CN110438567A - A kind of preparation method of semiconductor selenium bismuth oxide single crystal thin-film material - Google Patents

A kind of preparation method of semiconductor selenium bismuth oxide single crystal thin-film material Download PDF

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CN110438567A
CN110438567A CN201910658855.6A CN201910658855A CN110438567A CN 110438567 A CN110438567 A CN 110438567A CN 201910658855 A CN201910658855 A CN 201910658855A CN 110438567 A CN110438567 A CN 110438567A
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preparation
substrate
single crystal
bismuth oxide
film material
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李卓君
宋叶凯
彭炜
牟刚
谢晓明
江绵恒
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Shanghai Institute of Microsystem and Information Technology of CAS
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Shanghai Institute of Microsystem and Information Technology of CAS
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    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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    • C30B23/00Single-crystal growth by condensing evaporated or sublimed materials
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    • C30B23/00Single-crystal growth by condensing evaporated or sublimed materials
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Abstract

The present invention provides a kind of preparation method of semiconductor selenium bismuth oxide single crystal thin-film material, comprising the following steps: S1: being sintered Bi using solid phase method2O2Se polycrystal target;S2: one cube or cubic crystalline form substrate are provided;S3: the substrate is started the cleaning processing with organic solvent;S4: the substrate after cleaning is made annealing treatment in impulse laser deposition system;S5: the target described in ablation S1 step in impulse laser deposition system, in above-mentioned substrate surface epitaxial semiconductor Bi2O2Se monocrystal thin films.The present invention utilize pulsed laser deposition technique, by high-vacuum equipment, excimer laser hardware, the synthesis of polycrystal target, the selection of substrate, the processing of substrate, Film synthesis parameter stability contorting, the Bi of high quality is prepared2O2Se monocrystal thin films material.Preparation method of the invention has great value to the application level accelerated the research of film growth mechanism, improve film.

Description

A kind of preparation method of semiconductor selenium bismuth oxide single crystal thin-film material
Technical field
The invention belongs to materials synthesis fields, are related to a kind of semiconductor Bi2O2The system of Se (selenium bismuth oxide) monocrystal thin films material Preparation Method
Background technique
Foundation stone of the semiconductor material as modern information technologies, experienced using Si as the element semiconductor of representative, with GaAs, GaP is the compound semiconductor of representative, and using GaN, SiC as the development of the wide bandgap semiconductor three phases of representative, all kinds of The ingredient and structure regulating technology of common semiconductor material have tended to be mature.As the processing technology of conventional semiconductors is got over To be difficult to further excavate new performance closer to physics limit, existing semiconductor technology and material.Therefore, it is suitable to seek The novel high-performance semiconductor material of forbidden bandwidth and high mobility becomes the coke that current information technology and related fields are paid close attention to Point.
The discovery of graphene (Graphene) promotes two chalcogen compound of magnesium-yttrium-transition metal (MX2), black phosphorus (B-P) etc. two The research boom of layer structure semiconductor material is tieed up, this kind of material is because of its special crystal structure and electronic band structure effect on the scene It answers and is excellent in transistor, phototransistor and light absorption device.Single layer atomic crystal has reached the thickness pole of material Limit, therefore two-dimensional layered-structure material is expected to the semiconductor material as rear mole of epoch.However to have excellent performance at present, energy Stablize and the ultra-thin semiconductor material that experimentally easily obtains is still in the exploratory stage.Therefore, superior electron mobility, suitable is found Band gap, ambient stable and ultra-thin semiconductor material the features such as can prepare in batches are still the weight of current research.
Bi2O2Se is the layer structure semiconductor material of a kind of modulation doping type, high electron mobility, by Bi2O2Se thin slice The fieldtron room temperature mobilities of processing reach 450cm2/V-1s-1, more up to 28900cm2/V-1s-1 under low temperature 2K, device Part on-off ratio is more than 106.Research also indicates that, reduces with thickness, Bi2O2The band gap of Se changes to single layer by the 0.8eV of body material 1.9eV.From the point of view of current technology, Bi2O2Se preparation process is simple, has a possibility that large-scale production, and the material is negative by band The Bi of electricity2O2Layer and positively charged Se atomic layer are alternately stacked composition, the presence of oxygen in crystal, make it in air and have and is splendid Stability.
