CN115573036B - High-kappa layered bismuth oxyselenite dielectric material and preparation method and application thereof - Google Patents
High-kappa layered bismuth oxyselenite dielectric material and preparation method and application thereof Download PDFInfo
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- 239000003989 dielectric material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229910052797 bismuth Inorganic materials 0.000 title description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title description 5
- 239000013078 crystal Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000010453 quartz Substances 0.000 claims abstract description 18
- 239000002135 nanosheet Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 11
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 9
- 239000013590 bulk material Substances 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 238000000137 annealing Methods 0.000 claims description 11
- 239000002390 adhesive tape Substances 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000003776 cleavage reaction Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 230000007017 scission Effects 0.000 claims description 5
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 3
- 230000005669 field effect Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000012159 carrier gas Substances 0.000 claims description 2
- 238000005229 chemical vapour deposition Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- 238000005538 encapsulation Methods 0.000 claims 1
- 238000007789 sealing Methods 0.000 abstract description 4
- 238000005086 pumping Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 10
- 239000002064 nanoplatelet Substances 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 238000000089 atomic force micrograph Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000004098 selected area electron diffraction Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Classifications
-
- 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
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
-
- 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
- C30B28/00—Production of homogeneous polycrystalline material with defined structure
- C30B28/02—Production of homogeneous polycrystalline material with defined structure directly from the solid state
-
- 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
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/64—Flat crystals, e.g. plates, strips or discs
-
- 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
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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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
- H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
- H01L29/51—Insulating materials associated therewith
- H01L29/517—Insulating materials associated therewith the insulating material comprising a metallic compound, e.g. metal oxide, metal silicate
Abstract
The invention discloses a high-kappa layered Bi 2 SeO 5 A dielectric material and a method for preparing the same. The layered Bi 2 SeO 5 The preparation method of the dielectric material comprises the following steps: bi is used as 2 O 3 Powder and SeO 2 Taking the powder as a raw material, carrying out high-temperature solid-phase reaction in a vacuum-pumping quartz tube, and obtaining the layered Bi after the reaction is finished 2 SeO 5 High purity powder. Bi obtained by the reaction 2 SeO 5 Taking out the powder, grinding, secondarily sealing in a quartz tube for chemical vapor transport, and obtaining the layered Bi after the reaction is finished 2 SeO 5 Monocrystalline bulk material. The method is simple and feasible, and the obtained Bi 2 SeO 5 The dielectric material single crystal block has large size and is easy to cleave into large-area nano sheets, and has wide application prospect.
Description
Technical Field
The invention belongs to the field of dielectric materials, and particularly relates to a high-k (k, namely relative dielectric constant) layered bismuth oxyselenite dielectric material, and a preparation method and application thereof.
Background
The two-dimensional layered material layer has strong chemical bonding, weak interaction between layers, and obvious bonding anisotropy. The surface of the two-dimensional material has no dangling bond, has natural thickness advantage and flexibility, and has wide application in the fields of electronic devices, photoelectric devices and energy catalysis. Bismuth oxyselenite (Bi) 2 SeO 5 ) Belongs to an orthorhombic system Z=8) is a two-dimensional layered structure stacked layer by layer along the a direction. Two-dimensional semiconductor Bi by Tianran Li and Teng Tu et al 2 O 2 Polycrystalline and amorphous Bi obtained by in situ oxidation of Se 2 SeO 5 The electric transport research of the (C) shows that the (C) has higher dielectric constant, and the dielectric constant is higher than 20, and belongs to a high-kappa dielectric material. Meanwhile, related theoretical calculation shows that Bi 2 SeO 5 Has larger bulk band gap (-3.9 eV), belonging to direct band gap. Therefore, bi 2 SeO 5 Is a potential high-k insulating dielectric material and can be applied to the fields of high-performance field effect transistors, logic devices and the like.
In the current gate dielectric material, hfO 2 、Al 2 O 3 The equal-height kappa medium belongs to bulk gate dielectric materials, and when a suspension bond existing on the surface of the equal-height kappa medium is combined with a two-dimensional semiconductor material, the equal-height kappa medium can influence the performance of the material, so that the mobility of the material is reduced. The two-dimensional dielectric material without dangling bonds on the surface can effectively solve the problem, but the existing two-dimensional layered dielectric material is very few, wherein the typical materials are hexagonal boron nitride (h-BN) and MoO 3 And V 2 O 5 Etc. h-BN is the only widely used two-dimensional dielectric material at present, but has smaller relative dielectric constant (3-4) and limited regulation capability on a semiconductor channel. High-kappa MoO 3 (. About.3.0 eV) and V 2 O 5 The (-2.8 eV) band gap is smaller, and when matched with semiconductor material, the delta E of the gate dielectric and the semiconductor channel is harder to meet C And deltaev exceeding the requirement of 1Ev may result in a larger gate leakage current.
