CN117468095A - Ternary layered telluride and preparation method of single crystal thereof - Google Patents
Ternary layered telluride and preparation method of single crystal thereof Download PDFInfo
- Publication number
- CN117468095A CN117468095A CN202311397754.0A CN202311397754A CN117468095A CN 117468095 A CN117468095 A CN 117468095A CN 202311397754 A CN202311397754 A CN 202311397754A CN 117468095 A CN117468095 A CN 117468095A
- Authority
- CN
- China
- Prior art keywords
- temperature
- telluride
- powder
- ternary layered
- single crystal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000013078 crystal Substances 0.000 title claims abstract description 93
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 66
- 239000000126 substance Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000011651 chromium Substances 0.000 claims description 47
- 239000010453 quartz Substances 0.000 claims description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 36
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 34
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 34
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 34
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 24
- 239000011630 iodine Substances 0.000 claims description 24
- 229910052740 iodine Inorganic materials 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000007789 sealing Methods 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 238000004321 preservation Methods 0.000 claims description 11
- 238000010304 firing Methods 0.000 claims description 10
- 238000004806 packaging method and process Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 5
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical group Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 claims description 2
- 239000010410 layer Substances 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 239000002356 single layer Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 16
- 230000003287 optical effect Effects 0.000 description 13
- 229910052804 chromium Inorganic materials 0.000 description 6
- 229910052715 tantalum Inorganic materials 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 230000036632 reaction speed Effects 0.000 description 3
- 238000003746 solid phase reaction Methods 0.000 description 3
- 229910052714 tellurium Inorganic materials 0.000 description 3
- -1 transition metal chalcogenide Chemical class 0.000 description 3
- 230000005355 Hall effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention discloses a preparation method of a ternary layered telluride and a single crystal thereof, and relates to the technical field of layered single crystal materials, wherein the chemical general formula of the ternary layered telluride is as follows: ta 1‑x Cr 1+x Te 4 Wherein, -0.1 is less than or equal to x is less than or equal to 0.3. The ternary layered telluride has semiconductor characteristics and can be used in the technical field of nano electronic devices. The Ta 1‑x Cr 1+x Te 4 The crystal is prepared by a chemical vapor transport method, is a ternary layered massive crystal with large size and high quality, is convenient to obtain a few-layer or single-layer material by a mechanical stripping method, and can be widely applied to functional devices.
Description
Technical Field
The invention relates to the technical field of layered single crystal materials, in particular to a ternary layered telluride and a preparation method of a single crystal thereof.
Background
The transition metal chalcogenide with the layered structure has very rich types and shows a plurality of novel physical properties, and has good application prospects in the fields of field effect transistors, optoelectronic devices, photoelectric detectors, photoelectrocatalysis, batteries and the like. In particular, compared with binary transition metal chalcogenides, ternary layered structure transition metal chalcogenides can effectively regulate and control the band gap structure, crystal structure and functional characteristics of materials by changing the types and stoichiometric ratio of transition metals, so that the materials are widely focused in the aspects of performance research and potential application.
Wherein MM' Te 4 (m=nb, ta; M' =ir, rh, os, fe, ru, cr) is a type of multifunctional ternary layered telluride. In the system, the structural symmetry characteristic of the material is easy to cause the appearance of a Weyl node, and the material has novel properties such as in-plane strong anisotropy, room temperature third-order nonlinear Hall effect, nonlinear optical response and the like. Therefore, in the fields of photoelectric detection, hall effect and other devices, ternary layered telluride MM' Te 4 Has good application potential.
Seeking MM' Te 4 The new compound existing in the system further enriches the material types in the system, and has positive promotion effect on the possible new physical properties in the system. Since the performance and application of the series of compounds are studied, a large-size high-quality novel compound single crystal material needs to be obtained first, and therefore, how to obtain large-size high-quality MM' Te 4 The preparation of single crystals has important significance for researching the intrinsic physical properties of materials and further promoting the application of the materials in the field of nano photoelectric devices. In the prior material, no ternary lamellar telluride with Ta and Cr M is reported, and ternary lamellar MM' Te with Ta and Cr M cannot be obtained by a conventional solid phase reaction method 4 Ternary layered MM ' Te with M being Ta, M ' being Cr, and the number of atoms of M, M ' and 2 has not been reported for telluride crystals 4 The telluride crystals, which results in performance studies on this ternary layered telluride, are not feasible. Thus, the preparation technology is improved and large-size and high-quality TaCrTe is obtained 4 Single crystals are particularly important for material property research and functional device fabrication.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide a ternary layered telluride and a preparation method of a single crystal thereof, and aims to solve the problem that a ternary layered telluride single crystal containing Ta and Cr elements does not exist in the prior art.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a ternary layered telluride, wherein the ternary layered telluride has the chemical formula: ta 1-x Cr 1+x Te 4 Wherein, -0.1 is less than or equal to x is less than or equal to 0.3.