Bi at present2O2The preparation of Se thin-film material is mainly by chemical vapour deposition technique, it is difficult to realize;Chemical gaseous phase simultaneously Sedimentation incompatible metal mask version in thin film growth process, needs to grow by cumbersome technique with particular geometric The Bi of pattern2O2Se film.It would therefore be highly desirable to explore and develop it is a kind of overcome drawbacks described above prepare semiconductor Bi2O2Se film material The method of material.
Summary of the invention
Therefore, the purpose of the present invention is to provide a kind of semiconductor Bi2O2The preparation method of Se monocrystal thin films material, with reality Now Bi on entire substrate2O2The uniformity of Se film thickness, while just need not can be grown with particular geometric by cumbersome technique The Bi of pattern2O2Se film.
To achieve the above object and other related purposes, the present invention provide a kind of semiconductor Bi2O2Se monocrystal thin films material Preparation method includes the following steps:
S1: Bi is sintered using solid phase method2O2Se polycrystal target;
S2: one cube or cubic crystalline form substrate are provided;
S3: the substrate is started the cleaning processing with organic solvent;
S4: to the lining after cleaning in pulse laser deposition (Pulsed Laser Deposition, abbreviation PLD) system Bottom is made annealing treatment;
S5: the target described in ablation S1 in impulse laser deposition system, in the substrate surface epitaxial semiconductor Bi2O2Se monocrystal thin films.
Further, the step S1 is comprised the following processes: weighing raw material, vacuum sealing, first sintering, grinding, pressure Type, again vacuum sealing, second of sintering is made.
Further, the raw material of the weighing is Bi, Se, Bi that molar ratio is 2:3:22O2
Further, the raw material after the weighing is sealed in quartz ampoule of the vacuum degree not less than 5E10-4Pa.
Further, the step of first sintering is that the quartz ampoule for loading raw material is put into box Muffle furnace, It is first to heat to 900-1000 DEG C, the quartz ampoule for loading raw material keeps the temperature 12-36 hours at such a temperature, is subsequently cooled to room Temperature makes raw material become block.
Further, the block is ground 20-60 minutes in inert-atmosphere glove box, forming fineness is 100-200 Purpose powder.
Further, the powder is fitted into mold, diameter 8-10mm, thickness 2- is pressed under the pressure of 7-9Mpa The disk of 3mm.
Further, the disk is sealed in quartz ampoule of the vacuum degree not less than 5E10-4Pa.
Further, the quartz ampoule for loading disk is put into box Muffle furnace, 400-500 DEG C is first to heat to, at this At a temperature of keep the temperature 6-24 hours, then cool to room temperature.
Further, described cube or cubic crystalline form substrate are selected from one of following compound cubic crystal: SrTiO3、 LaAlO3、MgO、CaF2Or MgF2
Further, the SrTiO3Substrate is the monocrystal chip of<001>crystal orientation.
Further, in the step S3, the substrate is sequentially placed into acetone, alcohol or isopropanol and carries out ultrasound Cleaning, scavenging period is respectively 1-60 minutes, is then dried up the substrate using inert gas.
Further, the inert gas is nitrogen or argon gas.
Further, in the step S4, the substrate after cleaning is passed to the vacuum of impulse laser deposition system Chamber set temperature is 500-600 DEG C, keeps the temperature 60-180 minutes at the set temperature.
Further, in the step S5, laser is the KrF of wavelength 248nm in the impulse laser deposition system Excimer laser, laser energy 120-150mJ, system vacuum are better than 5E10-5Pa, and the underlayer temperature is 300-550 ℃。
Further, when the epitaxial growth, the underlayer temperature is 450 DEG C.
