CN1309020C - A method for preparing high-quality ZnO single crystal film on magnesium aluminate substrate - Google Patents
A method for preparing high-quality ZnO single crystal film on magnesium aluminate substrate Download PDFInfo
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- CN1309020C CN1309020C CNB2005100646537A CN200510064653A CN1309020C CN 1309020 C CN1309020 C CN 1309020C CN B2005100646537 A CNB2005100646537 A CN B2005100646537A CN 200510064653 A CN200510064653 A CN 200510064653A CN 1309020 C CN1309020 C CN 1309020C
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Abstract
The present invention discloses a method for preparing a high grade ZnO monocrystal film on a magnesium aluminate substrate, which comprises the steps: oxygen plasma preprocessing is carried out to the surface of the magnesium aluminate (111) substrate at low temperature to form an oxygen termination surface, and a magnesium film is deposited at low temperature in ultrahigh vacuum; the substrate temperature rises to anneal the magnesium superthin layer, magnesium atoms and oxygen atoms on the magnesium aluminate (111) substrate are bounded, transferred and desorbed, and a very thin magnesium oxide adsorption layer with magnesium enriched surfaces is finally obtained; the present invention provides a uniform nucleation layer for the epitaxial growth of oxygen polarity ZnO, and an atomic scale high grade ZnO film with single oxygen polarity is prepared and obtained by a two step growth method. The surface of the ZnO monocrystal film prepared by the present invention has clear growth step, the surface roughness within the range of 1*1m<2> is below 1 nm, and the present invention is suitable for preparing high performance photoelectronic devices, such as an ultraviolet detector, etc.
Description
Technical field
The present invention relates to a kind of method for preparing wide bandgap semiconductor zinc oxide (ZnO) monocrystal thin films, especially technology controlling and process surface and interfaces such as the deposition of the preparation preliminary treatment by substrate surface and magnesium metal thin layer during zinc-oxide film and annealing on magnesium aluminate (111) face, thereby the method for acquisition zinc-oxide film.
Background technology
ZnO has multiple superior function, has a wide range of applications at aspects such as nesa coating, surface acoustic wave device and piezoelectric ceramic.ZnO also is an a kind of direct transition type II-VI family semiconductor, and the room temperature energy gap is 3.37eV.Because its very high free exciton binding energy (60meV), ZnO has become another important semiconductor material with wide forbidden band behind GaN, aspect the low threshold value of preparation, the high efficiency short-wavelength light electronic device very wide application prospect is being arranged.The preparation of device quality zno-based epitaxial film is the basic point that realizes its device application.Though the commercialization of ZnO single crystalline substrate, its price are still very expensive, therefore, the isoepitaxial growth technology of ZnO monocrystal thin films also can't realize commercial Application at present.Similar to GaN, ZnO film prepares by big mismatch heteroepitaxy mostly, problems such as the thin film strain that needs the big mismatch heterostructure system of solution to be brought is big, defect concentration height.Therefore, suitable epitaxially grown backing material of ZnO of exploration and corresponding high-quality thin film technology of preparing have crucial meaning.
Magnesium aluminate (MgAl
2O
4) monocrystalline (spinelle) is widely used in sound wave and microwave device and the epitaxial substrate of IC fast; Recently, discover that it also can be as the substrate of III-V nitride devices, but since at high temperature during growing gallium nitride (GaN) film the oxygen in the substrate can be diffused in the epitaxial film, cause the background electron concentration 1 * 10
18Cm
-3More than, greatly limited this extension system in industrial application.Zinc oxide has identical crystal structure and close lattice constant with gallium nitride, in addition, temperature is relatively low during the preparation zinc-oxide film, the diffusion in epitaxial film of magnesium, aluminium and oxygen is less in the substrate, therefore, magnesium aluminate is considered to the good substrate of zinc oxide, and lattice mismatch is 13.6% between them, and it is little by nearly 5% that the mismatch (18.3%) than zinc oxide growth on the c surface sapphire substrate time is wanted.
