CN102776567B - Method for preparing wurtzite phase MxZn1-xO single crystal film on Si substrate - Google Patents
Method for preparing wurtzite phase MxZn1-xO single crystal film on Si substrate Download PDFInfo
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Abstract
The invention provides a method for preparing a wurtzite phase MxZn1-xO (M=Mg, Be) single crystal film on a Si substrate. The method comprises the steps of depositing a Be metal single crystal film on the surface of the Si substrate; oxidizing the Be metal single crystal film to obtain a BeO single crystal layer; and depositing the MxZn1-xO single crystal film on the BeO single crystal layer.
Description
Technical field
The present invention relates to the preparation method of photoelectric semiconductor material, particularly relate to M
xzn
1-xthe preparation method of O (M=Mg, Be) monocrystal thin films.
Background technology
In recent years, ultraviolet detector receives much concern because all having major application value in civilian and military field, as medical science, biology, ozone detection, flame sensing, pollution monitoring, secure communication, the detection of guided missile plumage cigarette, Air Vehicle Detection and ultraviolet technology field, space etc.The ultraviolet detector of current practicality is based on photomultiplier and silica-based ultraviolet photodiode.Although use photomultiplier can sensitive detection to UV-light, but high-resolution detector array cannot be prepared with the demand of high resolution detection in satisfied military affairs, and the response wave band of photomultiplier is wide, also have response to the visible ray that sunlight background is launched, therefore need additional expensive ultraviolet filter plate with get rid of sunlight background to military target launch the interference of UV signal; In addition, photomultiplier needs just can work under high voltages, and volume is heavy, efficiency is low, fragile and cost is higher, is unfavorable for military miniaturization and safe.And although silicon and gallium arsenide (GaAs) photodiode can realize array, its detectivity is low, and equally also need expensive ultraviolet filter plate (assembly), working range cannot close to day-old chick.Therefore, traditional ultraviolet detector has certain limitation in practical application.The more superior wide bandgap semiconductor base solid-state UV detector of exploitation performance carrys out alternative above-mentioned ultraviolet detector becomes the research topic that recent domestic scholar pays much attention to.
Compared with traditional ultraviolet detector, wide bandgap semiconductor detector has detectivity high (quantum yield is high), response fast (electronic mobility is high), spectral response distributes, be blind area to visible and infrared light, dark current low (signal to noise ratio is high), high temperature resistant, radioprotective, volume is little, existing semiconductor technology can be utilized to realize the advantages such as arrayed devices manufacture in enormous quantities, be very suitable for being formed in particular surroundings (as life science) and severe environment (as fire, space, battlefield) under work, high-level efficiency, high performance ultraviolet detector.The focus of current research mainly concentrates on GaN and ZnO and alloy A l thereof
xga
1-xn and Mg
xzn
1-xo, Be
xzn
1-xon O.This different materials is by adjusting respective elementary composition in theory, can realize the regulation and control (Al of energy gap
xga
1-xn:3.4 ~ 6.2eV, Mg
xzn
1-xo:3.37 ~ 7.8eV, Be
xzn
1-xo:3.37 ~ 10.6eV), thus complete the detection of ultraviolet to day-old chick.Compared with AlGaN, ZnO alloy material----MgZnO, BeZnO have better photoelectric properties (exciton binding energy is high), higher crystalline quality (having the single crystalline substrate of coupling), better chemical property and the advantage such as thermostability, stronger Radiation hardness, are therefore applicable to very much doing the ultraviolet under various environment and even deep ultraviolet detecting material; But due to the strong self-compensation mechanism of semiconductor material with wide forbidden band, reliable and stable p-type material is difficult to obtain, because which limit their application in the pn homogeneity junction type ultraviolet detector that performance is more superior.How avoiding a difficult problem for p-type doping, look for another way from device aspect, break through the making bottleneck of ultraviolet detector, is the primary goal of domestic and international many seminars research.