As described above, semiconductor Bi of the invention2O2The preparation method of Se monocrystal thin films material, has the advantages that The present invention utilize pulsed laser deposition technique, by high-vacuum equipment, impulse laser deposition system, excimer laser hardware, The synthesis of polycrystal target, the selection of substrate, the processing of substrate, Film synthesis parameter stability contorting, high quality is prepared Bi2O2Se monocrystal thin films material.The present invention utilizes Bi under high vacuum2O2The physical gas-phase deposite method of Se single crystal epitaxial film, no It only may be implemented the continuity and the thickness uniformity of film in large area, while compatible high vacuum characterizes equipment, and need not be by Cumbersome technique just can grow the Bi with particular geometric pattern2O2Se monocrystal thin films realize Bi2O2The growth in situ of Se film And test.The monocrystal thin films material possesses very big advantage compared to body material, to the material in basic research and semiconductor application On have great value.
Detailed description of the invention
Fig. 1 is shown as semiconductor Bi of the invention2O2The process flow chart of the preparation method of Se monocrystal thin films material;
Fig. 2 shows SrTiO when underlayer temperature is too low3The Bi grown on substrate2O2XRD spectrum outside the face of Se film;
Fig. 3 shows SrTiO when underlayer temperature is excessively high3The Bi grown on substrate2O2XRD spectrum outside the face of Se film;
Fig. 4 shows SrTiO when underlayer temperature is more excellent3The Bi grown on substrate2O2XRD spectrum outside the face of Se film;
Fig. 5 shows SrTiO when underlayer temperature is more excellent3The Bi grown on substrate2O2The room temperature 300K and low temperature 2K of Se film are moved The comparison of shifting rate;
Fig. 6 shows SrTiO when underlayer temperature is optimal3The Bi grown on substrate2O2XRD spectrum in the face of Se film.
Specific embodiment
Embodiments of the present invention are illustrated below in conjunction with attached drawing, those skilled in the art can be as disclosed by this specification Content other advantages and efficacy of the present invention can be easily understood.The present invention can also be by way of a different and different embodiment It is embodied or practiced, the various details in this specification can also be based on different viewpoints and application, without departing from the present invention Spirit under carry out various modifications or alterations.
The present invention provides a kind of semiconductor Bi2O2The preparation method of Se monocrystal thin films material, the process flow of this method is as schemed Shown in 1, include the following steps:
S1: Bi is sintered with solid phase method2O2Se polycrystal target;
S2: one cube or cubic crystalline form substrate are provided;
S3: the substrate is started the cleaning processing with organic solvent;
S4: the substrate after cleaning is made annealing treatment in impulse laser deposition system;
S5: the target described in ablation S1 in impulse laser deposition system, in above-mentioned substrate surface epitaxial semiconductor Bi2O2Se monocrystal thin films.
Pulsed laser deposition prepare film basic principle and process be focus after laser beam and target interact Plasma is generated, plasma transports to be formed with height-oriented plumage brightness in space, and the high energy particle that plumage brightness carries is serving as a contrast It is agglomerated on bottom and forms film.Therefore the acquisition of target is the primary link that PLD prepares film.The chemistry of target under normal circumstances Ingredient and component and required film to be prepared are almost the same, having a size of several millimeters of diameter or more, the several millimeters of thickness and Above fine and close round sheet uses round sheet, certainly also because target needs to rotate in PLD coating process herein It can be the other shapes such as similar round, rectangular.
Step S1 is first carried out, is sintered Bi with solid phase method2O2Se polycrystal target.
As an example, solid phase method is sintered Bi2O2Se polycrystal target comprises the following processes:
1) weigh raw material: in the present embodiment, the raw material of weighing is Bi, Se, Bi2O3 that molar ratio is 2:3:2, it is therefore an objective to be protected It is consistent with the film of required preparation to demonstrate,prove target chemical component;More raw material selections and broader molar ratio range depend on giving birth to Long film.