Thus, the controlled synthesis of high- κ two-dimensional layered dielectric materials is a key and bottleneck problem for device scaling in the latter molar age. So far, the high-kappa two-dimensional layered material which can be widely used as a gate dielectric and a packaging layer for a nano device has not been reported yet, and it is important to find a high-kappa two-dimensional layered material with universality.
Disclosure of Invention
The invention aims to provide a high-kappa layered bismuth oxyselenite dielectric material and a preparation method thereof.
The invention provides layered Bi 2 SeO 5 The preparation method of the dielectric material comprises the following steps:
1) Bi is used as 2 O 3 Powder and SeO 2 Taking the powder as a raw material, carrying out high-temperature solid-phase reaction, and obtaining the layered Bi after the reaction is finished 2 SeO 5 High-purity powder;
2) The Bi is subjected to 2 SeO 5 Grinding the high-purity powder into Bi 2 SeO 5 Powder, add transport agent I 2 The crystal is evenly mixed and then grows Bi by a chemical vapor transport method 2 SeO 5 A bulk single crystal; after the growth is completed, annealing to remove the surface residue I 2 Obtaining the layered Bi 2 SeO 5 Monocrystalline bulk material.
In the above method step 1), the Bi 2 O 3 Powder and SeO 2 The molar ratio of the powder is 1:1.
in the step 1) of the method, the reaction temperature of the high-temperature solid phase reaction is 550-890 ℃, and can be 600 ℃, 800 ℃ or 850 ℃; the reaction time is 6 to 36 hours, and may be specifically 6, 12 or 24 hours.
In the step 1) of the method, the high-temperature solid-phase reaction is specifically carried out in a sealed quartz tube which is vacuumized;
more specifically, the bottom of the evacuated sealed quartz tube is positioned at the center of the tube furnace with a temperature gradient.
The length of a temperature zone with a temperature gradient on one side of the tube furnace is 15cm, and the length of a sealed quartz tube part is 13cm.
The method further comprises the following steps after the step 1) and before the step 2): and naturally cooling the system to room temperature after the high-temperature solid-phase reaction step.
In the above method step 2), the Bi 2 SeO 5 Powder and transport agent I 2 The mass ratio of the single crystal is 1: 0.005-0.02, withThe body can be 1:0.005, 1:0.01 or 1:0.015.
in the step 2), the reaction temperature of the chemical vapor transport method is 800-890 ℃, specifically 800 ℃, 850 ℃, 870 ℃ or 890 ℃; the reaction time is 1 to 60 days, and may be specifically 20, 40, 45 or 60 days.
In the method step 2), bi is reacted with 2 SeO 5 The particle size of the powder is not critical, and is usually 20 μm or less.
In the step 2), the chemical vapor transport method is specifically performed in a vacuum-pumped sealed quartz tube;
more specifically, the bottom of the evacuated sealed quartz tube is positioned at the center of the tube furnace with a temperature gradient.
The length of a temperature zone with a temperature gradient on one side of the tube furnace is 15cm, and the length of a sealed quartz tube part is 13cm.
The method in step 2) further comprises the following steps: and naturally cooling the system to room temperature after the chemical vapor transport method.
FIG. 1 shows the growth of Bi according to the present invention 2 SeO 5 Schematic diagram of bulk single crystal process.
In the method step 2), the annealing step is specifically performed in a chemical vapor deposition system configured with a low-pressure system;
in the annealing step, the carrier gas is argon; the flow rate of the argon is 50-200 standard milliliters/min, and can be specifically 50, 100 and 150 standard milliliters/min;
the system pressure is not additionally arranged, and the final balance pressure is determined by the argon flow rate;
the annealing temperature may be 80-120 ℃, and specifically may be 80 ℃, 100 ℃ or 120 ℃.
The annealing time may be 30 to 120 minutes, and may be specifically 30, 60 or 90 minutes.
The method further comprises the following steps: for the layered Bi 2 SeO 5 The single crystal block material is mechanically cleaved to obtain Bi 2 SeO 5 And a step of two-dimensional nano-sheets.
