.The purpose of ball milling has two: at first be for ZnO, MgO and Ag
2The O powder mixes is even, with the homogeneity of the target that guarantees to prepare; Secondly, be for ZnO, MgO and Ag
2The O powder fining is beneficial to the moulding and the sintering of mixed powder subsequently.
After ball milling finished, it was 3 mm that powder compression is become thickness, and diameter is the disk of 50 mm.Earlier 800 ℃ of pre-burnings 1 hour, 1200 ℃ of sintering 8 hours, obtain target then.
2) with the quartz be substrate, put into the growth room of pulsed laser deposition device after substrate surface is cleaned, growth room's back of the body end vacuum tightness is evacuated to 10
-4Pa, heated substrate then, making underlayer temperature is 400 ℃, with above-mentioned make mix MgO and Ag
2The ZnO of O is a target, and the distance of adjusting substrate and target is 5.5 cm, with pure O
2(purity 99.99%) is growth atmosphere, control O
2Pressure 45 Pa, laser frequency is 5 Hz, and laser energy is to begin deposition growing under 300 mJ, and the time of growth is 60 min.Growth back original position under 100 Pa oxygen protective atmospheres is incubated 30 min, and slowly cooling obtains Ag doped p type ZnMgO crystal film afterwards.Its x ray diffraction (XRD) collection of illustrative plates is seen Fig. 2, and the room temperature photoluminescence spectrum is seen Fig. 3.
The Ag doped p type ZnMgO crystal film that makes at room temperature has excellent electric property: resistivity is 65.26 Ω cm, and mobility is 0.294 cm2V
-1s
-1, hole concentration is 3.25 * 10
17Cm
-3And the electric property of placing the several months rear film does not have considerable change.
Embodiment 2
1) get purity and be 99.99% zinc oxide, magnesium oxide and silver oxide powder, wherein the molar content of Mg is 10%, and the molar content of Ag is 1%,, with ZnO, MgO and Ag
2The mixed powder of O is poured in the agate ball cup, is placed on that ball milling is after 24 hours on the ball mill, and being pressed into thickness is 3 mm, and diameter is the disk of 50 mm.Earlier 800 ℃ of pre-burnings 1 hour, 1200 ℃ of sintering 8 hours, obtain target then.
2) with the quartz be substrate, put into the growth room of pulsed laser deposition device after substrate surface is cleaned, growth room's back of the body end vacuum tightness is evacuated to 10
-4Pa, heated substrate then, making underlayer temperature is 600 ℃, with above-mentioned make mix MgO and Ag
2The ZnO of O is a target, and the distance of adjusting substrate and target is 5.5 cm, with pure O
2(purity 99.99%) is growth atmosphere, control O
2Pressure 45 Pa, laser frequency is 5 Hz, and laser energy is to begin deposition growing under 300 mJ, and the time of growth is 60 min.Growth back original position under 100 Pa oxygen protective atmospheres is incubated 30 min, and slowly cooling obtains Ag doped p type ZnMgO crystal film afterwards.
The Ag doped p type ZnMgO crystal film that makes at room temperature has excellent electric property: resistivity is 4126 Ω cm, and mobility is 0.261 cm2V
-1s
-1, hole concentration is 5.80 * 10
15Cm
-3And the electric property of placing the several months rear film does not have considerable change.
Embodiment 3
1) get purity and be 99.99% zinc oxide, magnesium oxide and silver oxide powder, wherein the molar content of Mg is 10%, and the molar content of Ag is 0.6%,, with ZnO, MgO and Ag
2The mixed powder of O is poured in the agate ball cup, is placed on that ball milling is after 24 hours on the ball mill, and being pressed into thickness is 3 mm, and diameter is the disk of 50 mm.Earlier 800 ℃ of pre-burnings 1 hour, 1200 ℃ of sintering 8 hours, obtain target then.