2) vacuum sealing: as an example, it is mesh in 5E10-4Pa quartz ampoule that the raw material of the weighing, which should be sealed in vacuum degree, Be prevent high-temperature sintering process occur volatility of raw material, oxidation situations such as;
3) first sintering: box Muffle furnace, the heating unit of the Muffle furnace will be put into the quartz ampoule for loading raw material Part is resistance wire, 1100 DEG C of maximum operation (service) temperature, is first to heat to 950 DEG C, and keeping the temperature preset time at such a temperature is 24 hours, is made Raw material, which melts completely at such a temperature and has enough time sufficiently to react, generates polycrystalline Bi2O2Se block, then naturally cools to room Temperature;Temperature range during this can adjust between 900-1000 DEG C, and soaking time can be 12-36 hours, cooling Process can also cool down in such a way that cooling process is arranged in temperature controller.
4) grind: the process of lapping grinds 30 points in argon atmosphere glove box, by the block after the first sintering Clock or so becomes 100~200 mesh of fineness, and quality is not more than the powder of 1.5g, and the fineness of the powder is 100-200 mesh, with Just next step compression moulding;Wherein argon gas can also be replaced with inert gases such as nitrogen, and milling time can be 20-60 minutes.
5) the ground powder compression moulding: is fitted into mold) in, the mold such as Tianjin essence opens up instrument science and technology D0102- (PM-B) the pattern tool of Co., Ltd's production, is pressed into diameter 8-10mm, thickness 1-2mm under the pressure of 7-9Mpa Disk.
6) vacuum sealing again: it is in 5E10-4Pa quartz ampoule, to prevent high temperature from burning that the disk, which is sealed in vacuum degree, Situations such as element evaporation leads to Segregation of Chemical Composition in disk, occurs for knot process;
7) it is sintered for second: the quartz ampoule for loading disk being put into box Muffle furnace, is first to heat to 450 DEG C;By institute The quartz ampoule for stating loading disk keeps the temperature 12 hours at 450 DEG C, and the disk of the compression moulding is sintered, and increases disk The consistency of target, then by the quartz ampoule cooled to room temperature for loading disk.400 DEG C of the heating temperature range~ 500 DEG C, soaking time can be 6-24 hours.
Then step S2 is executed, a cubic oxide substrate is provided.
Specifically, the four directions oxide substrate is SrTiO3。SrTiO3(strontium titanates) is (special with typical cube Four directions) perovskite structure, it is nontoxic chemical substance, is a kind of widely used electric function ceramic material, there is dielectric constant High, the advantages that dielectric loss is low, thermal stability is good, it is widely used in electronics, machinery and ceramic industry;Meanwhile as a kind of function Energy material, strontium titanates has the characteristics that forbidden bandwidth high (3.4eV), photocatalytic activity are excellent, and has unique electromagnetic property With redox catalysis activity, urged in light such as photocatalytic hydrogen production by water decomposition, photocatalysis degradation organic contaminant and photochemical cells Change field is also widely used.In addition, substrate material is also an option that LaAlO3, MgO, CaF2, MgF2Deng cube/tetra- The substrate of prismatic crystal type.
As an example, described cube or cubic crystalline form SrTiO3Substrate can directly adopt the monocrystal chip of<001>crystal orientation, Surface flatness with higher.SrTiO3The face ab and Bi2O2The lattice mismatch in the face ab of Se is 0.6%, be can guarantee The thin film epitaxial growth that c is orientated outside good face.
Then step S3 is executed, the substrate is started the cleaning processing using organic solvent, removal substrate surface absorption Organic impurities are subsequent growth semiconductor Bi2O2Se monocrystal thin films material provides a clean surface, reduces defect growth Probability.
Organic solvent used by cleaning treatment, in the present embodiment, it is preferred to use acetone is cleaned by ultrasonic.Certainly, In In other embodiments, other organic solvents, such as ethyl alcohol can also be used to be cleaned.
