CN114717657B - Method for growing nickel oxide monocrystal film based on plasma-assisted laser molecular beam epitaxy - Google Patents
Method for growing nickel oxide monocrystal film based on plasma-assisted laser molecular beam epitaxy Download PDFInfo
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- CN114717657B CN114717657B CN202210272003.5A CN202210272003A CN114717657B CN 114717657 B CN114717657 B CN 114717657B CN 202210272003 A CN202210272003 A CN 202210272003A CN 114717657 B CN114717657 B CN 114717657B
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
- C30B23/02—Epitaxial-layer growth
- C30B23/025—Epitaxial-layer growth characterised by the substrate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a method for growing a nickel oxide monocrystal film based on plasma-assisted laser molecular beam epitaxy. Firstly, preprocessing an oxide substrate; and then carrying out heteroepitaxy on nickel oxide on the oxide substrate at normal temperature by using laser molecular beam epitaxy assisted by oxygen plasma to obtain single crystal nickel oxide. According to the invention, the substrate pretreatment and the oxygen plasma auxiliary deposition are combined, the growth condition is optimized through the laser molecular beam epitaxy, the NiO monocrystal is obtained at normal temperature, the crystal quality is improved, the surface roughness is reduced, and the device performance is improved considerably. The substrate surface forms a macroscopic step flow structure thanks to the effective pretreatment of the substrate, thereby being beneficial to the formation of NiO monocrystal; in addition, oxygen atoms are activated by the assistance of oxygen plasma, and NiO is heteroepitaxially grown at normal temperature. The natural p-type material is high-quality heteroepitaxy on the gallium oxide substrate, and the realization way of the gallium oxide-based high-power device is widened.
Description
Technical Field
The invention relates to a method for epitaxially growing a nickel oxide single crystal film based on a plasma-assisted laser molecular beam, belonging to the technical field of preparation of wide-bandgap semiconductor material devices.
Background
Ga as an ultra-wideband semiconductor material 2 O 3 Has larger forbidden bandwidth (4.5-4.9 eV) and high breakdown field strength (8 MV/cm), the Baliga figure of merit exceeds 3000, is 5-10 times of wide band gap semiconductor GaN and SiC, and has wide application in the fields of power devices, radio frequency devices and the likeThe scene. However, ga 2 O 3 Many challenges remain in research, and the lack of p-type doping capability is still based on Ga 2 O 3 Is a major limitation of the power electronics of (a). Exploring other p-type wide bandgap semiconductor materials and combining with Ga 2 O 3 Forming a heterogeneous integration of high quality is one possible solution.
NiO is a natural p-type oxide semiconductor, and has attracted considerable attention due to its bandgap of 3.2-3.8eV, excellent chemical stability, and high visible light transmittance. In addition, the large exciton binding energy (110 meV) makes it more widely used than GaN, znO, etc., and NiO and Ga 2 O 3 There is a well-matched epitaxial relationship and band structure between them. Common nickel oxide epitaxy methods include magnetron sputtering, laser molecular beam epitaxy, and the like. The nickel oxide obtained by magnetron sputtering is usually polycrystalline and amorphous, the surface roughness of the film obtained by the particle bombardment deposition mode is larger, various defects exist in the crystal, and the existence of multiple crystal boundaries also prevents the transportation of carriers, so that the improvement of the performance of the device is still limited greatly.
At present, high-temperature epitaxy is often required to obtain a heteroepitaxial film of high-quality oxide, and the epitaxial cost is high and the process is complex. In addition, common growth means such as magnetron sputtering, usually particle bombardment deposition rather than epitaxial growth, usually obtain polycrystalline and amorphous nickel oxide, with larger surface roughness and poor crystal quality, so that the improvement of device performance still has a bottleneck.
Disclosure of Invention
The invention aims at: aiming at improving the quality of nickel oxide crystals and breaking through the bottleneck of device performance, a method for obtaining a nickel oxide single crystal with low surface roughness through Laser Molecular Beam Epitaxy (LMBE) at normal temperature by combining substrate pretreatment and oxygen plasma assisted deposition is provided. The oxygen plasma assisted NiO growth in the invention does not need high temperature, simplifies the growth step, optimizes the pretreatment of the substrate and the growth condition to ensure that common polycrystalline and amorphous products are optimized into single crystal NiO, improves the crystal quality, reduces the surface roughness and ensures that the device performance is improved considerably.
The invention adopts the following technical scheme for solving the technical problems:
the method for growing the nickel oxide monocrystal film based on the plasma-assisted laser molecular beam epitaxy combines substrate pretreatment and oxygen plasma assistance, and obtains the nickel oxide monocrystal through the laser molecular beam epitaxy at normal temperature, and specifically comprises the following steps:
(1) Pre-treating an oxide substrate;
(2) And carrying out heteroepitaxy of nickel oxide on the oxide substrate at normal temperature by using laser molecular beam epitaxy assisted by oxygen plasma to obtain single-crystal nickel oxide.