Si substrate prepares M
xzn
1-xo (M=Mg, Be) device then can solve this difficult problem, because silicon is as first-generation semi-conductor, its crystalline quality and electrically regulation and control have been a kind of materials doing best at present, are therefore suitable for very much the modulation of the epitaxy of film, device architecture and performance; In addition, Si substrate not only low price, crystalline quality is good, and the electroconductibility of its uniqueness makes follow-up device preparation technology easier, be expected to make monolithic integrated circuit, combine with the microelectronic technology effective of advanced person, thus explore and prepare high quality M on a si substrate
xzn
1-xo (M=Mg, Be) epitaxial film has very important scientific value and Research Significance, will have huge commercial application potentiality; Based on this, in recent years, Si base M
xzn
1-xthe technology of preparing of O (M=Mg, Be) film is extremely paid attention to.
But, because Si is easy to the Si oxide (SiO being oxidized to amorphous structure under oxygen atmosphere
x), thus to high quality M
xzn
1-xthe epitaxy of O causes great difficulty; In addition, M
xzn
1-xo (M=Mg, Be) monocrystal thin films, especially high Mg component Mg
xzn
1-xthe structure of preparation to interfacial layer of O has very strict requirement, in order to reduce alloy system energy, the Atomic coordinate number of interfacial layer will consistent with epitaxial film, the degreeof tortuosity of lattice Atom Cheng Jian so just may be made to be down to minimum, thus obtain the mutually high Mg component Mg of single wurtzite of metastable phase
xzn
1-xo alloy firm.Develop some interfacial layer growing technologies at present abroad to protect Si surface, to provide epitaxy template, thus prepare MgZnO film, as Vispute group of Univ Maryland-Coll Park USA adopts at Si (100) deposited on substrates SrTiO
3, Bi
2ti
3o
12, the buffer layer such as TiN method protection Si surface, prepared Emission in Cubic MgZnO monocrystal thin films (patent US007132668, Appl.Phys.Lett.82 (2003) 3424); The Narayan group of North Carolina, US university utilizes PLD technology first to deposited TiN interfacial layer on Si (111) substrate, has then prepared the wurtzite structure Mg that Mg component is only 10%
0.1zn
0.9o film; The people such as the Koike of Osaka polytechnical university of Japan adopt first depositing monocrystalline CaF
2layer, the method depositing ZnO buffer have again prepared wurtzite phase MgZnO monocrystal thin films on Si (111) substrate, and its Mg component and band gap are the highlyest adjustable to 34%, about 4.1eV (J.Cryst.Growth 278 (2005) 288); The people such as Fujita of Waseda university of Japan adopts at 350 DEG C, first deposits Mg, open the MgO buffer layer that first method of oxygen prepared about 3nm on Si (111) substrate again, then deposited again the ZnO buffer of 80nm as epitaxy template, obtain the wurtzite phase MgZnO film that band gap is about 3.8eV, their XRD result of study shows: if do not have the intervention of ZnO buffer, the MgZnO of wurtzite structure just cannot grow on MgO buffer layer, because MgO is rock salt structure, MgZnO grows on MgO that to be easy to relaxation be Emission in Cubic.But ZnO buffer can to long wavelength ultraviolet radiation generation strong absorption, and therefore the detection performance of device is had a strong impact on.In order to realize the day blind detection of a target, this step of ZnO buffer in process of growth, must be removed.
It can thus be appreciated that, need exploitation one can available protecting Si (111) surface from oxidation, again can for wurtzite phase M
xzn
1-xo (M=Mg, Be) monocrystal thin films provides the interface engineering technology of suitable epitaxy template, can prepare high quality Si base wurtzite phase M
xzn
1-xo (M=Mg, Be) monocrystal thin films, especially high Mg component Mg
xzn
1-xo monocrystal thin films.