In order to avoid secondary pollution, using acetone carry out ultrasonic cleaning and then by the substrate be sequentially placed into alcohol, It is cleaned by ultrasonic in isopropanol, ultrasound 1-60 minutes respectively, is dried up the substrate using inert gas after cleaning.
As a specific embodiment, cleaning is divided into four steps: first step acetone is 20 minutes ultrasonic, it is therefore an objective to wash off substrate table The organic matter of face absorption;Second step was with alcohol ultrasound 20 minutes, in order to wash off the remaining acetone of substrate surface;Third step With isopropanol ultrasound 5 minutes, in order to wash off the remaining alcohol of substrate surface, and isopropanol itself can be waved rapidly Hair, will not remain in substrate surface;4th step is quickly dried up substrate with high pure nitrogen.
Step S4 is executed again, and the substrate is made annealing treatment in impulse laser deposition system.The mesh of annealing Be to reset substrate surface part of atoms, be subsequent growth high-quality semiconductor to repair the defect of substrate surface Bi2O2Se monocrystal thin films material provides more preferably platform.
In the present embodiment, annealing carries out in impulse laser deposition system.Impulse laser deposition system is high vacuum Device hardware, in the present embodiment, it is desirable that system vacuum is better than 5E10-5Pa.
As an example, the annealing comprises the following processes:
1) substrate is passed to the vacuum chamber of impulse laser deposition system, and is heated to 500-600 DEG C, is in this example 550 DEG C, so that the adsorbate of substrate surface remnants is desorbed under high vacuum heating condition, and emit substrate surface part of atoms It resets, to repair the defect of substrate surface;Then the substrate is kept the temperature 60-180 minutes at such a temperature, in this case, it is 60 minutes.
Finally execute step S5, the target described in ablation S1 in impulse laser deposition system, in above-mentioned substrate surface extension Grow semiconductor Bi2O2Se monocrystal thin films.The laser is the KrF excimer laser of wavelength 248nm, the laser energy For 120-150mJ, laser energy is too low or the too high generation for being all unfavorable for high-quality thin film, and laser energy is preferred in the present embodiment For 130mJ;System vacuum is better than 5E10-5Pa when the epitaxial growth.In this respect it is to be noted that system when vacuum degree is low In foreign gas can scatter plumage brightness carrying particle, to film grow when nucleation, at mutually and orientation cause unfavorable shadow It rings, while can also introduce impurity in the film.In the present embodiment, the vacuum degree the high when epitaxial growth more is conducive to the outer of film Prolong growth.In other embodiments, system vacuum can be adjusted flexibly according to the actual situation when the epitaxial growth.The lining Bottom temperature is 300-550 DEG C, preferably 450 DEG C.
Specifically, the substrate made annealing treatment in the impulse laser deposition system after without taking out, can be with Directly carry out epitaxial manufacture process.
The present invention utilizes pulsed laser deposition technique, more by high-vacuum equipment, excimer laser hardware, high-compactness The synthesis of brilliant target, the selection of substrate, the processing of substrate, Film synthesis parameter stability contorting, single take can be prepared High, the symmetrical high quality Bi of quadruple to, mobility2O2Se monocrystal thin films material.
The semiconductor Bi being prepared under different technical parameters will be concentrated below2O2The test result of Se monocrystal thin films material It compares.Characterization method is X-ray diffraction technology (X-ray Diffraction, XRD), electronic transport measures resistance and Hall Effect is with computation migration rate.To pass through different epitaxial conditions in SrTiO3Semiconductor Bi is prepared on substrate2O2Se film Out-of-plane orientation XRD spectrum.
