CN117107193A - Zinc stannate single crystal film and preparation method thereof - Google Patents
Zinc stannate single crystal film and preparation method thereof Download PDFInfo
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- CN117107193A CN117107193A CN202311080447.XA CN202311080447A CN117107193A CN 117107193 A CN117107193 A CN 117107193A CN 202311080447 A CN202311080447 A CN 202311080447A CN 117107193 A CN117107193 A CN 117107193A
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- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 239000013078 crystal Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 65
- 239000000758 substrate Substances 0.000 claims abstract description 44
- 229910052594 sapphire Inorganic materials 0.000 claims abstract description 22
- 239000010980 sapphire Substances 0.000 claims abstract description 22
- 238000002834 transmittance Methods 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 238000004544 sputter deposition Methods 0.000 claims description 121
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 80
- 238000000137 annealing Methods 0.000 claims description 49
- 229910052786 argon Inorganic materials 0.000 claims description 40
- 238000005245 sintering Methods 0.000 claims description 26
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 20
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 18
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- 239000011787 zinc oxide Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 9
- 238000007731 hot pressing Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 abstract description 21
- 239000004065 semiconductor Substances 0.000 abstract description 9
- 230000007547 defect Effects 0.000 abstract description 5
- 239000010408 film Substances 0.000 description 87
- 230000001105 regulatory effect Effects 0.000 description 17
- 239000011701 zinc Substances 0.000 description 15
- 230000003287 optical effect Effects 0.000 description 12
- 238000000465 moulding Methods 0.000 description 8
- 239000013077 target material Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 238000005086 pumping Methods 0.000 description 7
- 238000000151 deposition Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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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
-
- 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
- C30B29/22—Complex 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
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
- C30B33/02—Heat treatment
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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
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
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Abstract
The invention belongs to the technical field of semiconductor film materials, and particularly relates to a zinc stannate single crystal film and a preparation method thereof. The preparation method comprises the following steps: and C-plane sapphire is selected as a substrate, a zinc stannate film grows on the C-plane sapphire substrate through magnetron sputtering bombardment of a zinc stannate target, and the grown zinc stannate film is annealed to obtain the zinc stannate single crystal film. The zinc stannate single crystal film prepared by the preparation method has a single crystal structure, complete lattice structure, fewer defects, average relative transmittance in the visible light range of more than 88 percent, excellent photoelectric property and good adhesion performance, and is suitable for manufacturing semiconductor quantum well devices.
Description
Technical Field
The invention belongs to the technical field of semiconductor film materials, and particularly relates to a zinc stannate single crystal film and a preparation method thereof.
Background
In recent years, transparent electronics and transparent oxide optoelectronics have received extensive attention and have been rapidly developed, and are now the leading research field of the world's enthusiasm. The wide forbidden band oxide semiconductor material is an important material for manufacturing transparent electronic devices and transparent optoelectronic devices, has extremely wide application prospect in the aspects of light emitting diodes, lasers, ultraviolet detectors, transparent thin film transistors, solar cells, flat panel displays, transparent electromagnetic shielding and the like, and is a currently and internationally popular leading edge research field.
Zinc stannate (Zn) 2 SnO 4 ) Has excellent photoelectric properties, is safe and nontoxic, does not contain rare elements, is an excellent functional material, and is Zn compared with other common Transparent Conductive Oxides (TCO) such as ITO (In-Sn-O) and CTO (Cd-Sn-O) 2 SnO 4 Cheaper and more environmentally friendly, notably Zn 2 SnO 4 Thermal stability in hydrogen environment compared to SnO 2 Higher stability in acid-base solution than ZnO, has wide application prospect in the field of semiconductor photoelectric devices, and gradually arouses great interest of researchers.
