CN1303650C - p-Zn1-XMgXO crystal film and method for making same - Google Patents

p-Zn1-XMgXO crystal film and method for making same Download PDF

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Publication number
CN1303650C
CN1303650C CNB200310108467XA CN200310108467A CN1303650C CN 1303650 C CN1303650 C CN 1303650C CN B200310108467X A CNB200310108467X A CN B200310108467XA CN 200310108467 A CN200310108467 A CN 200310108467A CN 1303650 C CN1303650 C CN 1303650C
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crystal film
purity
target
gas
subjected
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CN1542915A (en
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叶志镇
张银珠
黄靖云
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Zhejiang University ZJU
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Zhejiang University ZJU
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Abstract

The present invention relates to a p-Zn<1-x>Mg<x>O crystal film. One or some of B, Al, Ga and In are used as donors, one or some of N, P and As gases are used as acceptors, and the donors and the acceptors are doped in the p-Zn<1-x>Mg<x>O crystal film, wherein the mole content of x is more than 0 and less than 40%, and the doping concentration is 10<15> to 10<19> cm<-3>. The film can be prepared with a pulsed laser deposition method, and a target is a ceramic target which is formed by mixing and sintering high-purity ZnO, MgO and donor dopant powder, wherein the mole content of MgO is more than 0 and less than 40%, and the mole content of the donor dopant is more than 0 and less than 3%. The growth temperature is from 400 to 700 DEG C, and the growth atmosphere is mixed gas of a gas which is activated by plasma and contains acceptors, and high-purity O2. The doping concentration can be controlled by regulating the partial pressure ratio of the input gas containing acceptors and the high-purity O2, the mole content of the donor dopant in the target, and the temperature of subsequent annealing treatment.