Fig. 2-Fig. 4 be respectively indicated as epitaxial temperature it is too low when (300-400 DEG C), epitaxial temperature it is excessively high when (475-550 DEG C) And epitaxial temperature it is more excellent when (425-450 DEG C) SrTiO3The Bi grown on substrate2O2The out-of-plane orientation XRD spectrum of Se film.Such as figure Shown in 2, when growth temperature is too low, noncrystal membrane or the Bi containing miscellaneous phase can be obtained2O2Se film;As shown in figure 3, growth temperature When spending high, will form out-of-plane orientation and substrate orientation is inconsistent or face outside be not single-orientated Bi2O2Se film.Such as figure Shown in 4, when growth temperature is more excellent, XRD shows the Bi for be outside face be single (002) orientation being prepared outside face2O2Se, film Out-of-plane orientation is consistent with substrate out-of-plane orientation.
As it can be seen that selecting suitable epitaxial temperature to preparing semiconductor Bi2O2Se monocrystal thin films material is extremely important.
SrTiO when Fig. 5 display display underlayer temperature is more excellent3The Bi grown on substrate2O2The room temperature 300K and low temperature of Se film The comparison of 2K electron mobility.Mobility has reacted the quality of carrier in material, service life and by physical properties such as dispersion effects.Half Carrier is at low temperature mainly by the scattering of defect and impurity in conductor, is mainly generated by being vibrated by atomic lattice under high temperature Phonon scattering.Scattering is stronger, and mobility is lower.For semiconductor material, mobility is higher, indicates to a certain extent Defect and impurity concentration is small in material, and sample quality is good.By comparison as can be seen that Bi2O2Room temperature mobilities of Se film and low Warm mobility all increases with underlayer temperature and is increased, and illustrates that properly increasing underlayer temperature in 425-450 DEG C of this warm area is conducive to Improve sample quality.
As it can be seen that being suitble to Bi2O2The underlayer temperature window of this Material growth of Se is relatively narrow, and finding 450 DEG C in the present embodiment is Bi2O2The optimal growth temperature of Se film.
Fig. 6 shows SrTiO when underlayer temperature is optimal3The Bi grown on substrate2O2In the face in Se film (011) faceScanning Map.It is always seen along film surface method, it is single-orientated that film, which is grown along c-axis,.But the XRD scanning of out-of-plane orientation cannot Arrangement architecture information in pellicular front is provided.Therefore we select and (002) face is at (011) face of 72.279 angles, study and obtain With relevant information is orientated in pellicular front.It can be seen that Bi2O2In the face in Se film (011) faceScanning four fold symmetry of display Property, and with substrate S rTiO3Irrotationality transfers the registration of Party membership, etc. from one unit to another.Indicate SrTiO when underlayer temperature is optimal3The Bi grown on substrate2O2Se film is The monocrystal thin films of high quality.
In conclusion the present invention utilize pulsed laser deposition technique, by high-vacuum equipment, excimer laser hardware, The synthesis of polycrystal target, the selection of substrate, the processing of substrate, Film synthesis parameter stability contorting, high quality is prepared Bi2O2Se monocrystal thin films material.Bi provided by the invention2O2The preparation method of Se monocrystal thin films material is to quickening film growth machine Reason research, the application level for improving film have great value.
Above-described embodiment is merely exemplary to illustrate the principle of the present invention and its effect, and is not intended to limit the present invention.It is any ripe The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as At all equivalent modifications or change, be still covered by the claims of the present invention.

Claims (16)

1. a kind of preparation method of semiconductor selenium bismuth oxide single crystal thin-film material, which is characterized in that in turn include the following steps:
S1: Bi is sintered using solid phase method2O2Se polycrystal target;
S2: one cube or cubic crystalline form substrate are provided;
S3: the substrate is started the cleaning processing with organic solvent;
S4: the substrate after cleaning is made annealing treatment in impulse laser deposition system;
S5: the target described in ablation S1 in impulse laser deposition system, in the substrate surface epitaxial semiconductor Bi2O2Se monocrystal thin films.
2. the preparation method of semiconductor selenium bismuth oxide single crystal thin-film material according to claim 1, it is characterised in that: described Step S1 is comprised the following processes: weighing raw material, vacuum sealing, first sintering, grinding, compression moulding, again vacuum sealing, the Double sintering.