2000, people such as Chen have reported result (the Yefan Chen of preparation zinc-oxide film on magnesium aluminate (111) face, etc., Appl.Phys.Lett., 76,245 (2000)), epitaxial growth zinc-oxide film under 550 ℃ the temperature on their magnesium aluminate (111) face after passing through chemical etching, atomic force microscope (AFM) test result shows that the surface of gained monocrystal thin films presents island structure, at 2 * 2 μ m
2Surface roughness in the scope is 4nm.The test result of X-ray diffraction (XRD) shows that the crystalline quality of crystal is relatively poor, and defect concentration is higher; Its reason is that the atom packing of magnesium aluminate on [111] direction is-O-Al-O-Mg-Al-Mg-O-in proper order, wherein the oxygen atomic layer in (111) face is not to arrange by the hexagonal structure of strictness, has certain distortion, direct growth zinc oxide will produce a large amount of defectives on this face, thereby has influenced this application of extension system in industrialization.Therefore, invent and a kind ofly can carry out correction on the atomic scale to magnesium aluminate (111) surface, the template that obtains a suitable zinc oxide epitaxial growth is the key point of this extension system.
Summary of the invention
The purpose of this invention is to provide a kind of new method for preparing zinc oxide thin film, this method is prepared has atomically smooth zinc oxide monocrystalline film, and its superior photoelectric properties show that this film is very suitable for the making of high-performance optical electronic device.
The preparation of zinc-oxide film of the present invention realizes by the following technical solutions:
1) magnesium aluminate (111) substrate back is plated molybdenum, and clean, then substrate is imported the molecular beam epitaxial growth system;
2) carry out radio frequency oxygen plasma treatment about 30 minutes under 20～200 ℃ of low temperature, radio-frequency power is 300～450W, and oxygen flow is 1～3sccm, with magnesium aluminate (111) substrate that obtains the oxygen terminal surface; Selecting the purpose of low temperature is the desorption that prevents surperficial oxygen atom;
3) in air pressure＜1 * 10
-6Pa and underlayer temperature be plated metal magnesium between 20～200 ℃, and the control sedimentation time is to obtain the thick sheet metal magnesium of 3～5mm;
4) 200～500 ℃ of down annealing, allow magnesium atom combines with the oxygen atom of magnesium aluminate (111) substrate surface, migration, desorption, obtain the even magnesium oxide layer of surperficial rich magnesium at last, for epitaxial growth of ZnO provides a forming core layer;
5) temperature deposit thickness between 200～500 ℃ is the ZnO resilient coating of 10～30nm, and oxygen, zinc line are adjusted to the scope of the rich zinc near stoichiometric(al) during with growth, can obtain oxygen polarity ZnO;
6) under 700～800 ℃ of temperature, oxygen atmosphere, anneal; Annealing time is 10～30 minutes;
7) 500～700 ℃ of growths of carrying out epitaxial loayer; Oxygen, zinc line are adjusted to the scope of the rich zinc near stoichiometric(al) in the time of will growing by known means; Behind the ZnO film growth ending, under 700～800 ℃ of temperature, oxygen atmosphere, anneal; Annealing time is 10～30 minutes.
The difference of above-mentioned oxygen polarity ZnO monocrystal thin films preparation method and existing method mainly be to grow the substrate surface preliminary treatment before the ZnO resilient coating and the deposition and the annealing of magnesium thin layer.At a lower temperature magnesium aluminate (111) substrate surface is carried out sufficient oxygen plasma treatment, obtain uniform oxygen terminal surface; Lower treatment temperature can avoid oxygen atom from the substrate surface desorption.Fast the air pressure of growth chamber is reduced to then＜1 * 10
-6Pa is for low temperature depositing magnesium thin layer provides condition.Magnesium metal combines with the oxygen of magnesium aluminate substrate surface, and anneals under higher temperature, forms magnesium oxide (111) adsorption layer of surperficial rich magnesium uniformly; Because the saturated vapor pressure of magnesium metal is very high, and magnesium oxide is stable in very wide temperature range, therefore above-mentioned annealing region very wide (200～500 ℃), and technology is simple, be easy to control.The magnesium atom or the oxygen atom of magnesium oxide (111) face have complete hexagonal symmetry, the mismatch of its lattice and ZnO (0001) lattice is 8.9%, therefore, magnesium oxide (111) face that obtains through said method provides a very ideal template for the ZnO forming core, not only solve the influence that the oxygen atom lattice that twists in magnesium aluminate (111) face causes the ZnO forming core, simultaneously mismatch has been reduced to 8.9% from 13.6%.The forming core at zinc oxide growth initial stage has decisive influence for the release of film misfit strain and the raising of film quality, the method that this method combines with MgO forming core layer by the substrate surface preliminary treatment is easy and controlled MgO (111)/MgAl very effectively
2O
4(111) and ZnO (000-1)/MgO (111) heterogeneous interface atomic structure, thus realized the single epitaxial orientation and the growth of single oxygen Polarity Control of ZnO monocrystal thin films.Reflected high energy electron diffraction (RHEED) home position observation result shows that gained ZnO epitaxial film surface has clearly 3X3 surface structure again, the high temperature epitaxy layer is a step-flow formula two-dimensional growth pattern, the test result of atomic force microscope (AFM) shows, the surface has gem-pure growth step, at 1 * 1 μ m
2Surface roughness in the scope is all below 1nm.In addition, this film of test shows of X-ray diffraction (XRD) has extraordinary crystallinity, is fit to the making of high-performance zinc oxide base optical electronic part fully.
