CN102586867A - Method for preparing zinc oxide single crystal film by using iron oxide buffer layer - Google Patents
Method for preparing zinc oxide single crystal film by using iron oxide buffer layer Download PDFInfo
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- CN102586867A CN102586867A CN2012100667660A CN201210066766A CN102586867A CN 102586867 A CN102586867 A CN 102586867A CN 2012100667660 A CN2012100667660 A CN 2012100667660A CN 201210066766 A CN201210066766 A CN 201210066766A CN 102586867 A CN102586867 A CN 102586867A
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Abstract
The invention discloses a method for preparing a zinc oxide single crystal film by using an iron oxide buffer layer. The method is characterized by comprising the following steps of: (1) cleaning the surface of a Mo (110) substrate of a single crystal; (2) preheating evaporation sources of high-purity iron and zinc under an ultrahigh vacuum condition respectively to remove impurities and oxidation layers which are adsorbed on the surfaces of the evaporation sources; (3) evaporating iron to the Mo (110) substrate in the existence of oxygen to form an iron oxide single crystal film; and (4) evaporating Zn in the existence of the oxygen, depositing to an iron oxide film, and growing to form the ZnO (0001) single crystal film. The method has the advantages that: the iron oxide film grows on the Mo (110) substrate and is used as the buffer layer, so that the crystallization degree and the deposition rate of the ZnO film are improved, and the stability of a crystallization phase of the film is improved.
Description
Technical field
The invention belongs to technical field of semiconductors, relate to a kind of method for preparing oxide semiconductor thin-film, relate in particular to a kind of method of utilizing the red stone impact plies to prepare zinc oxide monocrystalline film.
Background technology
Zinc oxide (ZnO), is subjected to people's attention just gradually and obtains industrial application because of its unique physicochemical properties and photoelectric properties as the semi-conductive typical case's representative of the third generation.ZnO except have wide can band gap (3.37 eV), its free exciton intensity of activation is 60 meV, makes it to become the semiconductor material of the broad-band gap more superior than GaN (28 meV) and ZnSe (19 meV).Especially up to exciton intensity of activation and the plumbous zinc ore stability of structure of 60 meV, short wavelength's (blue light) photodiode or the laser apparatus that make this kind material process have very big application potential.For example, the ZnO stimulated emission that excites of at room temperature observed optical pumping is just significant to the application of exploitation ZnO photovaltaic material.In recent years, along with to the research of ZnO and associated materials thereof with its deepening continuously of area researches such as photoelectron, microelectronics, the crystal mass of ZnO is had higher requirement.How further to improve the crystal mass of ZnO, thereby reduce its defect and impurity, realize that stability p type doping preferably is the target that scientists is made great efforts.
Discovering on various substrates, to be difficult to prepare the extraordinary ZnO monocrystal thin films of percent crystallinity, mainly is because the lattice parameter between ZnO and the substrate differs big or surface energy differs less, is unfavorable for the initial forming core growth of ZnO monocrystalline.Scientist once proposed to utilize the impact plies as growth ZnO such as MgO (111) film, but because MgO (111) is the polarity oxide compound, at high temperature unstable, thus its effect influenced as impact plies.In addition, 9% lattice mismatch also is unfavorable for the initial forming core of ZnO monocrystalline between MgO (111) and ZnO (0001) face.But, compare direct growth ZnO on substrate, utilize impact plies to increase the nucleating center of ZnO initial growth, can improve the growth quality of ZnO really.Therefore, the more approaching ferric oxide monocrystalline film of utilization of the present invention and zinc oxide surface crystalline structure and lattice parameter might be prepared the ZnO monocrystal thin films of better quality fully as impact plies.
Summary of the invention
The object of the present invention is to provide a kind of method of utilizing the red stone impact plies to prepare zinc oxide monocrystalline film; This method is on Mo (110) substrate, to adopt thermal evaporation one deck sull of at first growing, and epitaxy goes out ZnO (0001) monocrystal thin films on this sull then.Through optimizing processing parameters such as growth temperature, annealing temperature, oxygen pressure, improve the quality of ZnO epitaxial film effectively, and improve its surface finish simultaneously.