In the ternary layered telluride, the Ta 1-x Cr 1+x Te 4 Is of rhombic structure, and the space group is
A method for producing a ternary layered telluride single crystal as described above, comprising the steps of:
step S1, batching and packaging: mixing tantalum powder, chromium powder and tellurium powder according to a proportion, placing the mixture into a quartz tube, adding iodine particles, vacuumizing, and sealing the quartz tube;
step S2, firing: placing the sealed quartz tube in a double-temperature-zone tube furnace, positioning one end with materials at the high-temperature-zone end of the double-temperature-zone tube furnace, positioning one end without materials at the low-temperature-zone end of the double-temperature-zone tube furnace, heating at a speed of 2-5 ℃/min, enabling the temperature of the low-temperature-zone end to be 575-625 ℃, enabling the temperature of the high-temperature-zone end to be 675-725 ℃, and preserving heat for 7-10 days; after the heat preservation is finished, cooling to room temperature, and cleaning and drying to obtain ternary lamellar telluride Ta 1-x Cr 1+x Te 4 。
In the preparation method of the ternary layered telluride, the mole ratio of the tantalum powder to the chromium powder to the tellurium powder is (1-x): (1+x): 4.
In the preparation method of the ternary layered telluride single crystal, the purity of the tantalum powder, the chromium powder and the tellurium powder is more than or equal to 99.99 percent.
In the preparation method of the ternary layered telluride single crystal, the molar ratio of the tantalum powder to the chromium powder to the tellurium powder is 1:1:4, and the molecular formula of the ternary layered telluride prepared is TaCrTe 4 。
In the preparation method of the ternary layered telluride single crystal, the heat preservation time is 7 days.
In the preparation method of the ternary layered telluride single crystal, the adding amount of the iodine particles is 5mg/mL.
In the preparation method of the ternary layered telluride single crystal, the cleaning step is to clean with alcohol.
In the preparation method of the ternary layered telluride single crystal, the vacuum degree in the quartz tube after vacuumizing is less than or equal to 1Pa.
The beneficial effects are that:
the invention provides a preparation method of a ternary layered telluride and a monocrystal thereof, wherein the chemical general formula of the ternary layered telluride is as follows: ta 1-x Cr 1+x Te 4 Wherein, -0.1 is less than or equal to x is less than or equal to 0.3, has the semiconductor conductive characteristic, and can be used in the technical field of nano electronic devices. The Ta 1-x Cr 1+x Te 4 The crystal is prepared into a layered large-size and high-quality blocky crystal by a chemical vapor transport method, so that a few-layer or single-layer material can be conveniently obtained by a mechanical stripping method, and the ternary layered Ta can be conveniently studied deeply 1-x Cr 1+x Te 4 Performance and use of telluride.
Drawings
FIG. 1 shows TaCrTe 4 A block crystal image taken by an optical microscope of the crystal.
FIG. 2 is TaCrTe 4 X-ray diffraction pattern of the crystal.
FIG. 3 is TaCrTe 4 X-ray diffraction pattern of powder.
FIG. 4 is TaCrTe 4 Energy spectrum of single crystal.
FIG. 5 is TaCrTe 4 Surface topography of single crystals.
FIG. 6 is a physical diagram of the material prepared in comparative example 1.
FIG. 7 is an X-ray diffraction pattern of the material prepared in comparative example 2.