Summary of the invention
One is the object of the present invention is to provide to prepare M on a si substrate
xzn
1-xthe method of O (M=Mg, Be) monocrystal thin films, can solve protection and the M on Si substrate cleaning surface
xzn
1-xan epitaxial template difficult problem for O monocrystal thin films, successfully obtains Si base wurtzite phase M
xzn
1-xo monocrystal thin films, especially high Mg component Mg
xzn
1-xo monocrystal thin films.
The invention provides one and prepare M on a si substrate
xzn
1-xthe method of O (M=Mg, Be) monocrystal thin films, comprising:
1) on Si substrate surface, Be metal single crystal film is deposited;
2) Be metallic film is oxidized to obtain BeO single crystalline layer;
3) on BeO single crystalline layer, M is deposited
xzn
1-xo monocrystal thin films, wherein M is Mg or Be.
According to preparation method provided by the invention, wherein step 1) also comprise treatment S i substrate before, to obtain clean Si (111) surface.
According to preparation method provided by the invention, wherein utilize molecular beam epitaxy system to deposit Be metal single crystal film, the thickness of Be metal single crystal film is that the line of 1 ~ 20nm, Be reaches about 5 × 10
-4pa, Si substrate temperature controls at 20 ~ 800 DEG C.
According to preparation method provided by the invention, wherein utilize active oxygen source to be oxidized Be metallic film, described active oxygen source comprises the oxygen containing oxygen plasma or ozone.The described oxygen plasma that contains comprises radio-frequency plasma, Ecr plasma.
According to preparation method provided by the invention, the temperature being wherein oxidized Be metallic film is 100 ~ 500 DEG C, and oxidization time is 1 ~ 30 minute.
According to preparation method provided by the invention, wherein step 4) can comprise:
Carry out low M to medium M component M
xzn
1-xthe epitaxy of O (M=Mg, Be) layer;
Carry out high M component M
xzn
1-xthe epitaxy of O (M=Mg, Be) layer.
Wherein low Mg is to the Mg of medium Mg component
xzn
1-xin O layer, the value of x is 0 ~ 0.3, the Mg of high Mg component
xzn
1-xin O layer, the value of x is 0.3 ~ 1; Low Be is to the Be of medium Be component
xzn
1-xin O layer, the value of x is 0 ~ 0.2, the Be of high Be component
xzn
1-xin O layer, the value of x is 0.2 ~ 1.
Accompanying drawing explanation
Referring to accompanying drawing, embodiments of the present invention is further illustrated, wherein:
Fig. 1 is for prepare Mg according to embodiments of the invention 1
0.5zn
0.5reflected high energy electron diffraction (RHEED) home position observation pattern during O monocrystal thin films (wherein a, b, c, d, e comprise two width opposing upper and lower respectively scheme corresponding to the RHEED of different directions);
The Mg of Fig. 2 prepared by embodiments of the invention 1
0.5zn
0.5the atomic force microscope figure on O monocrystal thin films surface;
Fig. 3 is the Mg prepared by embodiments of the invention 1
0.5zn
0.5x-ray diffraction θ-2 θ scanning curve of O monocrystal thin films;
Fig. 4 is the Mg prepared by embodiments of the invention 1
0.5zn
0.5the X-ray diffraction φ scanning curve of O monocrystal thin films;
Fig. 5 is the Mg prepared by embodiments of the invention 1
0.5zn
0.5the room temperature reflectance spectrum of O monocrystal thin films;
Fig. 6 is for prepare Mg according to embodiments of the invention 2
0.4zn
0.6reflected high energy electron diffraction home position observation pattern during O monocrystal thin films (wherein a, b, c, d comprise two width opposing upper and lower respectively scheme corresponding to the RHEED of different directions);
Fig. 7 is according to the reflected high energy electron diffraction home position observation pattern (wherein a, b, c, d comprise two width opposing upper and lower respectively scheme corresponding to the RHEED of different directions) during embodiments of the invention 7 making ZnO monocrystal thin films.