The mechanical cleavage step toolMechanical cleavage of Bi by using tape 2 SeO 5 Attaching the monocrystalline block material on a substrate;
in the mechanical cleavage step, the adhesive tape is a scotch adhesive tape, a blue film adhesive tape, etc., specifically, may be a scotch 600, a scotch 610, or a blue film 1007R;
the adhesive tape is adhered to and separated for 1 to 15 times, and can be 1, 7 or 10 times in particular;
the laminating time on the substrate is 1-60 minutes, and can be 1, 10 or 30 minutes;
the heating temperature is room temperature-100 ℃ during bonding, and can be specifically room temperature, 50 ℃ or 80 ℃;
the substrate is 300nm SiO 2 a/Si substrate, a fused silica substrate, etc.
In addition, the layered Bi prepared by the above method 2 SeO 5 Dielectric material and layered Bi thereof 2 SeO 5 The dielectric material is used as a packaging layer and a gate dielectric layer to be applied to field effect transistors, logic devices, hall devices and the like, and also belongs to the protection scope of the invention.
The layered Bi 2 SeO 5 The dielectric material can have a dielectric constant of, in particular, 16 and a maximum breakdown field strength of, in particular, 30MV/cm at room temperature.
The invention provides a chemical vapor transport synthesis method for high-kappa layered Bi 2 SeO 5 A method for preparing a dielectric material. The method is simple and feasible, and the obtained Bi 2 SeO 5 The dielectric material single crystal block has large size and is easy to be cleaved into large-area nano sheets, and has wide application prospect.
Drawings
FIG. 1 shows the growth of Bi according to the present invention 2 SeO 5 Schematic diagram of bulk single crystal process;
FIG. 2 shows a layered Bi according to the present invention 2 SeO 5 A crystal structure diagram of (2);
FIG. 3 is a layered Bi obtained in example 1 of the present invention 2 SeO 5 Macroscopic crystal pictures of single crystal bulk;
FIG. 4 shows the layered Bi obtained in example 1 of the present invention 2 SeO 5 Typical X-ray diffraction number of single crystal bulkAccording to the above;
FIG. 5 shows the layered Bi obtained in example 1 of the present invention 2 SeO 5 Scanning electron microscope pictures after single crystal block bending;
FIG. 6 is a two-dimensional Bi obtained in example 2 of the present invention 2 SeO 5 Optical microscope photograph of the nanoplatelets;
FIG. 7 is a two-dimensional Bi obtained in example 2 of the present invention 2 SeO 5 Optical microscope pictures of the nano-sheets and corresponding atomic force microscope images;
FIG. 8 is a two-dimensional Bi obtained in example 2 of the present invention 2 SeO 5 Scanning transmission electron microscope-high angle annular dark field (STEM-HAADF) low resolution, selected area electron diffraction and high resolution images after the nano-sheets are transferred to the transmission carrier net;
FIG. 9 is a two-dimensional Bi obtained in example 2 of the present invention 2 SeO 5 A typical polarization charge versus voltage curve for a nanoplatelet;
FIG. 10 is a two-dimensional Bi obtained in example 2 of the present invention 2 SeO 5 A current density profile of the nanoplatelets as a function of voltage (and electric field strength);
FIG. 11 is a two-dimensional Bi obtained in example 3 of the present invention 2 SeO 5 Optical microscopy photographs of nanoplatelets and corresponding atomic force microscopy images.
Detailed Description
The invention will be further illustrated with reference to the following specific examples, but the invention is not limited to the following examples. The methods are conventional methods unless otherwise specified. The starting materials are available from published commercial sources unless otherwise specified.
