CN1327042C - Method for growing single-crystal zinc oxide film by using zinc oxide buffer layer - Google Patents
Method for growing single-crystal zinc oxide film by using zinc oxide buffer layer Download PDFInfo
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- CN1327042C CN1327042C CNB2005100627432A CN200510062743A CN1327042C CN 1327042 C CN1327042 C CN 1327042C CN B2005100627432 A CNB2005100627432 A CN B2005100627432A CN 200510062743 A CN200510062743 A CN 200510062743A CN 1327042 C CN1327042 C CN 1327042C
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Abstract
The present invention relates to a method for growing single crystal zinc oxide films by using zinc oxide buffer layers. The present invention is characterized in that the present invention has the procedures that a substrate is taken; a zinc oxide buffer layer is grown on a silicon (001) crystal surface arranged on the substrate in low temperature by utilizing the method of magnetron sputtering; a zinc oxide epitaxial film is grown on the zinc oxide buffering layer in low temperature by utilizing the MOCVD method.
Description
Technical field
The invention belongs to technical field of semiconductors, refer in particular under the cold condition, on silicon substrate, utilize magnetically controlled sputter method developing zinc oxide (ZnO) buffer layer earlier, the method that re-uses metal-organic chemical vapor deposition equipment (MOCVD) grows the method for single-crystal zinc-oxide crystal film.
Background technology
II-VI compound semiconductor zinc oxide (ZnO) because of it has unique physics, chemistry and optical property, just is being subjected to people's concern and research more and more widely as the representative of third generation semiconductor material.ZnO has wide band gap, very high chemical temperatures and hot temperature, is difficult for oxidizedly in atmosphere, compares with II-VI family selenide with the III-V group-III nitride, and the stability of its material is that other material is incomparable.Bound exciton up to 60meV can be added quantum limitation effect, makes that the potential using value of ultraviolet diode that this kind material is made or ultraviolet laser is very big.At room temperature observing the stimulated emission of sending out with optical pumping makes people denseer to the research interest of ZnO.Higher-quality ZnO is still waiting further research though grow, and it has demonstrated its unique advantages as another new wide bandgap semiconductor laser material after the selenide of III-V nitride and II-VI family.People also are in the initial stage to the research of ZnO at present, and mainly still in substrate sapphire (0001), silicon (111) carries out epitaxy on (100) crystal face to ZnO.We adopt silicon substrate growth, though difficulty is big, according to present device and integrated technology, the growth on silica-based just has more realistic meaning.Although the MOCVD technology can prepare high quality, big area, uniform extension or polycrystal film, utilize MOCVD technology, direct growth ZnO is very difficult on silicon substrate.This is because exist bigger lattice mismatch and thermal mismatching between ZnO and the Si substrate.So adopt magnetron sputtering technique deposition layer of ZnO film as buffer layer growing ZnO thin-film on silicon substrate to be had very big benefit in advance, this can learn from growth result.Because the organic source electrode that uses in the laboratory is easily oxidized, the flow velocity of accurately controlling oxygen source in addition neither a nothing the matter simultaneously.Because it is deep not enough that above-mentioned difficulties adds the understanding of ZnO, what obtain on silicon substrate all is polycrystalline ZnO epitaxial film only also mostly.Along with the optimization of growth conditions, the crystal mass of ZnO epitaxial film is progressively improved, but generally speaking, and the monocrystalline quality of ZnO also has with a certain distance from the requirement of element manufacturing at present, also needs to be further improved and perfect.
The present invention's ZnO epitaxial growth method in the past adopts method growth ZnO or MBE method direct epitaxial growth of ZnO on Sapphire Substrate such as magnetron sputtering mostly, seldom grows quality ZnO epitaxy single-crystal film preferably on the Si substrate.Because of the ZnO facile hydrolysis, the equilibrium air pressure to the surface in process of growth requires to have the optimization and the control problem of growth conditions than higher, has influence on the homogeneity of film growth simultaneously.Because these problems that exist in the ZnO process of growth at present make that the epitaxial film quality of ZnO is not very high, the requirement that does not also reach element manufacturing.We adopt the method for this use buffer layer, can be on silicon substrates, and growing single-crystal zinc oxide film and carry out the technology preparation for the preparation of later device and integrated technology.
Summary of the invention
The object of the present invention is to provide a kind of method of utilizing the zinc bloom buffer layer growing single-crystal zinc oxide film, this method is to adopt the method for magnetron sputtering at first grow one deck zinc-oxide film, isoepitaxial growth zinc-oxide film on zinc-oxide film then on substrate silicon (001) crystal face; Underlayer temperature is about 300-350 ℃ during the zinc-oxide film deposition, the about 20Torr of pressure, growth thickness 0.5-1.0 μ m.Optimize growth conditions simultaneously,, can on silicon substrate, obtain single-crystal zinc oxide film, and improve the quality of ZnO epitaxial film effectively, and improve the planeness on surface by these measures as the control of temperature, pressure.