Detailed Description
The invention provides a preparation method of ternary layered telluride and a monocrystal thereof, which aims to make the purposes, technical schemes and effects of the invention clearer and more definite, and the invention is further described in detail in the following examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The first aspect of the invention provides a ternary layered telluride prepared by a chemical vapor transport method, which has a chemical general formula: ta 1-x Cr 1+x Te 4 Wherein, -0.1.ltoreq.x.ltoreq.0.3, the Ta 1-x Cr 1+x Te 4 Is of rhombohedral structure, the space group is. Due to the Ta 1-x Cr 1+x Te 4 The crystal is ternary telluride with a layered structure and has semiconductor characteristics, so that the crystal can be used for nano electronic device materials.
The second aspect of the invention also provides a ternary layered Ta 1-x Cr 1+x Te 4 The preparation method of single crystal is chemical gas phase transport method, which uses tantalum powder, chromium powder and tellurium powder as raw materials, iodine particles as transport agent, and carries out transport growth in a double temperature zone to obtain large-size high-quality bulk crystal with layered structure, thereby solving the problem that TaCrTe can not be prepared by conventional solid phase reaction method 4 Technical problems of (2). The bulk crystal with the large-size lamellar structure is convenient for obtaining a sample with a few layers by a mechanical stripping method, so that the performance of the bulk crystal is convenient to study and the application of the bulk crystal in the aspect of functional devices is expanded.
Specifically, the ternary layered telluride Ta 1-x Cr 1+x Te 4 The preparation method of the single crystal comprises the following steps:
step S1, batching and packaging: according to the general formula Ta 1-x Cr 1+x Te 4 Mixing tantalum powder, chromium powder and tellurium powder according to the proportion, placing the materials into a quartz tube, adding iodine particles, vacuumizing to ensure that the vacuum degree in the quartz tube is less than or equal to 1Pa, and sealing the quartz tube by flame sealing equipment or a device; step S2, firing: the sealed quartz tube is horizontally arranged in a tube furnace with double temperature areas, so that one end with materials is positioned at double temperatureThe high temperature area end of the tube furnace, the end without material is positioned at the low temperature area end of the tube furnace with double temperature areas, the temperature is raised at the speed of 2-5 ℃/min, the temperature in the low temperature area is 575-625 ℃, the temperature in the high temperature area is 675-725 ℃, and the temperature is kept for 7-10 days; cooling to room temperature after heat preservation, placing the crystal obtained by the reaction in alcohol for cleaning for multiple times, removing iodine in the crystal, and drying after cleaning to obtain Ta with ternary lamellar structure 1-x Cr 1+ x Te 4 And (5) a crystal.
Through the preparation method, ta with a ternary lamellar structure can be prepared 1-x Cr 1+x Te 4 And (3) single crystals. In the preparation method, the temperature at two ends of the quartz tube can be different by adopting a tube furnace with double temperature areas, tantalum, chromium and tellurium can be brought to a low temperature area by the transportation effect of iodine, and the tantalum, the chromium and the tellurium react in the low temperature area to form high-quality massive ternary lamellar Ta 1-x Cr 1+x Te 4 The size of the single crystal can reach 10mm, so that a large-size crystal material can be provided for subsequent performance research, and the problem that Ta cannot be obtained by conventional solid phase reaction in the prior art is solved 1-x Cr 1+x Te 4 Materials, which lead to the defect that the performance and the functionality of the materials cannot be researched.
To obtain a compound of the general chemical formula Ta 1-x Cr 1+x Te 4 The amounts of tantalum powder, chromium powder and tellurium powder need to be controlled in the preparation process. In the preparation method, the corresponding ternary lamellar telluride crystal can be obtained by limiting the mole ratio of tantalum powder, chromium powder and tellurium powder to (1-x): (1+x): 4. For example, when the target product is TaCrTe 4 When the crystal is prepared, controlling the mole ratio of tantalum powder, chromium powder and tellurium powder to be 1:1:4; when the prepared target product is Ta 0.8 Cr 1.2 Te 4 When the crystal is prepared, controlling the mole ratio of tantalum powder, chromium powder and tellurium powder to be 0.8:1.2:4; when the prepared target product is Ta 1.1 Cr 0.9 Te 4 When the crystal is used, the mol ratio of tantalum powder, chromium powder and tellurium powder is controlled to be 1.1:0.9:4. Similarly, according to the difference of x, the corresponding mole ratio of tantalum powder, chromium powder and tellurium powder can be calculated, thereby controllingAnd preparing the additive amount of tantalum powder, chromium powder and tellurium powder to obtain a target product.