Example 1
Weigh 6.9894 grams of Bi 2 O 3 Powder and 1.6644 g SeO 2 Powder (molar ratio 1:1), and placing the powder at the bottom of a quartz tube with the outer diameter of 15mm and the length of 25cm and the bottom end seal after uniformly mixing the powder. Then, a self-built tube sealing system is adopted, vacuumizing is carried out, argon is introduced, then gas washing is carried out, the operation is repeated for 2-3 times, the system pressure is maintained to be less than 5Pa, and a high-temperature oxyhydrogen flame is used for sealing a place 13cm away from the bottom of the quartz tube. Placing quartz tube in tubeHeating in a furnace, wherein the reaction temperature is 850 ℃, the reaction time is 12h, and naturally cooling to room temperature after the reaction is finished. Bi obtained by the reaction 2 SeO 5 Taking out the powder, grinding into powder, taking 8.0g Bi 2 SeO 5 Powder and 0.04g I 2 After mixing uniformly, the mixture was placed at the bottom of a quartz tube having an outer diameter of one inch and a length of 25cm, and the previous tube sealing step was repeated. Heating the quartz tube in a tube furnace at 870 ℃ for 45 days, and naturally cooling to room temperature after the reaction is finished. Bi is mixed with 2 SeO 5 The single crystal block is taken out from the quartz tube and heated to 100 ℃ for annealing for 1h in argon with the flow rate of 50 standard milliliters per minute, and the layered Bi provided by the invention is obtained 2 SeO 5 Monocrystalline bulk material.
FIG. 2 shows the layered Bi obtained in this example 2 SeO 5 Crystal structure diagram of dielectric material; from the figure, bi 2 SeO 5 Is a two-dimensional layered material which is stacked layer by layer along the direction a;
FIG. 3 shows the layered Bi obtained in this example 2 SeO 5 Macroscopic crystal pictures of single crystal bulk; as can be seen from the figure, the layered Bi obtained 2 SeO 5 The growth of the single crystal bulk material shows anisotropy, the shape is rectangle, and the crystal size is about 0.5 cm to 2.0 cm;
FIG. 4 shows the layered Bi obtained in this example 2 SeO 5 Typical X-ray diffraction data for single crystal bulk; as can be seen from the figure, the Bi was obtained 2 SeO 5 The dielectric material has high crystallization quality, and the display (100) crystal face group proves that the interlayer direction is a direction;
FIG. 5 shows the layered Bi obtained in this example 2 SeO 5 Scanning electron microscope pictures after single crystal block bending; as can be seen from the figure, bi was obtained 2 SeO 5 The dielectric material is layered and has a certain flexibility.
Example 2
Taking Bi obtained in example 1 2 SeO 5 The single crystal block material is stuck on a blue film adhesive tape, repeatedly stuck-torn, repeatedly repeated for 8 times, stuck on 300nm SiO at room temperature 2 The Si substrate is peeled off after 20 minutes, i.e. on the substrateObtaining two-dimensional Bi 2 SeO 5 A nano-sheet.
FIG. 6 is a two-dimensional Bi obtained in example 2 of the present invention 2 SeO 5 Optical microscope photograph of the nanoplatelets; from the figure, the two-dimensional Bi was obtained 2 SeO 5 The maximum domain size of the nanoplatelets is greater than 100 microns;
FIG. 7 is a two-dimensional Bi obtained in example 2 of the present invention 2 SeO 5 Optical microscope pictures of the nano-sheets and corresponding atomic force microscope images; from the figure, the two-dimensional Bi was obtained 2 SeO 5 The step height of the nano sheet is 1.1nm and 2.2nm, and the nano sheet is equal to Bi 2 SeO 5 The single-layer step is matched with the double-layer step in height;
FIG. 8 is a two-dimensional Bi obtained in this example 2 SeO 5 Scanning transmission electron microscope-high angle annular dark field (STEM-HAADF) low resolution, selected area electron diffraction and high resolution images after the nano-sheets are transferred to the transmission carrier net; as can be seen from the figure, bi was obtained 2 SeO 5 The crystallinity of the two-dimensional crystal is very good, wherein the high resolution STEM-HAADF image givesAnd->Is respectively with Bi 2 SeO 5 Theoretical values of b and c lengths in Crystal unit cell +.>Consistent;
FIG. 9 is a two-dimensional Bi obtained in this example 2 SeO 5 A typical polarization charge versus voltage curve for a nanoplatelet; in the illustration, the thickness of the nano-sheet is 35.1nm, and the electrode area is 158 mu m 2 From the formula(C is capacitance, A is electrode plate area, ε) 0 For vacuum dielectric constant, ε r Relative permittivity, d is the thickness of the sample), the two-dimensional Bi obtained 2 SeO 5 The dielectric constant of the nano-sheet at room temperature can reach 15.5.
FIG. 10 is a two-dimensional Bi obtained in this example 2 SeO 5 A current density profile of the nanoplatelets as a function of voltage (and electric field strength); from the figure, the two-dimensional Bi was obtained 2 SeO 5 The breakdown field intensity of the nano sheet can reach 30MV/cm.