A kind of method of utilizing the zinc bloom buffer layer growing single-crystal zinc oxide film of the present invention is characterized in that, comprises the steps:
(1) gets a substrate;
(2) the method low-temperature epitaxy zinc bloom buffer layer of employing magnetron sputtering on the silicon on this substrate (001) crystal face;
(3) on zinc bloom buffer layer, adopt MOCVD method low-temperature epitaxy zinc oxide epitaxial film.
Wherein substrate is big mismatch silicon substrate.
Wherein the temperature of Zinc oxide single crystal epitaxial film low-temperature epitaxy is 300-350 ℃, and growth pressure is 20Torr, and growth thickness is 0.5-1.0 μ m.
Wherein the surfaceness of Zinc oxide single crystal epitaxial film is 6-10nm.
Wherein the XRD curve peak width at half height of Zinc oxide single crystal epitaxial film is 0.33 °.
Wherein a ultra-violet light-emitting peak and peak width at half height are only arranged is 21.03nm for the PL of Zinc oxide single crystal epitaxial film spectrum.
Wherein the RHEED image of Zinc oxide single crystal epitaxial film is regular point-like.
Description of drawings
For further specifying content of the present invention, below in conjunction with specific embodiment and accompanying drawing the present invention is explained in detail, wherein:
Fig. 1 is the structural representation of single-crystal zinc-oxide epitaxial film of the present invention;
Fig. 2 is the X ray θ-2 θ test result of single-crystal zinc-oxide epitaxial film of the present invention;
Fig. 3 is the surface test result of single-crystal zinc-oxide epitaxial film of the present invention;
Fig. 4 is the photoluminescence spectrum test result of single-crystal zinc-oxide epitaxial film of the present invention;
Fig. 5 is the RHEED photo of single-crystal zinc-oxide epitaxial film of the present invention.
Embodiment
See also shown in Figure 1ly, key of the present invention is to solve ZnO poor problem of the crystal mass in the process of growth on silicon substrate.Because ZnO and Si substrate have bigger mismatch, and ZnO makes that with the difficult control of MOCVD method growth conditions the epitaxy of ZnO monocrystalline is relatively more difficult.The present invention has proposed a kind of method of utilizing the zinc bloom buffer layer growing single-crystal zinc oxide film in order to solve the problem that extension ZnO grows on silicon substrate, it is characterized in that, comprises the steps:
(1) get a substrate 30, substrate 30 is big mismatch silicon substrates;
(2) the method low-temperature epitaxy zinc bloom buffer layer 20 of employing magnetron sputtering on silicon (001) crystal face on this substrate 30;
(3) on zinc bloom buffer layer 20, adopt MOCVD method low-temperature epitaxy zinc oxide epitaxial film 10, the temperature of these zinc oxide epitaxial film 10 low-temperature epitaxies is 300-350 ℃, and growth pressure is 20Torr, and growth thickness is 0.5-1.0 μ m; The surfaceness of this Zinc oxide single crystal epitaxial film 10 is 6-10nm; The XRD curve peak width at half height of this Zinc oxide single crystal epitaxial film 10 is 0.33 °; It is 21.03nm that the PL spectrum of this Zinc oxide single crystal epitaxial film 10 only has a ultra-violet light-emitting peak and peak width at half height; The RHEED image of this Zinc oxide single crystal epitaxial film 10 is regular point-like.
Sample by above step obtains is carrying out test analysis to sample, and the zinc oxide of growing with this method is the higher zinc oxide monocrystalline film of crystal mass, and its structural representation is as (Fig. 1).Have only ZnO (0002) peak to exist in X ray θ-2 θ diffracting spectrum, the curve peak width at half height is less than 0.3 ° (Fig. 2), its film surface very even (Fig. 3).The PL spectrum shows that it is 21.03nm (Fig. 4) that ultra-violet light-emitting peak and peak width at half height are only arranged.Zinc oxide RHEED photo is a rule point banded (Fig. 5).This explanation the present invention can increase substantially the surface finish of ZnO epitaxial film and obtain high-quality ZnO monocrystal epitaxial film on silicon substrate.
Make extension ZnO film isoepitaxial growth on buffer layer that relative mass is higher like this, the growth conditions of optimizing MOCVD simultaneously reaches the purpose that improves extension ZnO film crystal mass.The present invention utilizes MOCVD technology low-temperature epitaxy on Si (100) substrate to go out high-quality ZnO epitaxial film.The ZnO crystal quality of growing on the big mismatch substrate is improved, and the suitable industrialized mass of MOCVD technology, low temperature technique can well reduce production costs.
Claims (7)
1. a method of utilizing the zinc bloom buffer layer growing single-crystal zinc oxide film is characterized in that, comprises the steps:
(1) gets a substrate;
(2) the method developing zinc oxide buffer layer of employing magnetron sputtering on the silicon on this substrate (001) crystal face;
(3) on zinc bloom buffer layer, adopt MOCVD method developing zinc oxide epitaxial film.
2, the method for utilizing the zinc bloom buffer layer growing single-crystal zinc oxide film according to claim 1 is characterized in that, wherein substrate is big mismatch silicon substrate.
3, the method for utilizing the zinc bloom buffer layer growing single-crystal zinc oxide film according to claim 1 is characterized in that, wherein the temperature of zinc oxide epitaxial film growth is 300-350 ℃, and growth pressure is 20Torr, and growth thickness is 0.5-1.0 μ m.