Description of drawings
Fig. 1 prepares the process chart of ZnO monocrystal thin films on magnesium aluminate (111) face for the present invention;
Fig. 2 is the prepared ZnO sample thickness test result of the present invention;
Reflected high energy electron diffraction home position observation pattern when Fig. 3 prepares the ZnO monocrystal thin films for the present invention;
Fig. 4 is the atomic force microscope figure on the prepared ZnO monocrystal thin films surface of the present invention.
Embodiment
The present invention is described in detail below in conjunction with embodiment and accompanying drawing.
Process chart of the present invention as shown in Figure 1, the concrete steps of preparation ZnO monocrystal thin films are as follows on magnesium aluminate (111) substrate:
1. magnesium aluminate (111) substrate back is plated molybdenum, and clean, then substrate is imported the molecular beam epitaxial growth system;
2. carry out the radio frequency oxygen plasma treatment about 30 minutes under 100 ℃ of temperature, radio-frequency power is 350W, and oxygen flow is 2.5sccm, and with magnesium aluminate (111) substrate that obtains the oxygen terminal surface, selecting the purpose of low temperature is the desorption that prevents surperficial oxygen atom;
3. in air pressure＜1 * 10
-6Plated metal magnesium when 100 ℃ of Pa and underlayer temperatures, the equivalent vapour pressure of magnesium line is 1 * 10
-5About Pa, obtain the thick magnesium metal thin layer of 3～5nm;
4. 300 ℃ of down annealing, allow magnesium atom combines with the oxygen atom of magnesium aluminate (111) substrate surface, migration, desorption, obtain the magnesium oxide adsorption layer at last, for epitaxial growth of ZnO provides a homogeneous nucleation layer;
5. deposit thickness is the ZnO resilient coating of 15nm in the time of 300 ℃, and oxygen, zinc line are adjusted to the scope of the rich zinc near stoichiometric(al) during with growth, can obtain the ZnO of oxygen polarity;
6. anneal under 750 ℃ of temperature, oxygen atmosphere, annealing time is 20 minutes;
7. 650 ℃ of growths of carrying out epitaxial loayer, oxygen, zinc line are adjusted to the scope of the rich zinc near stoichiometric(al) during with growth, ZnO film growth 3 hours; After the end, anneal under 750 ℃ of temperature, oxygen atmosphere, annealing time is 30 minutes;
8. drop to room temperature at oxygen atmosphere, take out sample then, finish the preparation of sample.
Utilize step calibrator (Dektak 8) to measure the thickness of the zinc-oxide film of the present invention's preparation, its value is 780nm, as shown in Figure 2.In above-mentioned preparation thin-film process, we utilize reflection high energy electron diffraction (RHEED) that sample is carried out home position observation, its result as shown in Figure 3, wherein Fig. 3 (a) is magnesium aluminate (a 111) substrate through the clean surface after the oxygen plasma treatment; Fig. 3 (b) has 30 degree rotation farmlands for being deposited on magnesium metal layer on the magnesium aluminate (111) in this pattern displaying magnesium (0001) film, corresponding in the drawings the diffracted ray of arrow indication; After this magnesium metal layer is annealed, most of evaporated, the oxygen that only stays small part and substrate surface is bonding mutually again, forming core forms the MgO thin layer shown in Fig. 3 (c) then, and this moment, the pattern of magnesium metal disappeared, only stay rock salt phase oxidation magnesium (111) superthin layer, the rich magnesium of this laminar surface; Fig. 3 (d) is for having grown the surface of ZnO resilient coating; Fig. 3 (e) is for having grown the surface behind the ZnO epitaxial loayer, pattern displaying 3 * 3 structures more clearly, and 3 * 3 again the structure surface be the figuratrix of ZnO (000-1) face, confirmed (K.Iwata, etc. by a plurality of seminar that comprises us, Phys.Stat.Sol. (a) 180,287 (2002) .Z.Mei, etc., J.Appl.Phys., 96,7108 (2004)).The above results shows that the gained film is single oxygen polarity, single farmland ZnO.We utilize atomic force microscope that this film has been carried out the observation of surface topography, as shown in Figure 4, have shown atomic layer step clearly among the figure, and it highly is 0.5nm, at 1 * 1 μ m
2Surface roughness in the scope is 0.389nm.Show that this film has the surface of atomically flating, is highly suitable for the making of high-performance optical electronic device.