Zn 2 SnO 4 Has inverse spinel structure, belongs to cubic crystal system, and has lattice constant ofThe space group is Fd3m. Zn (zinc) 2 SnO 4 The semiconductor material is a novel wide-bandgap direct band-gap semiconductor material, and the bandgap width is more than 3.6 eV. The high-quality monocrystalline epitaxial oxide film material has the advantages of perfect structure, few defects, high mobility, excellent optical performance and the like, and shows the special superiority in the manufacture of high-performance transparent photoelectric devices. Thus, zn with high crystallization quality is prepared 2 SnO 4 The monocrystalline film can be used for researching the application of the monocrystalline film in the aspect of semiconductor devices, and is beneficial to expanding Zn 2 SnO 4 Application field of materials. However, the Zn reported so far 2 SnO 4 The preparation method is mainly conventional methods such as conventional solution, sol-gel, sputtering and the like, and the prepared Zn 2 SnO 4 The material is mostly nano or polycrystalline film material, has poor crystallization quality and excessive defects, and limits the materialThe application in the field of transparent semiconductor photoelectric devices.
Patent CN110172733A discloses a high-quality zinc stannate single crystal film and a preparation method thereof, wherein a pulse laser deposition process is adopted to deposit Zn 2 SnO 4 The powder is pressed and formed, and then sintered at high temperature to obtain a ceramic target, a zinc stannate film is grown on a magnesium oxide (MgO) (100) crystal face substrate by pulse laser deposition equipment under vacuum condition, and the film is subjected to heat treatment in air to obtain the zinc stannate single crystal film. However, the average relative transmittance of the zinc stannate single crystal film prepared by the method only reaches 80 percent, and the pulse laser deposition equipment is expensive, the maintenance cost is high, and the instrument structure is complex.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a zinc stannate single crystal film, the average relative transmittance of the zinc stannate single crystal film prepared by the invention in the visible light range exceeds 88 percent, and the crystal growth surface of the zinc stannate single crystal film is Zn 2 SnO 4 (111) The film has complete lattice structure and no twin crystal structure, and is a single crystal epitaxial film, and the epitaxial relationship Zn for film growth 2 SnO 4 (111)//α-Al 2 O 3 (0006) Andthe crystal quality is high, the photoelectric property is excellent, and the adhesion property is good;
the invention also aims to provide a preparation method of the zinc stannate single crystal film, which adopts a magnetron sputtering technology to prepare the zinc stannate single crystal film, has wide material selectivity, high deposition rate, can rapidly prepare the film, and can realize higher atomic deposition energy, thereby obtaining a more uniform and more compact film, and has simple and convenient process, good repeatability and convenient industrialization.
The technical scheme adopted by the invention is as follows:
the preparation method of the zinc stannate single crystal film comprises the following steps:
and C-plane sapphire is selected as a substrate, a zinc stannate film grows on the C-plane sapphire substrate through magnetron sputtering bombardment of a zinc stannate target, and the grown zinc stannate film is annealed to obtain the zinc stannate single crystal film.
The substrate is sapphire (alpha-Al) 2 O 3 ) The (0006) plane of the single crystal, i.e., the C plane.
The zinc stannate target is obtained by mixing zinc oxide and tin dioxide powder, hot-press molding, and sintering in a vacuum hot-press furnace.
The hot pressing pressure is 40-70MPa, the hot pressing time is 4-6min, the sintering temperature is 1100-1300 ℃, the sintering time is 2-4h, and the heat preservation and pressure maintaining are carried out for 5-8 hours.
The magnetron sputtering is carried out in a magnetron sputtering device, and the specific steps are as follows:
(1) Placing a substrate on a sample frame of a sputtering chamber of a magnetron sputtering device, placing a target on a target holder sputtered by the magnetron sputtering device, and adjusting the target spacing and the substrate rotating speed;
(2) Vacuumizing to adjust the pressure of the sputtering chamber: regulating the pressure of the sputtering chamber to be lower than 10 -4 Pa；
(3) Argon is introduced into the sputtering chamber, and the flow of the argon is regulated: opening an argon bottle, and adjusting a knob to the required flow;
(4) And (3) regulating sputtering pressure and sputtering power, starting sputtering, and growing to prepare the zinc stannate film: adjusting the pressure and the power, preheating the cabinet for 5min in advance, and starting the glow sputtering;
(5) And taking out the zinc stannate film sample after sputtering, and closing the instrument.