Description

A kind of p-Zn 1-xMg xO crystal film and preparation method thereof
Technical field
The present invention relates to the Zn that the p type mixes 1-xMg xO crystal film and preparation method thereof.
Background technology
When the molar content of Mg is no more than 33at%, Zn 1-xMg xO ternary alloy three-partalloy film has identical crystal structure with ZnO film, close lattice constant, but Mg mix the forbidden band broadening that makes ZnO, can realize the cutting of ZnO energy gap.In order to improve the luminous efficiency of zno-based photoelectric device, generally adopt shape such as p-Zn 1-xMg xO/ZnO/n-Zn 1-xMg xThe heterojunction of O, quantum well and superlattice structure not only require the lattice constant and the potential well coupling of barrier layer, and need growth stable, controlled n type and p type Zn 1-xMg xThe O crystal film.But plain Zn is only arranged in the world at present 1-xMg xThe report of O crystal film does not have n type and p type Zn 1-xMg xThe report of O crystal film.It is a global difficult problem that the p type of zno-based film mixes, and this doping techniques does not solve, and will influence the application of zno-based crystal film aspect photoelectric device greatly.
Summary of the invention
The purpose of this invention is to provide the Zn that a kind of p type mixes 1-xMg xO crystal film and preparation method thereof.
P-Zn of the present invention 1-xMg xThe O crystal film is to be the alms giver, to be the p-Zn that is subjected to main codope with in N, P, the As gas one or more with among B, Al, Ga, the In one or more 1-xMg xO crystal film, the molar content of x are 0＜x＜40%, and doping content is 10 15～10 19Cm -3
P-Zn of the present invention 1-xMg xThe preparation method of O crystal film is a pulsed laser deposition, and preparation process may further comprise the steps:
1) sintering of ceramic target: high-purity ZnO, the MgO of weighing purity＞99.99% and donor dopant powder, wherein the molar content x of MgO is 0＜x＜40%, the molar content y of donor dopant is 0＜y＜3%, above-mentioned powder is mixed with ball milling, grind back compression moulding, at 800～1200 ℃ of sintering temperatures, make the Zn that mixes the alms giver 1-xMg xThe O ceramic target;
2) preparation of film: the ceramic target that step 1) is made and put into the growth room of pulsed laser deposition device with the substrate that conventional method was cleaned, the distance between target and the substrate remains 4～6cm, and growth room's vacuum is extracted into 10 at least -3Pa, the substrate heating makes it to be warmed up to 400～700 ℃, is subjected to main gas and high-purity O plasma-activated high-purity containing with process 2Mist be growth atmosphere, be subjected to main gas and high-purity O 2Voltage ratio be 1: 1-4, pressure is 5～15Pa, opens laser, allows laser radiation to target surface, target atom breaks away from target, forms shock wave, alms giver wherein and activity are subjected to the principal phase mutual effect, are deposited on the substrate acquisition p-Zn 1-xMg xThe O crystal film;
3) annealing in process: to step 2) deposit the p-Zn that obtains 1-xMg xThe O crystal film carries out annealing in process, and annealing atmosphere is a high-purity N 2, 400～1000 ℃ of annealing temperatures, annealing time 1 hour.
Above-mentioned to be subjected to main gas be in N, P, the As gas one or more, and wherein N can be N 2, NH 3, N 2O, NO or NO 2Gas.Said donor dopant is one or more the oxide that contains among B, Al, Ga or the In.Adoptable substrate has sapphire, silicon, zinc oxide or glass.
Contain by adjusting and to be subjected to main gas and high-purity O 2Voltage ratio, target in alms giver's content and the p-Zn that temperature that subsequent anneal is handled can prepare different levels of doping 1-xMg xThe O film, growth time is by the thickness decision of required crystal film.
Advantage of the present invention:
1) adopts alms giver, mixing of being subjected to that main codope can promote to be led, improve doping content.
2) doping content can contain gas and the high-purity O that is led by adjusting 2Voltage ratio and target in the molar content of donor dopant control.
3) subsequent anneal is handled and not only can be improved the crystal mass of film, and can promote the doping led.
4) p-Zn of the present invention 1-xMg xThe energy gap of O crystal film is adjustable in 3.3～4.0eV scope.
5) method for manufacturing thin film has advantages such as growth temperature is low, deposition parameter is controlled easily, deposit film quality is better.
Description of drawings
Fig. 1 is the equipment schematic diagram of pulsed laser deposition.
Among the figure: 1 is laser; 2 is the growth room; 3 is target; 4 is substrate
Embodiment
Embodiment: with Al 2O 3Be donor dopant, N 2O is the acceptor doping source, is substrate growth p-Zn with the silicon chip 1-xMg xThe O film.Concrete steps are as follows:
1) sintering of ceramic target: high-purity ZnO, MgO and the Al of weighing purity＞99.99% 2O 3Powder makes that MgO and ZnO molar content ratio are 1: 4, Al 2O 3Molar content be 0.5%.With load weighted ZnO, MgO and Al 2O 3Powder is poured in the ball grinder that agate ball is housed, and ball milling is 20 hours on ball mill, and purpose is to allow raw material mix and refinement to a certain extent, is beneficial to the moulding and the sintering of ceramic target.Then raw material is separated and dried, add binding agent and grind compression moulding.At last the idiosome of moulding is put into sintering furnace, plain through low temperature (200～400 ℃) row, make the binding agent volatilization, be warming up to 800～1200 ℃ of sintering again 3 hours, obtaining thickness is 3mm, diameter is the ceramic disks of 5.5cm, Here it is Zn 1-x-yMg xAl yThe O ceramic target.
2) preparation of film: before deposit film, silicon chip surface cleans with the RCA method earlier.The ceramic target that sinters is contained on the target frame, embeds in the target holder of impulse laser deposition system.Again cleaned silicon chip is fixed on the specimen holder, puts into the growth room.The distance of regulating substrate and target is 5cm, and with baffle plate substrate and target is separated.Base vacuum to 5 * 10 are taken out by the growth room -3Pa, substrate is heated to 600 ℃ of film growth temperature then.Feed high-purity O 2With with plasma-activated N 2O, the two-way gas flow is controlled by flowmeter, voltage ratio N 2O: O 2=1: 1, pressure is controlled at 12Pa.Open laser (operating voltage 27KeV, frequency 1.5Hz), pre-deposition 5 minutes is to remove the contamination of target material surface, the baffle plate of outwarding winding then, deposit film.Substrate and target low speed rotation in the growth course are to improve the uniformity of film.
3) annealing in process: to the step 2) p-Zn that makes 1-xMg xThe O crystal film carries out annealing in process, and annealing atmosphere is the high-purity N of purity＞99.99% 2, 1 hour time, annealing temperature is 500 ℃.
By changing MgO and Al in the target 2O 3Content, contain N gas and high-purity O 2Voltage ratio; And the temperature of subsequent anneal processing can make the p-Zn of different levels of doping and component 1-xMg xO crystal film, doping content are 10 15～10 19Cm -3

Claims (5)