3. the preparation method of semiconductor selenium bismuth oxide single crystal thin-film material according to claim 2, which is characterized in that described The raw material of weighing is Bi, Se, Bi that molar ratio is 2:3:22O3
4. the preparation method of semiconductor selenium bismuth oxide single crystal thin-film material according to claim 2, which is characterized in that by institute It states the raw material after weighing and is sealed in vacuum degree not less than 5E10-4In the quartz ampoule of Pa.
5. the preparation method of semiconductor selenium bismuth oxide single crystal thin-film material according to claim 4, it is characterised in that: described The step of first sintering is that the quartz ampoule for loading raw material is put into box Muffle furnace, is first to heat to 900-1000 DEG C, institute The quartz ampoule for stating loading raw material keeps the temperature 12-36 hours at such a temperature, then cools to room temperature, and raw material is made to become block.
6. the preparation method of semiconductor selenium bismuth oxide single crystal thin-film material according to claim 5, it is characterised in that: by institute It states block to grind in inert-atmosphere glove box 20-60 minutes, forms the powder that fineness is 100-200 mesh.
7. the preparation method of semiconductor selenium bismuth oxide single crystal thin-film material according to claim 6, it is characterised in that: by institute It states powder to be fitted into mold, the disk of diameter 8-10mm, thickness 2-3mm is pressed under the pressure of 7-9Mpa.
8. the preparation method of semiconductor selenium bismuth oxide single crystal thin-film material according to claim 7, it is characterised in that: by institute It states disk and is sealed in vacuum degree not less than 5E10-4In the quartz ampoule of Pa.
9. the preparation method of semiconductor selenium bismuth oxide single crystal thin-film material according to claim 8, it is characterised in that: by institute The quartz ampoule for stating loading disk is put into box Muffle furnace, is first to heat to 400-500 DEG C, keeps the temperature 6-24 hours at such a temperature, so After be cooled to room temperature.
10. the preparation method of semiconductor selenium bismuth oxide single crystal thin-film material according to claim 1, it is characterised in that: institute It states cube or cubic crystalline form substrate is selected from one of following compound cubic crystal: SrTiO3、LaAlO3、MgO、CaF2Or MgF2
11. the preparation method of semiconductor selenium bismuth oxide single crystal thin-film material according to claim 10, it is characterised in that: institute State SrTiO3Substrate is the monocrystal chip of<001>crystal orientation.
12. the preparation method of semiconductor selenium bismuth oxide single crystal thin-film material according to claim 1, it is characterised in that: In In the step S3, the substrate is sequentially placed into acetone, alcohol or isopropanol and is cleaned by ultrasonic, scavenging period is respectively 1-60 minutes, then the substrate is dried up using inert gas.
13. the preparation method of semiconductor selenium bismuth oxide single crystal thin-film material according to claim 12, it is characterised in that: institute Stating inert gas is nitrogen or argon gas.
14. the preparation method of semiconductor selenium bismuth oxide single crystal thin-film material according to claim 1, it is characterised in that: In It is 500-600 by the vacuum chamber set temperature that the substrate after cleaning is passed to impulse laser deposition system in the step S4 DEG C, keep the temperature 60-180 minutes at the set temperature.
15. the preparation method of semiconductor selenium bismuth oxide single crystal thin-film material according to claim 1, it is characterised in that: In In the step S5, laser is the KrF excimer laser of wavelength 248nm, laser energy in the impulse laser deposition system Amount is 120-150mJ, and system vacuum is better than 5E10-5Pa, the underlayer temperature are 300-550 DEG C.
16. the preparation method of semiconductor selenium bismuth oxide single crystal thin-film material according to claim 15, which is characterized in that institute When stating epitaxial growth, the underlayer temperature is 450 DEG C.
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CN112824555A (en) * 2019-11-21 2021-05-21 中国科学院上海微系统与信息技术研究所 Preparation method of titanium oxide superconducting film
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