When the purity of tantalum powder, chromium powder and tellurium powder is not high, impurities in the raw materials may cause difficulty in obtaining a target product; alternatively, the intrinsic properties of the material are affected by the interference of impurities. In a preferred embodiment, the purity of the tantalum powder, the chromium powder and the tellurium powder is equal to or greater than 99.99%, and the purity of the tantalum powder, the chromium powder and the tellurium powder is improved to obtain high-purity and high-quality Ta 1-x Cr 1+x Te 4 Single crystals of telluride.
In a preferred embodiment, the holding time is 7 days, and Ta is held at a temperature of 600.+ -. 25 ℃ at the low temperature zone end and 700.+ -. 25 ℃ at the high temperature zone end for 7 days 1-x Cr 1+x Te 4 The telluride crystal grows slowly, so that on one hand, the crystal has better crystallinity and better physicochemical property, and on the other hand, a massive single crystal with large size can be obtained, which is convenient for Ta 1-x Cr 1+x Te 4 The physical and chemical properties of the telluride crystal were studied.
The adding amount of the iodine particles can influence the transportation speed of tantalum, chromium and tellurium, so that the reaction speed and the growth speed of crystals are influenced, and when the adding amount of the iodine particles is too large, the transportation speed is too high, so that the reaction speed is too high, and large-block high-quality crystals are difficult to form; and too small amount of iodine particles can cause too slow reaction speed and too high energy consumption. In a preferred embodiment, the iodine particles are added in an amount of 5mg/mL calculated by the volume of the quartz tube, and at the concentration of the iodine particles, the temperature settings of the high temperature region and the low temperature region are combined simultaneously to obtain the ternary layered Ta with the size of approximately 10mm 1-x Cr 1+x Te 4 And telluride crystals.
Therefore, according to the preparation method of the ternary layered telluride single crystal, the target product can be obtained by controlling the mole ratio of tantalum powder, chromium powder and tellurium powder; by controlling the temperature of the low temperature region and the high temperature region, the adding amount of iodine particles and the heat preservation time, the high-quality and massive Ta can be formed 1-x Cr 1+x Te 4 The telluride crystal provides materials for researching the performance and the application of the ternary layered telluride.
To further illustrate the ternary layered telluride TaCrTe provided by the invention 4 And a method for preparing the same, the following examples are provided.
Example 1
TaCrTe 4 The preparation method of the crystal comprises the following steps:
step S1, batching and packaging: mixing tantalum powder, chromium powder and tellurium powder according to the molar ratio of 1:1:4, placing the mixture into a quartz tube after uniform mixing, and adding 5mg/mL of iodine particles; vacuumizing to be less than or equal to 1Pa, and then sealing the quartz tube filled with the sample by using flame sealing equipment;
step S2, firing: placing the sealed quartz tube in a double-temperature-zone tube furnace, positioning one end with materials at the high-temperature-zone end of the double-temperature-zone tube furnace, positioning one end without materials at the low-temperature-zone end of the double-temperature-zone tube furnace, heating at a speed of 5 ℃/min, heating the temperature at the low-temperature-zone end to 600+/-25 ℃, heating the temperature at the high-temperature-zone end to 700+/-25 ℃, and preserving heat for 7 days under the temperature gradient; cooling to room temperature after heat preservation, washing with alcohol until iodine is absent, and drying to obtain ternary lamellar telluride TaCrTe 4 And (5) a crystal.
TaCrTe prepared in example 1 4 The crystal is characterized by analyzing the morphology, structure and chemical composition through an optical microscope, an X-ray diffractometer and a scanning electron microscope, and the analysis results are shown in figures 1-5. Wherein, the graph (1) is TaCrTe 4 A bulk crystal plot taken by an optical microscope of the crystal, the crystal having a size approaching 10mm, the large crystal size facilitating obtaining single or few layer samples by mechanical exfoliation means; FIG. 2 is TaCrTe 4 An X-ray diffraction pattern of the crystal, from fig. 2, it can be confirmed that the bulk is single crystal; FIG. 3 is TaCrTe 4 The X-ray diffraction pattern of the powder, from figure 3, can determine that the material is rhombohedral structure; FIG. 4 is TaCrTe 4 The energy spectrum of the single crystal, the element composition and TaCrTe in the single crystal can be known from the graph 4 The stoichiometric ratio of (a) is matched; FIG. 5 is TaCrTe 4 Surface topography of single crystals, from which the single crystals can be seenThe crystal has a relatively flat monocrystalline surface.