1. p-Zn 1-xMg xThe O crystal film is characterized in that it is to be the alms giver, to be the p-Zn that is subjected to main codope with in N, P, the As gas one or more with among B, Al, Ga, the In one or more 1-xMg xO crystal film, the molar content of x are 0＜x＜40%, and doping content is 10 15～10 19Cm -3
2. described p-Zn of claim 1 1-xMg xThe preparation method of O crystal film is characterized in that adopting pulsed laser deposition, may further comprise the steps:
1) sintering of ceramic target: high-purity ZnO, the MgO of weighing purity＞99.99% and donor dopant powder, wherein the molar content x of MgO is 0＜x＜40%, the molar content y of donor dopant is 0＜y＜3%, above-mentioned powder is mixed with ball milling, grind back compression moulding, at 800～1200 ℃ of sintering temperatures, make the Zn that mixes the alms giver 1-xMg xThe O ceramic target;
2) preparation of film: the ceramic target that step 1) is made and put into the growth room of pulsed laser deposition device with the substrate that conventional method was cleaned, the distance between target and the substrate remains 4～6cm, and growth room's vacuum is extracted into 10 at least -3Pa, the substrate heating makes it to be warmed up to 400～700 ℃, is subjected to main gas and high-purity O plasma-activated high-purity containing with process 2Mist be growth atmosphere, be subjected to main gas and high-purity O 2Voltage ratio be 1: 1-4, pressure is 5～15Pa, opens laser, allows laser radiation to target surface, target atom breaks away from target, forms shock wave, alms giver wherein and activity are subjected to the principal phase mutual effect, are deposited on the substrate acquisition p-Zn 1-xMg xThe O crystal film;
3) annealing in process: to step 2) deposit the p-Zn that obtains 1-xMg xThe O crystal film carries out annealing in process, and annealing atmosphere is a high-purity N 2, 400～1000 ℃ of annealing temperatures, annealing time 1 hour.
3. p-Zn according to claim 2 1-xMg xThe preparation method of O crystal film is characterized in that said to be subjected to main gas be in N, P, the As gas one or more, and wherein N is N 2, NH 3, N 2O, NO or NO 2Gas.
4. p-Zn according to claim 2 1-xMg xThe preparation method of O crystal film is characterized in that said donor dopant is one or more oxides that contain among B, Al, Ga or the In.
5. p-Zn according to claim 2 1-xMg xThe preparation method of O crystal film is characterized in that said substrate is sapphire, silicon, zinc oxide or glass.
CNB200310108467XA 2003-11-04 2003-11-04 p-Zn1-XMgXO crystal film and method for making same Expired - Fee Related CN1303650C (en)

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Publication number Priority date Publication date Assignee Title
CN100406620C (en) * 2006-05-11 2008-07-30 浙江大学 Li-doped p-Zn1-xMgxO crystal film and method for preparing same
CN101805885B (en) * 2010-04-06 2011-10-05 南昌航空大学 Method for preparing MgZnO ternary compound ordered film
CN102787294B (en) * 2011-05-19 2014-08-27 海洋王照明科技股份有限公司 Preparation method and use of titanium-doped zinc-magnesium aluminate film
CN103866265B (en) * 2012-12-11 2016-12-21 中国科学院微电子研究所 Double acceptor based on nitrogen is co-doped with the preparation method of zinc-oxide film
CN103866276B (en) * 2012-12-11 2016-08-03 中国科学院微电子研究所 The method of the zinc-oxide film that ald preparation is co-doped with
CN103866284A (en) * 2012-12-14 2014-06-18 中国科学院微电子研究所 Preparation method of zinc oxide thin film
CN103166112B (en) * 2013-03-01 2016-03-02 溧阳华晶电子材料有限公司 A kind of p-type zinc-oxide film of nitrogen magnesium codope
CN110923667A (en) * 2019-12-18 2020-03-27 北京工业大学 Efficient and simple preparation method of secondary electron emission thin film material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001044499A (en) * 1999-07-26 2001-02-16 Agency Of Ind Science & Technol ZnO COMPOUND SEMICONDUCTOR LIGHT-EMITTING DEVICE USING SILICON SUBSTRATE AND MANUFACTURING METHOD THEREFOR
WO2002089223A1 (en) * 2001-04-27 2002-11-07 Shin-Etsu Handotai Co., Ltd. Production method for light emitting element absract:
CN1440053A (en) * 2003-03-25 2003-09-03 浙江大学 P-ZnO thin film and preparation thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001044499A (en) * 1999-07-26 2001-02-16 Agency Of Ind Science & Technol ZnO COMPOUND SEMICONDUCTOR LIGHT-EMITTING DEVICE USING SILICON SUBSTRATE AND MANUFACTURING METHOD THEREFOR
WO2002089223A1 (en) * 2001-04-27 2002-11-07 Shin-Etsu Handotai Co., Ltd. Production method for light emitting element absract:
CN1440053A (en) * 2003-03-25 2003-09-03 浙江大学 P-ZnO thin film and preparation thereof

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