The present invention realizes like this, it is characterized in that method steps is:
(1) make pure source of iron and zinc source: first is after iron wire and zinc silk more than 99.99% carries out ultrasonic cleaning with alcohol and acetone with purity; Tightly be wrapped on the purified tungsten filament; Again iron and these two kinds of source metal of zinc are packed into and be fixed in the supervacuum chamber, form the evaporation source of iron and zinc.Adopt the galvanic current heating method to these two source metal heating,, thereby guarantee that the atoms metal that is evaporated has very high purity with the gaseous impurities and the zone of oxidation of removing surface adsorption;
(2) single-crystal metal substrate surface clean: promptly in Vakuumkammer, feed 1 * 10
-5The O of Pa
2, metal M o (110) substrate was annealed 10 minutes under 800～900 ℃ of temperature, close oxygen again and rapidly substrate is heated to 1300 ℃; According to the said process repeatable operation several times after, make substrate 1800～2000 ℃ of down annealing again, promptly obtain the surface metal substrate of cleaning fully;
(3) measure the source metal vaporator rate: connect direct current to source metal, treat to utilize thickness tester to measure the vaporator rate of iron and zinc after steady state is heated evenly, is reached to source metal.Regulate the dc electric power of source metal, the vaporator rate in control source of iron and zinc source is at 0.1～0.4 nm/min;
(4) growth red stone impact plies: Mo (110) substrate is heated to 350-400 ℃, and keeps this temperature-resistant.After treating that the vaporator rate of source of iron is stable, substrate surface over against source metal, is fed pressure≤1 * 10
-4The O of Pa
2, according to needed film thickness, setting needs the time of growth.After treating that growth is accomplished, close oxygen valve, with the speed of 20-30 ℃/min underlayer temperature is reduced to room temperature from 350-400 ℃ lentamente again.The Fe that forms like this
3O
4(111) film is as the impact plies of growth ZnO.
(5) growth ZnO (0001) monocrystal thin films: after treating that the vaporator rate in zinc source is stable, feed pressure≤1 * 10
-4The O of Pa
2, ZnO at room temperature is grown in Fe
3O
4(111) on the film.According to needed film thickness, setting needs the time of growth.After treating that growth is accomplished, close source metal, with the temperature rise rate of 5-10 ℃/min underlayer temperature is increased to about 400 ℃, and kept 10-20 minute, naturally cool to room temperature then.The anneal that heats up after growth is accomplished helps the recrystallize of ZnO, thereby improves the crystalline quality of ZnO along (0001) face.
Wherein the formation of red stone impact plies and growth conditions are closely related, on Mo (110) substrate, can form Fe
3O
4(111), FeO (111) or Fe
2O
3(0001) film all can be used as the impact plies of growth ZnO (0001) monocrystal thin films but research shows these films.Therefore, so long as the oxide monocrystal film of iron all can be used as buffer growth ZnO (0001) monocrystal thin films.
Advantage of the present invention is: utilize thermal evaporation deposition process on the good metal M o of thermal conductivity (110) single crystalline substrate, to realize the preparation of ZnO (0001) monocrystal thin films as impact plies through sull; Through the interfacial interaction between sull in present method and the metal substrate, between zinc-oxide film and the sull; Strengthened the unicity of film crystal lattice orientation; Reduced and formed the possibility of polycrystalline phase, thereby realized the oriented growth of ZnO film along (0001) face; Present method adopts metal single crystal as substrate, utilizes the advantage of its surface energy, on thermodynamics, helps the oriented growth of sull.In addition, the oxide compound (Fe of three kinds of iron in present method
3O
4(111), FeO (111) or Fe
2O
3(0001)) all can be used as impact plies, thereby, increased feasibility and the convenience of implementing present method from experimentally having reduced valent requirement to iron.
Description of drawings
Fig. 1 utilizes sull to prepare the process flow sheet of ZnO monocrystal thin films as impact plies on the metal single crystal substrate for the present invention.
Fig. 2 is the phonon vibration spectrum on the ZnO monocrystal thin films surface of the present invention's preparation.
Fig. 3 is the surface topography of the ZnO monocrystal thin films of the present invention's preparation.
Embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is elaborated:
On the metal single crystal substrate, utilize sull to prepare the process flow sheet of ZnO monocrystal thin films as impact plies like Fig. 1 for the present invention.In order to guarantee the purity of ZnO (0001) monocrystal thin films, this preparation method need carry out under UHV condition.Source metal and oxygen all have very high purity.From surface treatment that is prepared into substrate of source metal etc., all need carry out clean.The present invention utilizes the red stone impact plies when preparation high-quality ZnO (0001) monocrystal thin films, and its concrete steps are following:
(1) is after iron wire and zinc silk 99.99% or more carries out ultrasonic cleaning with alcohol and acetone, tightly to be wrapped on the purified tungsten filament earlier, again iron and these two kinds of source metal of zinc packed into and be fixed in the supervacuum chamber evaporation source of formation iron and zinc purity.Adopt the galvanic current heating method to these two source metal heating,, improve the purity of source metal with the gaseous impurities and the zone of oxidation of removing surface adsorption;
(2) in Vakuumkammer, feed 1 * 10
-5The O of Pa
2, metal M o (110) substrate was annealed 10 minutes down at 800～900 ℃, close oxygen again and rapidly substrate is heated to 1300 ℃, mainly be to remove the small amount of carbon impurity in the Mo monocrystalline through high temperature oxidation; According to the said process repeatable operation several times after, make again substrate 1800～2000 ℃ down annealing remove the oxide compound of the Mo that the surface forms, thereby obtain the surface metal single crystal substrate of cleaning fully;
(3) give the heating of source of iron and zinc source respectively through direct supply, treat to utilize thickness tester to measure the vaporator rate of iron and zinc again after steady state is heated evenly, is reached to source metal.Regulate the dc electric power of source metal, the vaporator rate in control source of iron and zinc source is at 0.1～0.4 nm/min;
(4) Mo (110) substrate is heated to 350-400 ℃, and keeps this temperature-resistant.After treating that the vaporator rate of source of iron is stable, substrate surface over against source metal, is fed pressure≤1 * 10
-4The O of Pa
2, realize Fe
3O
4(111) growth of film on Mo (110) substrate.According to vaporator rate and the needed film thickness set, setting needs the time of growth.After treating that growth is accomplished, close oxygen valve, with the speed of 20-30 ℃/min underlayer temperature is reduced to room temperature from 350-400 ℃ lentamente again.The Fe that forms like this
3O
4(111) film is as the impact plies of growth ZnO.
(5) treat that the vaporator rate in zinc source is stable after, feed pressure≤1 * 10
-4The O of Pa
2, at room temperature ZnO is grown in Fe
3O
4(111) on the film.According to needed film thickness, setting needs the time of growth.After treating that growth is accomplished, close source metal, with the temperature rise rate of 5-10 ℃/min underlayer temperature is increased to about 400 ℃, and kept 10-20 minute, naturally cool to room temperature then, thereby obtained ZnO (0001) monocrystal thin films.
In above-mentioned each step, the temperature of metal substrate is that the direct supply through constant pressure and flow produces and directly measured by the thermocouple that point is welded in the metal substrate side.
In the preparation process or after the preparation completion, can utilize the variation of Auger electron spectrometer in-situ observation surface-element content at any time and utilize the surphon of high resolution electronic energy loss spectrometer monitoring ZnO film to vibrate and crystal lattice orientation.Fig. 2 prepares the surphon vibration spectrum of ZnO (0001) monocrystal thin films for adopting the inventive method.This spectrogram has shown that clearly the phonon vibration of ZnO (0001) film surface is very regular, explains that the crystal lattice orientation of prepared ZnO film is fine.Fig. 3 can find out that for the surface topography map of ZnO (0001) monocrystal thin films of 10 nanometer thickness of the present invention's preparation film surface is quite evenly smooth.The ZnO that utilization a process for preparing (0001) monocrystal thin films, the well-crystallized, the orientation unicity is good, and this preparing method's technology is simple, favorable repeatability can be applied based in the semiconductor material preparation of broad-band gap and the photoelectric device.