Further, the oxide substrate in the step (1) is c-plane sapphire, znO or Ga 2 O 3 。
Further, the pretreatment in the step (1) specifically comprises the following steps: the oxide substrate is corroded in hot concentrated sulfuric acid for 0.5 to 1 hour, and then annealed at high temperature for 12 to 24 hours.
Further, the temperature of the concentrated sulfuric acid is 120-180 ℃.
Further, the annealing temperature is 1000-1500 ℃.
Further, the laser wavelength in the step (2) is λ=248 nm, and the laser power density is 135-225 mJ; the laser frequency is 1-10 Hz.
Further, the oxygen plasma power in the step (2) is 150-300W, the oxygen flow is 1.5-3 sccm, and the growth pressure is 1X 10 -5 ～9×10 -5 Torr。
Further, the specific steps of the step (2) of heteroepitaxial nickel oxide on an oxide substrate are as follows:
placing the cleaned and nitrogen-dried substrate into a pre-pumping chamber of a laser molecular beam epitaxy device, and sending the substrate into a growth chamber after baking and degassing in the pre-pumping chamber; the target material uses nickel oxide, and the growth atmosphere is O 2 。
Further, the vacuum degree of the pre-pumping chamber is 6×10 -7 The background vacuum degree of the growth chamber is 6×10 under Torr -8 Torr or less; the distance d between the substrate and the target S-T 40-50 cm; the O is 2 The purity of (3) is above 99.99%The purity of the nickel oxide target is more than 99.99 percent.
The surface roughness of the nickel oxide single crystal film prepared by the method is reduced to 0.20nm.
Advantageous effects
(1) By combining substrate pretreatment and oxygen plasma assistance and optimizing the growth conditions, niO single crystals are obtained at normal temperature through laser molecular beam epitaxy, and the surface roughness can be reduced to 0.20nm.
(2) The substrate surface is formed by virtue of effective pretreatment of the substrate, so that the formation of NiO monocrystal is facilitated; oxygen plasma assisted deposition activates oxygen atoms enabling heteroepitaxy of NiO single crystals at ambient temperature.
In summary, the NiO obtained by heteroepitaxy is monocrystalline, and the surface roughness is greatly reduced.
Drawings
Fig. 1 is a reflection high-energy electron diffraction pattern of NiO obtained by normal-temperature epitaxy on a c-plane sapphire substrate.
Fig. 2 is an X-ray 2θ—ω scan of NiO epitaxially grown on a c-plane sapphire substrate at normal temperature.
Fig. 3 is a graph showing the rocking curve of the X-ray diffraction (111) plane of the NiO film thus produced.
Fig. 4 (a) is an atomic force microscope image of a pretreated c-plane sapphire substrate, and (b) is an atomic force microscope image of a prepared NiO single crystal thin film.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings. The embodiments described below by referring to the drawings are exemplary only for explaining the present invention and are not to be construed as limiting the present invention.
The oxide substrate used for NiO heteroepitaxy is c-plane sapphire, znO and Ga 2 O 3 。
Example 1
In this embodiment, on a sapphire substrate, epitaxy of a nickel oxide single crystal is performed at normal temperature by means of oxygen plasma, and the specific steps are as follows:
(1) C, preprocessing the c-plane sapphire substrate: corroding in hot concentrated sulfuric acid (150 ℃) for 30min, and annealing in an annealing furnace at high temperature (1200 ℃) for 12h;
(2) Heteroepitaxy NiO at normal temperature using laser molecular beam epitaxy (λ=248 nm): placing the cleaned and nitrogen-dried substrate into a pre-pumping chamber of a laser molecular beam epitaxy device, wherein the vacuum degree of the pre-pumping chamber is 6 multiplied by 10 -7 Torr, baking and degassing in a pre-pumping chamber, and feeding into a growth chamber with a background vacuum degree of 6×10 -8 Torr; niO (purity 99.99%) is used as target material, and the growth atmosphere is O 2 (purity 99.99% or more); substrate target spacing d S-T 45cm, a laser power density of 135mJ and a laser frequency of 2Hz;
(3) With the assistance of oxygen plasma for deposition, the power of the oxygen plasma is 200W, the oxygen flow is 2sccm, and the growth pressure is 6 multiplied by 10 -5 Torr, the epitaxy of NiO was carried out at normal temperature, and the growth time was 3 hours.