The magnetron sputtering process conditions are as follows:
the starting sputtering comprises pre-sputtering and formal sputtering; the pre-sputtering time is 10-15min, and the formal sputtering time is 10-35min.
The preparation method of the zinc stannate single crystal film comprises the following steps: putting the zinc stannate film prepared by magnetron sputtering into a muffle furnace for annealing to obtain a zinc stannate monocrystal film;
the annealing temperature is 600-1100 ℃, the annealing time is 1-3h, and the annealing atmosphere is air.
The average relative transmittance of the zinc stannate single crystal film in the visible light range is more than or equal to 88 percent.
Compared with the prior art, the invention has the following beneficial effects:
(1) The zinc stannate single crystal film prepared by the preparation method has the advantages of single crystal structure, complete lattice structure, few defects and no twin crystal structure in the interior, is a single crystal epitaxial film, and has epitaxial relationship Zn for film growth 2 SnO 4 (111)//α-Al 2 O 3 (0006) Andthe crystal quality is high, the average relative transmittance in the visible light range exceeds 88 percent, the photoelectric property is excellent, the adhesion performance is good, and the application prospect is wide;
(2) The preparation method disclosed by the invention has the advantages that the process conditions are easy to accurately control, the operation is simple, the uniformity and the repeatability of the film are good, the process control is easy to realize automation, and the industrialization is convenient;
(3) The magnetron sputtering technology adopted by the invention has larger energy of sputtered particles which can reach tens of electron volts, and can ensure that deposited atoms have enough kinetic energy, so that the binding force of the film and the substrate is better, and the compactness of the film is higher; the sputtering deposition rate is high, and the film can be rapidly prepared; the material has wide selectivity and sputtering range, and can deposit high-melting-point metal, alloy and compound materials; the sputtering deposition of the large-area target material can be realized, and the uniformity of the thin film of the large-size substrate is well controlled.
Drawings
FIG. 1 is an X-ray diffraction chart of a sample obtained by annealing zinc stannate films at different temperatures, wherein the annealing temperatures are 25 ℃ (room temperature), 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃ and 1100 ℃ respectively from bottom to top;
FIG. 2 is an ultraviolet-visible light transmittance spectrum of a sample obtained by annealing a zinc stannate film at different temperatures, wherein annealing temperatures corresponding to spectral lines 1-7 in the figure are 25 ℃ (room temperature), 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃ and 1100 ℃ respectively;
FIG. 3 is a graph of optical band gap versus annealing temperature for samples obtained by annealing zinc stannate films at different temperatures;
FIG. 4 is a phi scan pattern of a sample obtained by annealing a zinc stannate film at 900 ℃;
FIG. 5 is a low resolution transmission electron micrograph (x 36000 times) of a sample of a zinc stannate film annealed at 900 ℃;
FIG. 6 is a high resolution transmission electron micrograph (× 1050000) of a sample of a zinc stannate film annealed at 900 ℃.
Detailed Description
The invention is further illustrated below with reference to examples, which are not intended to limit the practice of the invention.
Example 1
Selecting polished alpha-Al 2 O 3 (0006) The crystal face (C face) is a substrate material, zinc oxide and tin dioxide powder are selected and mixed, hot-press molding is carried out, and then the zinc stannate target is obtained through sintering in a vacuum hot-press furnace, wherein the hot-press pressure is 60MPa, the hot-press time is 5min, the sintering temperature is 1200 ℃, the sintering time is 2h, and the heat preservation and pressure maintaining are carried out for 6 hours. And (3) bombarding the zinc stannate target material by magnetron sputtering to grow a zinc stannate film on the C-face sapphire substrate, and annealing the grown zinc stannate film.