2) with the sapphire be substrate, put into the growth room of pulsed laser deposition device after substrate surface is cleaned, growth room's back of the body end vacuum tightness is evacuated to 10
-4Pa, heated substrate then, making underlayer temperature is 400 ℃, with above-mentioned make mix MgO and Ag
2The ZnO of O is a target, and the distance of adjusting substrate and target is 5.5 cm, with pure O
2(purity 99.99%) is growth atmosphere, control O
2Pressure 30 Pa, laser frequency is 5 Hz, and laser energy is to begin deposition growing under 300 mJ, and the time of growth is 60 min.Growth back original position under 100 Pa oxygen protective atmospheres is incubated 30 min, and slowly cooling obtains Ag doped p type ZnMgO crystal film afterwards.
The Ag doped p type ZnMgO crystal film that makes at room temperature has excellent electric property: resistivity is 385.5 Ω cm, and mobility is 0.271 cm2V
-1s
-1, hole concentration is 5.98 * 10
16Cm
-3And the electric property of placing the several months rear film does not have considerable change.
Claims (4)
1.Ag the method for doped growing p type ZnMgO crystal film is characterized in that adopting pulsed laser deposition, comprises the steps:
1) the pure ZnO of weighing, pure MgO and pure Ag
2The O powder, wherein the molar content of Mg is 10%, and the molar content of Ag is 0.6 ~ 1%, and compression moulding after ball milling mixes more than 8 hours, makes target at 1200 ℃ of sintering then;
2) substrate after will cleaning is put into the growth room of pulsed laser deposition device, and the distance between target and the substrate is 5.5 cm, and growth room's back of the body end vacuum tightness is evacuated to 10
-4Pa, heated substrate then, making underlayer temperature is 300 ~ 600 ℃, with pure O
2Be growth atmosphere, control O
2Pressure 30 ~ 60 Pa, laser frequency is 3 ~ 5 Hz, grows, the film after the growth is cooled to room temperature under the oxygen atmosphere protection of 100 Pa.
2. the method for Ag doped growing p type ZnMgO crystal film according to claim 1 is characterized in that said substrate is silicon, sapphire, glass or quartz.
3. the method for Ag doped growing p type ZnMgO crystal film according to claim 1 is characterized in that pure O
2Purity be more than 99.99%.
4. the method for Ag doped growing p type ZnMgO crystal film according to claim 1 is characterized in that pure ZnO, pure MgO and pure Ag
2The purity of O powder is 99.99%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107177819A (en) * | 2017-05-15 | 2017-09-19 | 西安交通大学 | A kind of Ag MAX phases nano-composite plate and its deposition process |
| CN112708861A (en) * | 2020-12-16 | 2021-04-27 | 钢铁研究总院 | ZnO-based diluted magnetic semiconductor film with room-temperature ferromagnetism and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101037795A (en) * | 2007-01-29 | 2007-09-19 | 浙江大学 | Sb doped P-type ZnO crystal film and preparation method thereof |
| CN101319384A (en) * | 2008-06-03 | 2008-12-10 | 浙江大学 | Method for Na-doped growing p type Zn(1-x)MgxO crystal thin film |
-
2011
- 2011-04-01 CN CN 201110082020 patent/CN102162131A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101037795A (en) * | 2007-01-29 | 2007-09-19 | 浙江大学 | Sb doped P-type ZnO crystal film and preparation method thereof |
| CN101319384A (en) * | 2008-06-03 | 2008-12-10 | 浙江大学 | Method for Na-doped growing p type Zn(1-x)MgxO crystal thin film |
Non-Patent Citations (1)
| Title |
|---|
| 《Physica B》 20081231 Rui Deng等 Correlation between electrical,optical properties and Ag2+ centers of ZnO:Ag thin films 2004-2007 第403卷, * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107177819A (en) * | 2017-05-15 | 2017-09-19 | 西安交通大学 | A kind of Ag MAX phases nano-composite plate and its deposition process |
| CN112708861A (en) * | 2020-12-16 | 2021-04-27 | 钢铁研究总院 | ZnO-based diluted magnetic semiconductor film with room-temperature ferromagnetism and preparation method thereof |
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Application publication date: 20110824 |