Example 2
Ta (Ta) 1.1 Cr 0.9 Te 4 The preparation method comprises the following steps:
step S1, batching and packaging: taking tantalum powder, chromium powder and tellurium powder according to the mol ratio of 1.1:0.9:4, uniformly mixing, placing the mixture into a quartz tube, and adding 5mg/mL of iodine particles; vacuumizing to be less than or equal to 1Pa, and then sealing the quartz tube filled with the sample by using flame sealing equipment;
step S2, firing: placing the sealed quartz tube in a double-temperature-zone tube furnace, positioning one end with materials at the high-temperature-zone end of the double-temperature-zone tube furnace, positioning one end without materials at the low-temperature-zone end of the double-temperature-zone tube furnace, heating at a speed of 2 ℃/min, heating the temperature at the low-temperature-zone end to 600+/-25 ℃, heating the temperature at the high-temperature-zone end to 700+/-25 ℃, and preserving heat for 7 days under the temperature gradient; after the heat preservation is finished, cooling to room temperature, washing with alcohol until iodine is free, and drying to obtain ternary lamellar telluride Ta 1.1 Cr 0.9 Te 4 And (5) a crystal.
For the material prepared in example 2, the morphology, structure and chemical composition of the obtained material are analyzed and characterized by an optical microscope, an X-ray diffractometer and a scanning electron microscope, and the obtained material is determined to be single crystal under the condition, and the chemical formula of the material is Ta 1.1 Cr 0.9 Te 4 。
Example 3
Ta (Ta) 0.9 Cr 1.1 Te 4 The preparation method comprises the following steps:
step S1, batching and packaging: taking tantalum powder, chromium powder and tellurium powder according to the molar ratio of 0.9:1.1:4, uniformly mixing, placing the mixture into a quartz tube, and adding 5mg/mL of iodine particles; vacuumizing to be less than or equal to 1Pa, and then sealing the quartz tube filled with the sample by using flame sealing equipment;
step S2, firing: placing the sealed quartz tube in a double-temperature-zone tube furnace, placing one end with materials at the high-temperature-zone end of the double-temperature-zone tube furnace, placing one end without materials at the low-temperature-zone end of the double-temperature-zone tube furnace, and heating at a speed of 3 ℃/min to enable the low-temperature zoneThe temperature of the end is raised to 600+/-25 ℃, the temperature of the end of the high temperature area is raised to 700+/-25 ℃, and the temperature is kept for 7 days under the temperature gradient; after the heat preservation is finished, cooling to room temperature, washing with alcohol until iodine is free, and drying to obtain ternary lamellar telluride Ta 0.9 Cr 1.1 Te 4 And (5) a crystal.
For the material prepared in example 3, the morphology, structure and chemical composition of the obtained material were analyzed and characterized by an optical microscope, an X-ray diffractometer and a scanning electron microscope, and the obtained material was determined to be single crystal under the condition, and the chemical formula was Ta 0.9 Cr 1.1 Te 4 。
Example 4
Ta (Ta) 0.7 Cr 1.3 Te 4 The preparation method comprises the following steps:
step S1, batching and packaging: taking tantalum powder, chromium powder and tellurium powder according to the molar ratio of 0.7:1.3:4, uniformly mixing, placing the mixture into a quartz tube, and adding 5mg/mL of iodine particles; vacuumizing to be less than or equal to 1Pa, and then sealing the quartz tube filled with the sample by using flame sealing equipment;
step S2, firing: placing the sealed quartz tube in a double-temperature-zone tube furnace, positioning one end with materials at the high-temperature-zone end of the double-temperature-zone tube furnace, positioning one end without materials at the low-temperature-zone end of the double-temperature-zone tube furnace, heating at a speed of 4 ℃/min, heating the temperature at the low-temperature-zone end to 600+/-25 ℃, heating the temperature at the high-temperature-zone end to 700+/-25 ℃, and preserving heat for 8 days under the temperature gradient; after the heat preservation is finished, cooling to room temperature, washing with alcohol until iodine is free, and drying to obtain ternary lamellar telluride Ta 0.7 Cr 1.3 Te 4 And (5) a crystal.