The magnetron sputtering is carried out in a magnetron sputtering device, and the specific steps are as follows:
(1) Placing the C-plane sapphire substrate on a sample frame of a sputtering chamber of a magnetron sputtering device, placing a zinc stannate target on a target holder sputtered by the magnetron sputtering device, adjusting the target spacing to 40mm, and controlling the substrate rotating speed to 15r/min;
(2) Vacuumizing to adjust the pressure of the sputtering chamber: pumping the magnetron sputtering equipment to a high vacuum state, and adjusting the pressure of a sputtering chamber to be 1 multiplied by 10 -4 Pa；
(3) Argon is introduced into the sputtering chamber, and the flow of the argon is regulated: opening an argon bottle valve, setting argon flow to 15sccm, introducing high-purity argon into a vacuum reaction chamber, and keeping until the experiment is finished;
(4) And (3) regulating sputtering pressure and sputtering power, starting sputtering, and growing to prepare the zinc stannate film: adjusting the sputtering pressure to 0.5Pa, sputtering power to 80w, starting the sputtering, pre-sputtering for 10min, and performing formal sputtering for 10min;
(5) And taking out the zinc stannate film sample after sputtering, and closing the instrument.
And (3) placing the zinc stannate film prepared by magnetron sputtering in a muffle furnace, adjusting the annealing temperature to 700 ℃, and the annealing time to 1h, wherein the annealing atmosphere is air atmosphere, so as to obtain a sample.
The prepared sample has a cubic single crystal structure, the optical band gap is 4.03eV, and the average relative transmittance of the sample in the visible light range is 92.5%.
Example 2
Selecting polished alpha-Al 2 O 3 (0006) The crystal face (C face) is a substrate material, zinc oxide and tin dioxide powder are selected and mixed, hot-press molding is carried out, and then the zinc stannate target is obtained through sintering in a vacuum hot-press furnace, wherein the hot-press pressure is 60MPa, the hot-press time is 5min, the sintering temperature is 1200 ℃, the sintering time is 2h, and the heat preservation and pressure maintaining are carried out for 6 hours. And (3) bombarding the zinc stannate target material by magnetron sputtering to grow a zinc stannate film on the C-face sapphire substrate, and annealing the grown zinc stannate film.
The magnetron sputtering is carried out in a magnetron sputtering device, and the specific steps are as follows:
(1) Placing the C-plane sapphire substrate on a sample frame of a sputtering chamber of a magnetron sputtering device, placing a zinc stannate target on a target holder sputtered by the magnetron sputtering device, adjusting the target spacing to 45mm, and controlling the substrate rotating speed to 20r/min;
(2) Vacuumizing to adjust the pressure of the sputtering chamber: pumping the magnetron sputtering equipment to a high vacuum state, and adjusting the pressure of a sputtering chamber to be 5 multiplied by 10 -4 Pa；
(3) Argon is introduced into the sputtering chamber, and the flow of the argon is regulated: opening an argon bottle valve, setting argon flow to 15sccm, introducing high-purity argon into a vacuum reaction chamber, and keeping until the experiment is finished;
(4) And (3) regulating sputtering pressure and sputtering power, starting sputtering, and growing to prepare the zinc stannate film: adjusting the sputtering pressure to 1.5Pa, sputtering power to 110w, starting the sputtering, pre-sputtering for 15min, and performing formal sputtering for 20min;
(5) And taking out the zinc stannate film sample after sputtering, and closing the instrument.
And (3) placing the zinc stannate film prepared by magnetron sputtering in a muffle furnace, adjusting the annealing temperature to 800 ℃, and the annealing time to 1h, wherein the annealing atmosphere is air atmosphere, so as to obtain a sample.