Embodiment
The invention provides one and prepare M on a si substrate
xzn
1-xo (M=Mg; Be) method of monocrystal thin films; the method and existing methodical difference are to have employed method at Si substrate surface metal refining Be monocrystal thin films to protect clean Si surface, and utilize active oxygen process metal Be to obtain wurtzite structure BeO monocrystal thin films thus for wurtzite phase M
xzn
1-xthe growth of O (M=Mg, Be) monocrystal thin films provides good epitaxial template.
Due to Be and Si at very high temperatures (> 1000 DEG C) just may form alloy, therefore the deposition of Be metal on Si can be carried out in a wide temperature range, thus make this technique get a good chance of carrying out with the microelectronic technology of existing maturation integrating, realizing detecting-single-chip integration of amplifying circuit.
In addition, the saturated vapor pressure of Be is very low, and its desorption coefficient and migration length are also very little, so obtain smooth Be film easily via Optimizing Process Parameters, this for the clean Si surface of protection, the diffusion of anti-block advantageously.In 20 DEG C ~ 800 DEG C temperature ranges, Be can form the Be single crystalline layer that crystalline quality is high, surface is very smooth on Si.
Due to the Enthalpies of Formation Δ H of BeO
f(-609.4kJ/mol) is much smaller than SiO
2enthalpies of Formation Δ H
f(-910.7kJ/mol), therefore the combination of silicon and oxygen not easily occurs, thus protects Si surface.Because Be atom in BeO and O atom are 4 coordinations, and M
xzn
1-xin O (M=Mg, Be), the ligancy of Sauerstoffatom is also 4, and the two does not exist atomic bonding difference problem, works as M
xzn
1-xo (M=Mg, Be) is when BeO Epitaxial growth, and all can drop to minimum with the atomic bonding in BeO lattice and lattice distortion degree, be therefore M
xzn
1-xthe growth of O (M=Mg, Be) provides good epitaxial template, can obtain high-quality Si base wurtzite phase M
xzn
1-xo (M=Mg, Be) monocrystal thin films, especially high Mg component Mg
xzn
1-xo monocrystal thin films, and the perfection of lattice of film and crystalline quality are all relatively good.
Wherein low M to medium M component M
xzn
1-xo epitaxial film is suitable for ultraviolet detection, high M component M
xzn
1-xo layer is suitable for deep ultraviolet detection, can determine M according to the situation in actual detection
xzn
1-xthe component of M in O.
Embodiment 1
Embodiment 1 provides one to prepare Mg on a si substrate
0.5zn
0.5the method of O monocrystal thin films, comprising:
1) removed the zone of oxidation of Si (111) substrate surface by hf etching method, then import molecular beam epitaxy (MBE) system, be not less than 1 × 10
-8under the vacuum condition of mbar, carry out high-temperature heat treatment at substrate being warming up to 700 DEG C 30 minutes, utilize elevated temperature desorption effect to remove residual oxygen silicon layer, obtain clean Si substrate surface (111);
2) Si substrate temperature is controlled at 20 DEG C, utilize molecular beam epitaxy (MBE) system to deposit the thick Be metal single crystal film of 20nm, wherein heat Be diffusion furnace and make the line of Be reach 5 × 10
-4about Pa;
3) utilize radio frequency (rf) plasma body to carry out oxide treatment to Be film, obtain BeO monocrystal thin films, the flow of oxygen used is 1.5sccm, and radio frequency power is 200W, and oxidizing temperature is 100 DEG C, and oxidization time is 30 minutes;
4) molecular beam epitaxy (MBE) system is utilized, epitaxy Mg under 350 DEG C of conditions
0.3zn
0.7o layer, thickness is 30nm;
5) molecular beam epitaxy (MBE) system is utilized, epitaxy Mg under 350 DEG C of conditions
0.5zn
0.5o layer, thickness is 500nm.