Example 3
Taking Bi obtained in example 1 2 SeO 5 The single crystal block material is stuck on a blue film adhesive tape, repeatedly stuck-torn, repeatedly repeated 11 times, stuck on 300nm SiO at room temperature 2 The Si substrate is peeled off after 60 minutes, that is, two-dimensional Bi is obtained on the substrate 2 SeO 5 A nano-sheet.
FIG. 11 is a two-dimensional Bi obtained in this example 2 SeO 5 Optical microscope pictures of the nano-sheets and corresponding atomic force microscope images; from the figure, the two-dimensional Bi was obtained 2 SeO 5 The nanoplatelets can be as thin as a monolayer.
Claims (10)
1. Layered Bi 2 SeO 5 The preparation method of the dielectric material comprises the following steps:
1) Bi is used as 2 O 3 Powder and SeO 2 Taking the powder as a raw material, carrying out high-temperature solid-phase reaction, and obtaining the layered Bi after the reaction is finished 2 SeO 5 Powder;
2) The Bi is subjected to 2 SeO 5 Grinding the powder into Bi 2 SeO 5 Powder, add transport agent I 2 The crystal is evenly mixed and then grows Bi by a chemical vapor transport method 2 SeO 5 A bulk single crystal; after the growth is completed, annealing to remove the surface residue I 2 Obtaining the layered Bi 2 SeO 5 A dielectric material; the layered Bi 2 SeO 5 The dielectric material is layered Bi 2 SeO 5 Monocrystalline bulk material;
in the step 1), the Bi 2 O 3 Powder and SeO 2 The molar ratio of the powder is 1:1, a step of;
in the step 1), the reaction temperature of the high-temperature solid phase reaction is 550-890 ℃; the reaction time is 6-36 hours;
in the step 2), the Bi 2 SeO 5 Powder and transport agent I 2 The mass ratio of the single crystal is 1: 0.005-0.02;
in the step 2), the reaction temperature of the chemical vapor transport method is 800-890 ℃; the reaction time is 1-60 days;
in the step 2), the annealing temperature is 80-120 ℃ and the annealing time is 30-120 minutes.
2. The method of manufacturing according to claim 1, characterized in that: in the step 1), the high-temperature solid-phase reaction is carried out in a sealed quartz tube which is vacuumized;
the method further comprises the following steps after the step 1) and before the step 2): and naturally cooling the system to room temperature after the high-temperature solid-phase reaction step.
3. The preparation method according to claim 2, characterized in that: in the step 1), the bottom of the vacuumized sealed quartz tube is positioned at the center of the tube furnace with the temperature gradient.
4. The method of manufacturing according to claim 1, characterized in that: in the step 2), the chemical vapor transport method is performed in a sealed quartz tube which is vacuumized;
the step 2) further comprises the following steps: and naturally cooling the system to room temperature after the chemical vapor transport method.
5. The method of manufacturing according to claim 4, wherein: in the step 2), the bottom of the vacuumized sealed quartz tube is positioned at the center of the tube furnace with the temperature gradient.
6. The method of manufacturing according to claim 1, characterized in that: in the step 2), the annealing is performed in a chemical vapor deposition system configured with a low-pressure system;
in the annealing, the carrier gas is argon; the flow rate of the argon is 50-200 standard milliliters/minute.
7. The method of manufacturing according to claim 1, characterized in that: the method further comprises the steps of: for the layered Bi 2 SeO 5 The single crystal bulk material is mechanically cleaved to obtain layered Bi 2 SeO 5 A step of dielectric material, the layered Bi 2 SeO 5 The dielectric material is two-dimensional Bi 2 SeO 5 A nano-sheet.
8. The method of manufacturing according to claim 7, wherein: the mechanical cleavage mechanically cleaves Bi by using tape 2 SeO 5 Attaching the monocrystalline block material on a substrate;
in the mechanical cleavage step, the adhesive tape is a scotch adhesive tape or a blue film adhesive tape;
the opposite sticking-separating times of the adhesive tape are 1-15 times;
attaching the substrate for 1-60 minutes; the heating temperature is room temperature-100 ℃ during bonding.
9. The layered Bi prepared by the method of any one of claims 1 to 8 2 SeO 5 A dielectric material.
10. The layered Bi of claim 9 2 SeO 5 Use of a dielectric material as an encapsulation layer or gate dielectric layer in the preparation of a device comprising: field effect transistors, logic devices, hall devices.
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