As shown in fig. 1, a reflection high-energy electron diffraction pattern of NiO obtained by normal-temperature epitaxy on a c-plane sapphire substrate is shown, and as can be seen from diffraction fringes in the figure, the prepared NiO is single crystal, and the surface of a sample is very flat.
As shown in fig. 2, an X-ray 2θ—ω scan of NiO obtained by normal temperature epitaxy on a c-plane sapphire substrate was shown, and as can be seen from the figure, the diffraction peak of NiO was cubic NiO, and it was confirmed that hetero-epitaxy obtained was cubic NiO single crystal.
Fig. 3 is a rocking curve diagram of an X-ray diffraction (111) plane of the prepared NiO film, wherein the half-width of the rocking curve is an important index for representing the quality of single crystals, and the half-width of the rocking curve of the prepared NiO film (111) plane is 0.77 degrees, which indicates that the quality of the prepared NiO single crystal film crystals is good.
FIG. 4 (a) is an atomic force microscope image of a pretreated c-plane sapphire substrate, from which grooves can be seen, with a surface roughness of 0.23nm; (b) For an atomic force microscope image of the prepared NiO film, the surface roughness was 0.20nm.
Claims (6)
1. The method for growing the nickel oxide monocrystal film by the ion body assisted laser molecular beam epitaxy is characterized by combining substrate pretreatment and oxygen plasma assistance, and obtaining monocrystal nickel oxide by the laser molecular beam epitaxy at normal temperature, and specifically comprises the following steps:
(1) Pre-treating an oxide substrate; the pretreatment comprises the following specific steps: etching the oxide substrate in hot concentrated sulfuric acid for 0.5-1 h, and then annealing at high temperature for 12-24 h;
(2) Carrying out heteroepitaxy on nickel oxide on an oxide substrate at normal temperature by using laser molecular beam epitaxy assisted by oxygen plasma to obtain monocrystal nickel oxide; the specific steps of heteroepitaxial nickel oxide on an oxide substrate are as follows:
placing the cleaned and nitrogen-dried substrate into a pre-pumping chamber of a laser molecular beam epitaxy device, and sending the substrate into a growth chamber after baking and degassing in the pre-pumping chamber; the target material uses nickel oxide, and the growth atmosphere is O 2 ；
The annealing temperature is 1000-1500 ℃.
2. The method for plasma-assisted laser molecular beam epitaxy of a nickel oxide single crystal thin film according to claim 1, wherein the oxide substrate in step (1) is c-plane sapphire, znO or Ga 2 O 3 。
3. The method for epitaxial growth of a nickel oxide single crystal thin film based on plasma-assisted laser molecular beam according to claim 1, wherein the temperature of the concentrated sulfuric acid is 120-180 ℃.
4. The method for epitaxial growth of a nickel oxide single crystal thin film by plasma-assisted laser molecular beam according to claim 1, wherein the laser wavelength in the step (2) is λ=248 nm or 193 nm, and the laser power density is 135-225 mJ; the laser frequency is 1-10 Hz.
5. The method for plasma-assisted laser molecular beam epitaxy of a nickel oxide single crystal thin film according to claim 1, wherein the step (2) is performed byThe oxygen plasma power is 150-300W, the oxygen flow is 1.5-3 sccm, and the growth pressure is 1X 10 -5 ~9×10 -5 Torr。
6. The method for epitaxial growth of a nickel oxide single crystal thin film by plasma-assisted laser molecular beam according to claim 1, wherein the pre-pumping chamber has a vacuum degree of 6 x 10 -7 The background vacuum degree of the growth chamber is 6×10 under Torr -8 Torr or less; the distance d between the substrate and the target material S-T 40-50 cm; said O 2 The purity of the nickel oxide target material is more than 99.99 percent, and the purity of the nickel oxide target material is more than 99.99 percent.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102534767A (en) * | 2011-12-29 | 2012-07-04 | 浙江大学 | Na-mixing method for growing p-type ZnO single crystal film |
| CN111334856A (en) * | 2020-02-18 | 2020-06-26 | 浙江大学 | Method for growing high-quality ZnO single crystal film by quasi van der waals epitaxy using plasma-assisted molecular beam epitaxy |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102534767A (en) * | 2011-12-29 | 2012-07-04 | 浙江大学 | Na-mixing method for growing p-type ZnO single crystal film |
| CN111334856A (en) * | 2020-02-18 | 2020-06-26 | 浙江大学 | Method for growing high-quality ZnO single crystal film by quasi van der waals epitaxy using plasma-assisted molecular beam epitaxy |
Non-Patent Citations (1)
| Title |
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| 脉冲激光沉积制备NiO(111)外延薄膜及其结构研究;贝力等;《电子元件与材料》(第07期);第36-38页 * |
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