Fig. 1 is the Mg of embodiment 1
0.5zn
0.5rHEED pattern in O monocrystal thin films preparation process, wherein scheming (a) is the clean surface of Si (111) substrate in ultrahigh vacuum(HHV) after 700 DEG C of pyroprocessing; Figure (b), for being deposited on the RHEED pattern of the metal Be layer on Si (111), showing clear, sharp keen striated diffraction pattern, shows that Be (0001) has good crystallinity and even curface in figure.Be superimposed upon on Si (111) grid after in the face that pattern also shows Be (0001), grid have rotated 30 °, now Be<11-20>//Si<11-2>; Be<10-10>//Si<10-1>.Figure (c) is the surface after metal Be oxidation, this pattern is typical wurtzite phase BeO, its aufwuchsplate is (0001) face, grid in face overlaps with Be (0001), namely be also be superimposed upon on Si (111) grid after have rotated 30 °, BeO<11-20>//Si<1 1-2>; BeO<10-10>//Si<1 0-1>.Figure (d) is for have grown Mg
0.3zn
0.7the surface of O buffer layer, diffraction pattern has sixfold symmetry, illustrate that film is wurtzite structure, and dot pattern illustrates that film is three-dimensional island growth pattern, the huge stress that the lattice distortion that this growth pattern can help the strong ionic Mg-O key of release to bring produces, thus be conducive to follow-up high Mg component Mg
xzn
1-xthe growth of O film.Figure (e) is for have grown Mg
0.5zn
0.5surface after O epitaxial film, clear, sharp keen striped design display gained film is the high quality monocrystalline film with flat surface.
The Mg of Fig. 2 prepared by above-described embodiment
0.5zn
0.5the atomic force microscope figure of O monocrystal thin films surface topography, at 10 × 10 μm
2surfaceness in sweep limit is only 1.6nm, shows that film is very smooth.
Fig. 3 and Fig. 4 is respectively the Mg prepared by above-described embodiment
0.5zn
0.5x-ray diffraction θ-2 θ scanning curve of O monocrystal thin films and φ scanning curve, show Si (111) peak and Mg in Fig. 3
0.5zn
0.5o (0002) peak, demonstrates Mg
0.5zn
0.5o grows along c-axis, is wurtzite structure, be presented at 6 diffraction peaks in 360 ° of sweep limits and equidistantly arrange, and diffraction peak intensity is basically identical, illustrate that this film is high quality monocrystalline film in Fig. 4.
The Mg of Fig. 5 prepared by above-described embodiment
0.5zn
0.5the room temperature reflectance spectrum of O monocrystal thin films, the energy gap that room temperature reflectance spectrum test result shows this film is 280nm (4.43eV), shows that film enters non-solar-blind band, is very suitable for the making of high-performance deep ultraviolet detector.
Embodiment 2
The present embodiment provides one to prepare Mg on a si substrate
0.4zn
0.6the method of O monocrystal thin films, comprising:
1) removed the zone of oxidation of Si (111) substrate surface by hf etching method, then import molecular beam epitaxy (MBE) system, be not less than 1 × 10
-8under the vacuum condition of mbar, carry out high-temperature heat treatment 20 minutes at substrate being warming up to 800 DEG C, utilize elevated temperature desorption effect to remove residual oxygen silicon layer, obtain clean Si substrate surface (111), now surface is in typical 7 × 7 structures again;
2) Si substrate temperature is controlled at 300 DEG C, utilize molecular beam epitaxy (MBE) system to deposit the thick Be metal single crystal film of 10nm, wherein heat Be diffusion furnace and make the line of Be reach 5 × 10
-4about Pa;
3) utilize radio frequency (rf) plasma body to carry out oxide treatment to Be film, obtain BeO monocrystal thin films, the flow of oxygen used is 1.5sccm, and radio frequency power is 200W, and oxidizing temperature is 300 DEG C, and oxidization time is 15 minutes;
4) molecular beam epitaxy (MBE) system is utilized, epitaxy Mg under 450 DEG C of conditions
0.2zn
0.8o layer, thickness is 20nm;
5) molecular beam epitaxy (MBE) system is utilized, epitaxy Mg under 450 DEG C of conditions
0.4zn
0.6o layer, thickness is 200nm.