Claims (1)
1. the preparation method of a ZnO monocrystal thin films on the magnesium aluminate substrate is characterized in that, comprises the steps:
1) magnesium aluminate (111) substrate back is plated molybdenum, cleaning, then substrate is imported the molecular beam epitaxial growth system;
2) carry out radio frequency oxygen plasma treatment about 30 minutes under 20～200 ℃ of low temperature, radio-frequency power is 300～450W, and oxygen flow is 1～3sccm, with magnesium aluminate (111) substrate that obtains the oxygen terminal surface;
3) in air pressure＜1 * 10
-6Pa and underlayer temperature be plated metal magnesium between 20～200 ℃, to obtain the thick thin layer of 3～5nm;
4) 200～500 ℃ of down annealing, allow magnesium atom combines with the oxygen of magnesium aluminate (111) substrate surface, migration, desorption, obtain the even magnesium oxide layer of surperficial rich magnesium at last, for epitaxial growth of ZnO provides a forming core layer;
5) temperature deposit thickness between 200～500 ℃ is the ZnO resilient coating of 10～30nm, and oxygen, zinc line are adjusted to the scope of the rich zinc near stoichiometric(al) during with growth, can obtain oxygen polarity ZnO;
6) anneal under 700～800 ℃ of temperature, oxygen atmosphere, annealing time is 10～30 minutes;
7) 500～700 ℃ of growths of carrying out epitaxial loayer, oxygen, zinc line are adjusted to the scope of the rich zinc near stoichiometric(al) during with growth; Behind the ZnO film growth ending, anneal under 700～800 ℃ of temperature, oxygen atmosphere, annealing time is 10～30 minutes.
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| 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 |
| CN100422394C (en) * | 2006-03-20 | 2008-10-01 | 中国科学院物理研究所 | Method for preparing high-quality ZnO single-crystal film on si (111) substrate |
| CN100431101C (en) * | 2007-05-11 | 2008-11-05 | 北京交通大学 | Light auxiliary MBE system, and method for developing ZnO monocrystal film |
| CN102477527B (en) * | 2010-11-23 | 2014-07-30 | 鸿富锦精密工业（深圳）有限公司 | Manufacture method of shell and shell manufactured by method |
Citations (6)
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| JPH0766669A (en) * | 1993-08-30 | 1995-03-10 | Matsushita Electric Ind Co Ltd | Surface acoustic wave convolver |
| US6046464A (en) * | 1995-03-29 | 2000-04-04 | North Carolina State University | Integrated heterostructures of group III-V nitride semiconductor materials including epitaxial ohmic contact comprising multiple quantum well |
| CN1271966A (en) * | 2000-05-19 | 2000-11-01 | 山东大学 | Production method of high-brightness LED chip using zinc oxide as its window layer |
| US6362496B1 (en) * | 1997-12-02 | 2002-03-26 | Murata Manufacturing Co., Ltd. | Semiconductor light emitting device having a GaN-based semiconductor layer, method for producing the same and method for forming a GaN-based semiconductor layer |
| CN1513210A (en) * | 2001-04-27 | 2004-07-14 | ��Խ�뵼����ʽ���� | Method for producing light-emitting device |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0766669A (en) * | 1993-08-30 | 1995-03-10 | Matsushita Electric Ind Co Ltd | Surface acoustic wave convolver |
| US6046464A (en) * | 1995-03-29 | 2000-04-04 | North Carolina State University | Integrated heterostructures of group III-V nitride semiconductor materials including epitaxial ohmic contact comprising multiple quantum well |
| US6362496B1 (en) * | 1997-12-02 | 2002-03-26 | Murata Manufacturing Co., Ltd. | Semiconductor light emitting device having a GaN-based semiconductor layer, method for producing the same and method for forming a GaN-based semiconductor layer |
| CN1271966A (en) * | 2000-05-19 | 2000-11-01 | 山东大学 | Production method of high-brightness LED chip using zinc oxide as its window layer |
| CN1513210A (en) * | 2001-04-27 | 2004-07-14 | ��Խ�뵼����ʽ���� | Method for producing light-emitting device |
| 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 |
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