The prepared sample has a cubic single crystal structure, the optical band gap is 4.08eV, and the average relative transmittance of the sample in the visible light range is 88.79%.
Example 3
Selecting polished alpha-Al 2 O 3 (0006) The crystal face (C face) is a substrate material, zinc oxide and tin dioxide powder are selected and mixed, hot-press molding is carried out, and then the zinc stannate target is obtained through sintering in a vacuum hot-press furnace, wherein the hot-press pressure is 60MPa, the hot-press time is 5min, the sintering temperature is 1200 ℃, the sintering time is 2h, and the heat preservation and pressure maintaining are carried out for 6 hours. And (3) bombarding the zinc stannate target material by magnetron sputtering to grow a zinc stannate film on the C-face sapphire substrate, and annealing the grown zinc stannate film.
The magnetron sputtering is carried out in a magnetron sputtering device, and the specific steps are as follows:
(1) Placing the C-plane sapphire substrate on a sample frame of a sputtering chamber of a magnetron sputtering device, placing a zinc stannate target on a target holder sputtered by the magnetron sputtering device, adjusting the target spacing to be 50mm, and controlling the substrate rotating speed to be 20r/min;
(2) Vacuumizing to adjust the pressure of the sputtering chamber: pumping the magnetron sputtering equipment to a high vacuum state, and adjusting the pressure of a sputtering chamber to be 8 multiplied by 10 -4 Pa；
(3) Argon is introduced into the sputtering chamber, and the flow of the argon is regulated: opening an argon bottle valve, setting argon flow to 20sccm, introducing high-purity argon into a vacuum reaction chamber, and keeping until the experiment is finished;
(4) And (3) regulating sputtering pressure and sputtering power, starting sputtering, and growing to prepare the zinc stannate film: adjusting the sputtering pressure to 1Pa, sputtering power to 130w, starting the sputtering, pre-sputtering for 15min, and performing formal sputtering for 15min;
(5) And taking out the zinc stannate film sample after sputtering, and closing the instrument.
And (3) placing the zinc stannate film prepared by magnetron sputtering in a muffle furnace, adjusting the annealing temperature to 900 ℃, and the annealing time to 1h, wherein the annealing atmosphere is air atmosphere, so as to obtain a sample.
The prepared sample has a cubic single crystal structure, the thickness is 426nm, the optical band gap is 4.12eV, and the average relative transmittance of the sample in the visible light range is 86.77%.
Example 4
Selecting polished alpha-Al 2 O 3 (0006) The crystal face (C face) is a substrate material, zinc oxide and tin dioxide powder are selected and mixed, hot-press molding is carried out, and then the zinc stannate target is obtained through sintering in a vacuum hot-press furnace, wherein the hot-press pressure is 60MPa, the hot-press time is 5min, the sintering temperature is 1200 ℃, the sintering time is 2h, and the heat preservation and pressure maintaining are carried out for 6 hours. And (3) bombarding the zinc stannate target material by magnetron sputtering to grow a zinc stannate film on the C-face sapphire substrate, and annealing the grown zinc stannate film.
The magnetron sputtering is carried out in a magnetron sputtering device, and the specific steps are as follows:
(1) Placing the C-plane sapphire substrate on a sample frame of a sputtering chamber of a magnetron sputtering device, placing a zinc stannate target on a target holder sputtered by the magnetron sputtering device, adjusting the target spacing to be 60mm, and controlling the substrate rotating speed to be 25r/min;
(2) Vacuumizing to adjust the pressure of the sputtering chamber: pumping the magnetron sputtering equipment to a high vacuum state, and adjusting the pressure of a sputtering chamber to 9 multiplied by 10 -4 Pa；
(3) Argon is introduced into the sputtering chamber, and the flow of the argon is regulated: opening an argon bottle valve, setting argon flow to be 30sccm, introducing high-purity argon into a vacuum reaction chamber, and keeping until the experiment is finished;
(4) And (3) regulating sputtering pressure and sputtering power, starting sputtering, and growing to prepare the zinc stannate film: adjusting the sputtering pressure to 2Pa, sputtering power to 120w, starting the sputtering, pre-sputtering for 15min, and performing formal sputtering for 35min;
(5) And taking out the zinc stannate film sample after sputtering, and closing the instrument.