The preparation method that the present embodiment provides can obtain band gap be 295nm (4.2eV), be suitable for UV-B ultraviolet band detection high quality wurtzite phase Mg
0.4zn
0.6o monocrystal thin films.
Fig. 6 is the RHEED evolution pattern observed in this sample of preparation, 7 × 7 surfaces that in Fig. 6, (a) is Si (111), b () shows that Be film is monocrystal thin films, its aufwuchsplate is Be (0001), c () is the Mg finally prepared for BeO single crystal film, (d)
0.4zn
0.6o monocrystal thin films.
Embodiment 3
1) removed the zone of oxidation of Si (111) substrate surface by hf etching method, then import molecular beam epitaxy (MBE) system, be not less than 1 × 10
-8under the vacuum condition of mbar, carry out high-temperature heat treatment 10 minutes at substrate being warming up to 900 DEG C, utilize elevated temperature desorption effect to remove residual oxygen silicon layer, obtain clean Si substrate surface (111), now surface is in typical 7 × 7 structures again;
2) Si substrate temperature is controlled at 500 DEG C, utilize molecular beam epitaxy (MBE) system to deposit the thick Be metal single crystal film of 1nm, wherein heat Be diffusion furnace and make the line of Be reach 5 × 10
-4about Pa;
3) utilize radio frequency (rf) plasma body to carry out oxide treatment to Be film, obtain BeO monocrystal thin films, the flow of oxygen used is 1.5sccm, and radio frequency power is 200W, and oxidizing temperature is 500 DEG C, and oxidization time is 1 minute;
4) molecular beam epitaxy (MBE) system is utilized, epitaxy Mg under 550 DEG C of conditions
0.1zn
0.9o layer, thickness is 10nm;
5) molecular beam epitaxy (MBE) system is utilized, epitaxy Mg under 550 DEG C of conditions
0.3zn
0.7o layer, thickness is 800nm.
The present embodiment can obtain band gap be 318nm (3.9eV), be suitable for UV-B ultraviolet band detection high quality wurtzite phase MgZnO monocrystal thin films.
Compare with embodiment 2 with embodiment 1, the present embodiment have employed higher temperature (500 DEG C) and carrys out metal refining Be, and the thickness of Be is 1nm, in very short oxidization time (1 minute), just obtain good wurtzite phase BeO template.
Embodiment 4
1) removed the zone of oxidation of Si (111) substrate surface by hf etching method, then import molecular beam epitaxy (MBE) system, be not less than 1 × 10
-8under the vacuum condition of mbar, carry out high-temperature heat treatment 10 minutes at substrate being warming up to 900 DEG C, utilize elevated temperature desorption effect to remove residual oxygen silicon layer, obtain clean Si substrate surface (111), now surface is in typical 7 × 7 structures again;
2) Si substrate temperature is controlled at 500 DEG C, utilize molecular beam epitaxy (MBE) system to deposit the thick Be metal single crystal film of 1nm, wherein heat Be diffusion furnace and make the line of Be reach 5 × 10
-4about Pa;
3) utilize radio frequency (rf) plasma body to carry out oxide treatment to Be film, obtain BeO monocrystal thin films, the flow of oxygen used is 1.5sccm, and radio frequency power is 200W, and oxidizing temperature is 500 DEG C, and oxidization time is 1 minute;
4) molecular beam epitaxy (MBE) system is utilized, epitaxy Mg under 550 DEG C of conditions
0.3zn
0.7o layer, thickness is 800nm.
Compared with embodiment 3, the present embodiment eliminates Mg
0.1zn
0.9the deposition of O buffer layer, directly deposited Mg on BeO single crystalline layer
0.3zn
0.7o epitaxial film.