4, the method for utilizing the zinc bloom buffer layer growing single-crystal zinc oxide film according to claim 1 is characterized in that, wherein the surfaceness of Zinc oxide single crystal epitaxial film is 6-10nm.
5, the method for utilizing the zinc bloom buffer layer growing single-crystal zinc oxide film according to claim 1 is characterized in that, wherein the XRD curve peak width at half height of zinc oxide epitaxial film is 0.33 °.
6, a kind of method of utilizing the zinc bloom buffer layer growing single-crystal zinc oxide film according to claim 1 is characterized in that, wherein a ultra-violet light-emitting peak and peak width at half height are only arranged is 21.03nm for the PL of zinc oxide epitaxial film spectrum.
7, a kind of method of utilizing the zinc bloom buffer layer growing single-crystal zinc oxide film according to claim 1 is characterized in that, wherein the RHEED image of zinc oxide epitaxial film is regular point-like.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100627432A CN1327042C (en) | 2005-03-28 | 2005-03-28 | Method for growing single-crystal zinc oxide film by using zinc oxide buffer layer |
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| CNB2005100627432A CN1327042C (en) | 2005-03-28 | 2005-03-28 | Method for growing single-crystal zinc oxide film by using zinc oxide buffer layer |
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| CN1327042C true CN1327042C (en) | 2007-07-18 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101381891B (en) * | 2008-10-20 | 2011-08-31 | 中国科学院物理研究所 | Method for preparing MgZnO single crystal film |
| CN101494269B (en) * | 2008-12-18 | 2010-05-12 | 济南大学 | Method for preparing zinc oxide film using buffer layer |
| CN102168256B (en) * | 2011-03-21 | 2013-07-31 | 南开大学 | ZnO:B film grown by utilizing MOCVD (Metal Organic Chemical Vapor Deposition) gradient doping technology and application |
| CN102191487B (en) * | 2011-04-08 | 2012-06-27 | 南开大学 | Suede-structured ZnO film with flexible substrate by gradient temperature growth technology and its application |
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| JPH11335874A (en) * | 1998-05-25 | 1999-12-07 | Minolta Co Ltd | Working of zinc oxide film |
| US6136162A (en) * | 1998-02-17 | 2000-10-24 | Canon Kabushiki Kaisha | Method and apparatus for depositing zinc oxide film and method for producing photoelectric converter device |
| CN1308145A (en) * | 2000-11-17 | 2001-08-15 | 武汉大学 | Gallium nitride film preparing technology and special equipment |
| JP2001302673A (en) * | 2000-04-25 | 2001-10-31 | Mitsubishi Gas Chem Co Inc | Method for producing spiroglycol |
| CN1391259A (en) * | 2002-07-17 | 2003-01-15 | 浙江大学 | Process for growing P-type ZnO crystal film by real-time doping nitrogen |
| CN1461044A (en) * | 2003-06-11 | 2003-12-10 | 浙江大学 | Method for preparing p-type zinc oxide film |
| JP2004323941A (en) * | 2003-04-25 | 2004-11-18 | Central Glass Co Ltd | Method of depositing zinc oxide film |
| CN1180125C (en) * | 2002-01-30 | 2004-12-15 | 吉林大学 | MOCVD equipment and process for growing ZnO film |
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2005
- 2005-03-28 CN CNB2005100627432A patent/CN1327042C/en not_active Expired - Fee Related
Patent Citations (8)
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| US6136162A (en) * | 1998-02-17 | 2000-10-24 | Canon Kabushiki Kaisha | Method and apparatus for depositing zinc oxide film and method for producing photoelectric converter device |
| JPH11335874A (en) * | 1998-05-25 | 1999-12-07 | Minolta Co Ltd | Working of zinc oxide film |
| JP2001302673A (en) * | 2000-04-25 | 2001-10-31 | Mitsubishi Gas Chem Co Inc | Method for producing spiroglycol |
| CN1308145A (en) * | 2000-11-17 | 2001-08-15 | 武汉大学 | Gallium nitride film preparing technology and special equipment |
| CN1180125C (en) * | 2002-01-30 | 2004-12-15 | 吉林大学 | MOCVD equipment and process for growing ZnO film |
| CN1391259A (en) * | 2002-07-17 | 2003-01-15 | 浙江大学 | Process for growing P-type ZnO crystal film by real-time doping nitrogen |
| JP2004323941A (en) * | 2003-04-25 | 2004-11-18 | Central Glass Co Ltd | Method of depositing zinc oxide film |
| CN1461044A (en) * | 2003-06-11 | 2003-12-10 | 浙江大学 | Method for preparing p-type zinc oxide film |
Non-Patent Citations (3)
| Title |
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| RF磁控溅射法在Si衬底上生长ZnO薄膜界面的XPS研究 李万程等，吉林大学学报（理学版），第41卷第4期 2003 * |
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| 硅（001）衬底上生长的ZnO薄膜的AFM研究 张建隽，电子显微学报，第21卷第1期 2002 * |
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