And (3) placing the zinc stannate film prepared by magnetron sputtering in a muffle furnace, adjusting the annealing temperature to 1000 ℃, and the annealing time to 1h, wherein the annealing atmosphere is air atmosphere, so as to obtain a sample.
The prepared sample has a cubic single crystal structure, the optical band gap is 4.14eV, and the average relative transmittance of the sample in the visible light range is 89.27%.
Comparative example 1
Selecting polished alpha-Al 2 O 3 (0006) The crystal face (C face) is a substrate material, zinc oxide and tin dioxide powder are selected and mixed, hot-press molding is carried out, and then the zinc stannate target is obtained through sintering in a vacuum hot-press furnace, wherein the hot-press pressure is 60MPa, the hot-press time is 5min, the sintering temperature is 1200 ℃, the sintering time is 2h, and the heat preservation and pressure maintaining are carried out for 6 hours. And (3) bombarding the zinc stannate target material by magnetron sputtering to grow a zinc stannate film on the C-face sapphire substrate, and annealing the grown zinc stannate film.
The magnetron sputtering is carried out in a magnetron sputtering device, and the specific steps are as follows:
(1) Placing the C-plane sapphire substrate on a sample frame of a sputtering chamber of a magnetron sputtering device, placing a zinc stannate target on a target holder sputtered by the magnetron sputtering device, adjusting the target spacing to be 50mm, and controlling the substrate rotating speed to be 20r/min;
(2) Vacuumizing to adjust the pressure of the sputtering chamber: pumping the magnetron sputtering equipment to a high vacuum state, and adjusting the pressure of a sputtering chamber to be 8 multiplied by 10 -4 Pa；
(3) Argon is introduced into the sputtering chamber, and the flow of the argon is regulated: opening an argon bottle valve, setting argon flow to 20sccm, introducing high-purity argon into a vacuum reaction chamber, and keeping until the experiment is finished;
(4) And (3) regulating sputtering pressure and sputtering power, starting sputtering, and growing to prepare the zinc stannate film: adjusting the sputtering pressure to 1Pa, sputtering power to 130w, starting the sputtering, pre-sputtering for 15min, and performing formal sputtering for 15min;
(5) And taking out the zinc stannate film sample after sputtering, and closing the instrument.
And (3) placing the zinc stannate film prepared by magnetron sputtering in a muffle furnace, adjusting the annealing temperature to 25 ℃ (room temperature), and the annealing time to 1h, wherein the annealing atmosphere is air atmosphere, so as to obtain a sample.
The optical band gap of the prepared sample was 3.55eV, and the average relative transmittance of the sample in the visible light range was 85.42%.
Comparative example 2
Selecting polished alpha-Al 2 O 3 (0006) The crystal face (C face) is a substrate material, zinc oxide and tin dioxide powder are selected and mixed, hot-press molding is carried out, and then the zinc stannate target is obtained through sintering in a vacuum hot-press furnace, wherein the hot-press pressure is 60MPa, the hot-press time is 5min, the sintering temperature is 1200 ℃, the sintering time is 2h, and the heat preservation and pressure maintaining are carried out for 6 hours. And (3) bombarding the zinc stannate target material by magnetron sputtering to grow a zinc stannate film on the C-face sapphire substrate, and annealing the grown zinc stannate film.