Embodiment 5
1) removed the zone of oxidation of Si (111) substrate surface by hf etching method, then import molecular beam epitaxy (MBE) system, be not less than 1 × 10
-8under the vacuum condition of mbar, carry out high-temperature heat treatment 10 minutes at substrate being warming up to 900 DEG C, utilize elevated temperature desorption effect to remove residual oxygen silicon layer, obtain clean Si substrate surface (111), now surface is in typical 7 × 7 structures again;
2) Si substrate temperature is controlled at 500 DEG C, utilize molecular beam epitaxy (MBE) system to deposit the thick Be metal single crystal film of 1nm, wherein heat Be diffusion furnace and make the line of Be reach 5 × 10
-4about Pa;
3) utilize radio frequency (rf) plasma body to carry out oxide treatment to Be film, obtain BeO monocrystal thin films, the flow of oxygen used is 1.5sccm, and radio frequency power is 200W, and oxidizing temperature is 500 DEG C, and oxidization time is 1 minute;
4) molecular beam epitaxy (MBE) system is utilized, epitaxy Be under 450 DEG C of conditions
0.1zn
0.9o layer, thickness is 300nm.
Embodiment 6
1) removed the zone of oxidation of Si (111) substrate surface by hf etching method, then import molecular beam epitaxy (MBE) system, be not less than 1 × 10
-8under the vacuum condition of mbar, carry out high-temperature heat treatment 20 minutes at substrate being warming up to 700 DEG C, utilize elevated temperature desorption effect to remove residual oxygen silicon layer, obtain clean Si substrate surface (111), now surface is in typical 7 × 7 structures again;
2) Si substrate temperature is controlled at 800 DEG C, utilize molecular beam epitaxy (MBE) system to deposit the thick Be metal single crystal film of 20nm, wherein heat Be diffusion furnace and make the line of Be reach 5 × 10
-4about Pa;
3) utilize radio frequency (rf) plasma body to carry out oxide treatment to Be film, obtain BeO monocrystal thin films, the flow of oxygen used is 1.5sccm, and radio frequency power is 200W, and oxidizing temperature is 100 DEG C, and oxidization time is 30 minutes;
4) molecular beam epitaxy (MBE) system is utilized, epitaxy Be under 650 DEG C of conditions
0.3zn
0.7o layer, thickness is 200nm.
Embodiment 7
1) removed the zone of oxidation of Si (111) substrate surface by hf etching method, then import molecular beam epitaxy (MBE) system, be not less than 1 × 10
-8under the vacuum condition of mbar, carry out high-temperature heat treatment 20 minutes at substrate being warming up to 800 DEG C, utilize elevated temperature desorption effect to remove residual oxygen silicon layer, obtain clean Si substrate surface (111), now surface is in typical 7 × 7 structures again;
2) Si substrate temperature is controlled at 800 DEG C, utilize molecular beam epitaxy (MBE) system to deposit the thick Be metal single crystal film of 10nm, wherein heat Be diffusion furnace and make the line of Be reach 5 × 10
-4about Pa;
3) utilize radio frequency (rf) plasma body to carry out oxide treatment to Be film, obtain BeO monocrystal thin films, the flow of oxygen used is 1.5sccm, and radio frequency power is 200W, and oxidizing temperature is 200 DEG C, and oxidization time is 8 minutes;
4) utilize molecular beam epitaxy (MBE) system, under 650 DEG C of conditions, (namely M component is the M of 0 to epitaxy ZnO layer
xzn
1-xo), thickness is 1000nm;
In the present embodiment, the M that BeO single crystalline layer deposits
xzn
1-xin O monocrystal thin films, the value of x is zero, and the monocrystal thin films namely BeO single crystalline layer deposited is ZnO.RHEED home position observation result (as shown in Figure 7) shows that all process of growth are similar to embodiment 1 to embodiment 6,7 × 7 surfaces that in Fig. 7, (a) is Si (111), b () shows that Be film is monocrystal thin films, its aufwuchsplate is Be (0001), c () is BeO single crystal film, (d) ZnO monocrystal thin films for finally preparing, the making of its applicable high-performance ultraviolet detector.