Claims (1)
1. method of utilizing the red stone impact plies to prepare zinc oxide monocrystalline film is characterized in that method steps is:
(1) make pure source of iron and zinc source: first is after iron wire and zinc silk more than 99.99% carries out ultrasonic cleaning with alcohol and acetone with purity; Tightly be wrapped on the purified tungsten filament; Again iron and these two kinds of source metal of zinc are packed into and be fixed in the supervacuum chamber, form the evaporation source of iron and zinc, adopt the galvanic current heating method that these two source metal are heated; With the gaseous impurities and the zone of oxidation of removing surface adsorption, thereby guarantee that the atoms metal that is evaporated has very high purity;
(2) single-crystal metal substrate surface clean: promptly in Vakuumkammer, feed 1 * 10
-5The O of Pa
2, metal M o (110) substrate was annealed 10 minutes under 800～900 ℃ temperature, close oxygen again and rapidly substrate is heated to 1300 ℃; According to the said process repeatable operation several times after, make substrate 1800～2000 ℃ of down annealing again, promptly obtain the surface metal substrate of cleaning fully;
(3) measure the source metal vaporator rate: regulate the dc electric power of source metal, utilize thickness tester to measure the vaporator rate of iron and zinc, the vaporator rate in control source of iron and zinc source is between 0.1～0.4 nm/min;
(4) growth red stone impact plies: Mo (110) substrate is heated to 350-400 ℃, and keeps this temperature-resistant, treat that the vaporator rate of source of iron is stable after, substrate surface over against source metal, is fed pressure≤1 * 10
-4The O of Pa
2, according to needed film thickness, setting needs the time of growth; After treating that growth is accomplished, close oxygen valve, with the speed of 20-30 ℃/min underlayer temperature is reduced to room temperature from 350-400 ℃ lentamente again, formed Fe like this
3O
4(111) film is as the impact plies of growth ZnO;
(5) growth ZnO (0001) monocrystal thin films: after treating that the vaporator rate in zinc source is stable, feed pressure≤1 * 10
-4The O of Pa
2, ZnO at room temperature is grown in Fe
3O
4(111) on the film, according to needed film thickness, setting needs the time of growth; After treating that growth is accomplished, close source metal, underlayer temperature is increased to about 400 ℃ with the temperature rise rate of 5-10 ℃/min; And kept 10-20 minute; Naturally cool to room temperature then, the anneal that heats up after growth is accomplished helps the recrystallize of ZnO, thereby improves the crystalline quality of ZnO along (0001) face.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111161806A (en) * | 2019-12-30 | 2020-05-15 | 国电科学技术研究院有限公司 | Method for calculating oxide film thickness of martensite heat-resistant steel under supercritical high-temperature steam |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1517454A (en) * | 2003-01-13 | 2004-08-04 | 中国科学院长春光学精密机械与物理研 | Method of preparing oxide film by molecular beam epitaxy |
| CN101388345A (en) * | 2007-09-12 | 2009-03-18 | 中国科学院半导体研究所 | Process for growing ZnO thin-film on metal substrate |
| CN100545314C (en) * | 2005-12-14 | 2009-09-30 | 中国科学院物理研究所 | Be used to prepare the in-situ treatment method of sapphire substrate of high-quality zinc oxide film |
| CN101805885A (en) * | 2010-04-06 | 2010-08-18 | 南昌航空大学 | Method for preparing MgZnO ternary compound ordered film |
-
2012
- 2012-03-15 CN CN2012100667660A patent/CN102586867A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1517454A (en) * | 2003-01-13 | 2004-08-04 | 中国科学院长春光学精密机械与物理研 | Method of preparing oxide film by molecular beam epitaxy |
| CN100545314C (en) * | 2005-12-14 | 2009-09-30 | 中国科学院物理研究所 | Be used to prepare the in-situ treatment method of sapphire substrate of high-quality zinc oxide film |
| CN101388345A (en) * | 2007-09-12 | 2009-03-18 | 中国科学院半导体研究所 | Process for growing ZnO thin-film on metal substrate |
| CN101805885A (en) * | 2010-04-06 | 2010-08-18 | 南昌航空大学 | Method for preparing MgZnO ternary compound ordered film |
Non-Patent Citations (2)
| Title |
|---|
| KEFEI ZHENG ET AL: "A buffer layer for ZnO film growth on sapphire", 《SURFACE SCIENCE》 * |
| 杨斌等: "同质缓冲层厚度对掺铝氧化锌薄膜性能的影响", 《电子元件与材料》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111161806A (en) * | 2019-12-30 | 2020-05-15 | 国电科学技术研究院有限公司 | Method for calculating oxide film thickness of martensite heat-resistant steel under supercritical high-temperature steam |
| CN111161806B (en) * | 2019-12-30 | 2023-10-17 | 国家能源集团科学技术研究院有限公司 | Method for calculating oxide film thickness of martensitic heat-resistant steel under supercritical high-temperature steam |
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Application publication date: 20120718 |