The magnetron sputtering is carried out in a magnetron sputtering device, and the specific steps are as follows:
(1) Placing the C-plane sapphire substrate on a sample frame of a sputtering chamber of a magnetron sputtering device, placing a zinc stannate target on a target holder sputtered by the magnetron sputtering device, adjusting the target spacing to be 50mm, and controlling the substrate rotating speed to be 20r/min;
(2) Vacuumizing to adjust the pressure of the sputtering chamber: pumping the magnetron sputtering equipment to a high vacuum state, and adjusting the pressure of a sputtering chamber to be 8 multiplied by 10 -4 Pa；
(3) Argon is introduced into the sputtering chamber, and the flow of the argon is regulated: opening an argon bottle valve, setting argon flow to 20sccm, introducing high-purity argon into a vacuum reaction chamber, and keeping until the experiment is finished;
(4) And (3) regulating sputtering pressure and sputtering power, starting sputtering, and growing to prepare the zinc stannate film: adjusting the sputtering pressure to 1Pa, sputtering power to 130w, starting the sputtering, pre-sputtering for 15min, and performing formal sputtering for 15min;
(5) And taking out the zinc stannate film sample after sputtering, and closing the instrument.
And (3) placing the zinc stannate film prepared by magnetron sputtering in a muffle furnace, adjusting the annealing temperature to 600 ℃, and the annealing time to 1h, wherein the annealing atmosphere is air atmosphere, so as to obtain a sample.
The prepared sample has an amorphous structure, the optical band gap is 3.71eV, and the average relative transmittance of the sample in the visible light range is 93.5%.
Comparative example 3
Selecting polished alpha-Al 2 O 3 (0006) The crystal face (C face) is a substrate material, zinc oxide and tin dioxide powder are selected and mixed, hot-press molding is carried out, and then the zinc stannate target is obtained through sintering in a vacuum hot-press furnace, wherein the hot-press pressure is 60MPa, the hot-press time is 5min, the sintering temperature is 1200 ℃, the sintering time is 2h, and the heat preservation and pressure maintaining are carried out for 6 hours. And (3) bombarding the zinc stannate target material by magnetron sputtering to grow a zinc stannate film on the C-face sapphire substrate, and annealing the grown zinc stannate film.
The magnetron sputtering is carried out in a magnetron sputtering device, and the specific steps are as follows:
(1) Placing the C-plane sapphire substrate on a sample frame of a sputtering chamber of a magnetron sputtering device, placing a zinc stannate target on a target holder sputtered by the magnetron sputtering device, adjusting the target spacing to be 50mm, and controlling the substrate rotating speed to be 20r/min;
(2) Vacuumizing to adjust the pressure of the sputtering chamber: pumping the magnetron sputtering equipment to a high vacuum state, and adjusting the pressure of a sputtering chamber to be 8 multiplied by 10 -4 Pa；
(3) Argon is introduced into the sputtering chamber, and the flow of the argon is regulated: opening an argon bottle valve, setting argon flow to 20sccm, introducing high-purity argon into a vacuum reaction chamber, and keeping until the experiment is finished;
(4) And (3) regulating sputtering pressure and sputtering power, starting sputtering, and growing to prepare the zinc stannate film: adjusting the sputtering pressure to 1Pa, sputtering power to 130w, starting the sputtering, pre-sputtering for 15min, and performing formal sputtering for 15min;
(5) And taking out the zinc stannate film sample after sputtering, and closing the instrument.
And (3) placing the zinc stannate film prepared by magnetron sputtering in a muffle furnace, adjusting the annealing temperature to 1100 ℃, and the annealing time to 1h, wherein the annealing atmosphere is air atmosphere, so as to obtain a sample.
The optical band gap of the prepared sample was 4.17eV, and the average relative transmittance of the sample in the visible light range was 85.67%.
The testing method comprises the following steps:
the X-ray diffraction patterns, uv-visible light transmittance spectra, and calculated optical band gaps of the samples prepared in examples 1 to 4 and comparative examples 1 to 3 were measured, and the Φ -scan pattern, the low-resolution transmission electron microscope pattern, and the high-resolution transmission electron microscope pattern of the sample prepared in example 3 were measured, and the results are shown in the accompanying drawings.