According to one embodiment of present invention, high-temperature heat treatment Si substrate is to obtain in the step on clean substrate surface, and underlayer temperature can be 700 ~ 900 DEG C, and heat treatment time is 10 ~ 30 minutes.
According to one embodiment of present invention, when wherein depositing Be metal single crystal film, Si substrate temperature can be controlled at 20 ~ 800 DEG C, the thickness of Be metal single crystal film is 1 ~ 20nm, during oxidation Be metal single crystal film, Si substrate temperature can be controlled at 100 ~ 500 DEG C, oxidization time is 1 ~ 30 minute.
According to one embodiment of present invention, wherein radio frequency (rf) plasma body can be replaced by other active oxygen sources, as electron cyclotron resonace (ECR) plasma or ozone etc.
According to one embodiment of present invention, wherein low Mg to medium Mg component Mg
xzn
1-xin O epitaxial film, x is 0 ~ 0.3, and thickness is 10 ~ 1000nm, and depositing temperature can be 350 ~ 650 DEG C; High Mg component Mg
xzn
1-xin O layer, x is 0.3 ~ 1, and depositing temperature can be 350 ~ 650 DEG C, and thickness is 200 ~ 1000nm.
According to one embodiment of present invention, wherein low Be to medium Be B component e
xzn
1-xin O epitaxial film, x is 0 ~ 0.2, and thickness is 10 ~ 1000nm, and depositing temperature can be 350 ~ 650 DEG C; High Be B component e
xzn
1-xin O layer, x is 0.2 ~ 1, and depositing temperature can be 350 ~ 650 DEG C, and thickness is 200 ~ 1000nm.
It should be noted last that, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted.Although with reference to embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, modify to technical scheme of the present invention or equivalent replacement, do not depart from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of right of the present invention.
Claims (9)
1. prepare M on a si substrate for one kind
xzn
1-xthe method of O monocrystal thin films, comprising:
1) on Si (111) substrate surface, Be metal single crystal film is deposited;
2) Be metallic film is oxidized to obtain BeO single crystalline layer;
3) on BeO single crystalline layer, M is deposited
xzn
1-xo monocrystal thin films, wherein M is Mg or Be, 0≤x≤1.
2. preparation method according to claim 1, wherein step 1) also comprise treatment S i substrate before, to obtain clean Si (111) surface.
3. preparation method according to claim 1, wherein the thickness of Be metal single crystal film is 1 ~ 20nm.
4. preparation method according to claim 1, wherein step 1) in utilize molecular beam epitaxy system to deposit Be metal single crystal film, the line of Be reaches 5 × 10
-4pa, Si substrate temperature controls at 20 ~ 800 DEG C.
5. preparation method according to claim 1, wherein step 2) in utilize active oxygen source to be oxidized Be metallic film.
6. preparation method according to claim 5, wherein said active oxygen source comprises the oxygen containing oxygen plasma or ozone.
7. preparation method according to claim 1, wherein step 2) in the temperature of oxidation Be metallic film be 100 ~ 500 DEG C, the oxidization time of oxidation Be metallic film is 1 ~ 30 minute.
8. preparation method according to claim 1, wherein step 3) to be included in value BeO single crystalline layer first depositing x be the Be of 0 ~ 0.2
xzn
1-xo monocrystal thin films, then the value depositing x is the Be of 0.2 ~ 1
xzn
1-xo monocrystal thin films.
9. preparation method according to claim 1, wherein step 3) to be included in value BeO single crystalline layer first depositing x be the Mg of 0 ~ 0.3
xzn
1-xo monocrystal thin films, then the value depositing x is the Mg of 0.3 ~ 1
xzn
1-xo monocrystal thin films.
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