As can be seen from fig. 1, when the annealing temperature is less than 600 ℃, no sample peak other than the substrate peak is detected, and the structure is amorphous; with increasing annealing temperature, the sample exhibits cubic Zn at 700-1000 DEG C 2 SnO 4 (111) A single-orientation characteristic diffraction peak is of a single crystal structure; when the annealing temperature was raised to 1100 ℃, the sample turned into a polycrystalline structure. As can be seen from fig. 2, as the annealing temperature increases, the absorption edge of the sample moves in the short wavelength direction, the optical band gap of the sample becomes wider, and the average visible light transmittance of the sample exceeds 90%. As can be seen from fig. 3, the optical bandgap of the sample increases from 3.55 to 4.17eV as the annealing temperature increases. As can be seen from FIG. 4, the obtained zinc stannate single crystal film has a single crystal structure, a complete lattice structure and no twin crystal structure inside, and is a single crystal epitaxial film, and the epitaxial relationship Zn of film growth 2 SnO 4 (111)//α-Al 2 O 3 (0006) Andas can be seen from FIG. 5, the thickness of the zinc stannate single crystal film obtained by annealing the zinc stannate film at 900℃was 426nm. As can be seen from fig. 6, the zinc stannate single crystal film obtained by annealing the zinc stannate film at 900 ℃ has a cubic zinc stannate single crystal structure.
Claims (9)
1. A preparation method of a zinc stannate single crystal film is characterized by comprising the following steps:
and C-plane sapphire is selected as a substrate, a zinc stannate film grows on the C-plane sapphire substrate through magnetron sputtering bombardment of a zinc stannate target, and the grown zinc stannate film is annealed to obtain the zinc stannate single crystal film.
2. The method for producing a zinc stannate single crystal film according to claim 1, wherein the substrate is sapphire (α -Al 2 O 3 ) The (0006) plane of the single crystal, i.e., the C plane.
3. The method for preparing the zinc stannate single crystal film according to claim 1, wherein the magnetron sputtering is performed in a magnetron sputtering device, and comprises the following specific steps: placing a substrate on a sample frame of a sputtering chamber of a magnetron sputtering device, placing a target on a target holder of the sputtering chamber of the magnetron sputtering device, adjusting the distance between the targets and the rotation speed of the substrate, vacuumizing to adjust the pressure of the sputtering chamber, introducing argon into the sputtering chamber, adjusting the flow, the sputtering pressure and the sputtering power of the argon, starting up the sputtering, and growing to prepare the zinc stannate film.
4. The method for preparing a zinc stannate single crystal film according to claim 3, wherein the process conditions of the magnetron sputtering are as follows:
5. the method for producing a zinc stannate single crystal film according to claim 3, wherein the starting sputtering includes pre-sputtering and main sputtering; the pre-sputtering time is 10-15min, and the formal sputtering time is 10-35min.
6. The method for preparing a zinc stannate single crystal film according to claim 1, wherein zinc oxide and tin dioxide powder for zinc stannate targets are mixed, hot-pressed and molded, and sintered in a vacuum hot-pressing furnace.
7. The method for preparing a zinc stannate single crystal film according to claim 6, wherein the hot pressing pressure is 40-70MPa, the hot pressing time is 4-6min, the sintering temperature is 1100-1300 ℃, the sintering time is 2-4h, and the heat preservation and pressure maintaining are carried out for 5-8 hours.
8. The method for producing a zinc stannate single crystal film according to claim 1, wherein the annealing temperature is 600-1100 ℃, the annealing time is 1-3 hours, and the annealing atmosphere is air.
9. A zinc stannate single crystal film prepared by the preparation method of any one of claims 1-8, which is characterized in that the average relative transmittance of the zinc stannate single crystal film in the visible light range is more than or equal to 88%.
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