For the material prepared in example 4, the morphology, structure and chemical composition of the obtained material were analyzed and characterized by an optical microscope, an X-ray diffractometer and a scanning electron microscope, and the obtained material was determined to be single crystal under the condition, and the chemical formula was Ta 0.7 Cr 1.3 Te 4 。
Comparative example 1
Preparation of TaCrTe by conventional solid phase sintering method 4 The preparation method comprises the following steps:
step one, compounding and packaging, namely for the chemical formula TaCrTe 4 Mixing tantalum powder, chromium powder and tellurium powder with a molar ratio of 1:1:4, and placing the mixture in a quartz tube; vacuumizing to be less than or equal to 1Pa, and then sealing the quartz tube filled with the sample by using flame sealing equipment.
And step two, high-temperature firing in a double-temperature area, namely placing the vacuum sealed quartz tube in a single-temperature area pit furnace, raising the temperature from room temperature to 900 ℃ for 140min, and preserving the temperature for 7 days. Subsequently, the vacuum-sealed quartz tube was naturally cooled to room temperature.
The material prepared in comparative example 1 was characterized by analysis of morphology, structure and chemical composition by means of an optical microscope, an X-ray diffractometer and a scanning electron microscope.
Fig. 6 is a photograph taken by an optical microscope of the comparative example 1 preparation material. The material is in powder form and is not monocrystalline. Therefore, taCrTe cannot be synthesized by conventional solid phase sintering 4 A single crystal material.
Comparative example 2
Ta (Ta) 1.2 Cr 0.8 Te 4 The preparation method comprises the following steps:
step one, batching and packaging: taking tantalum powder, chromium powder and tellurium powder according to the molar ratio of 1.2:0.8:4, uniformly mixing, placing the mixture into a quartz tube, and adding 5mg/mL of iodine particles; vacuumizing to be less than or equal to 1Pa, and then sealing the quartz tube filled with the sample by using flame sealing equipment;
step two, firing: placing the sealed quartz tube in a double-temperature-zone tube furnace, positioning one end with materials at the high-temperature-zone end of the double-temperature-zone tube furnace, positioning one end without materials at the low-temperature-zone end of the double-temperature-zone tube furnace, heating at a speed of 5 ℃/min, heating the temperature at the low-temperature-zone end to 600+/-25 ℃, heating the temperature at the high-temperature-zone end to 700+/-25 ℃, and preserving heat for 9 days under the temperature gradient; and after the heat preservation is finished, cooling to room temperature, washing with alcohol until iodine is free, and drying to obtain the prepared material.
For the material prepared in comparative example 2, the morphology, structure and chemical composition of the material were analyzed and characterized by an optical microscope, an X-ray diffractometer and a scanning electron microscope, and as can be seen from the X-ray diffractogram (see fig. 7), the material was a polycrystalline material, so that when the molar ratio of tantalum powder, chromium powder and tellurium powder was 1.2:0.8:4, single crystals could not be obtained.
Comparative example 3
Ta (Ta) 0.5 Cr 1.5 Te 4 The preparation method comprises the following steps:
step one, batching and packaging: taking tantalum powder, chromium powder and tellurium powder according to the molar ratio of 0.5:1.5:4, uniformly mixing, placing the mixture into a quartz tube, and adding 5mg/mL of iodine particles; vacuumizing to be less than or equal to 1Pa, and then sealing the quartz tube filled with the sample by using flame sealing equipment;
step two, firing: placing the sealed quartz tube in a double-temperature-zone tube furnace, positioning one end with materials at the high-temperature-zone end of the double-temperature-zone tube furnace, positioning one end without materials at the low-temperature-zone end of the double-temperature-zone tube furnace, heating at a speed of 5 ℃/min, heating the temperature at the low-temperature-zone end to 600+/-25 ℃, heating the temperature at the high-temperature-zone end to 700+/-25 ℃, and preserving heat for 10 days under the temperature gradient; and after the heat preservation is finished, cooling to room temperature to obtain the prepared material.
The product obtained by the method described in comparative example 3 was characterized by analysis of morphology, structure and chemical composition by means of an optical microscope, an X-ray diffractometer and a scanning electron microscope, and it was confirmed that the material obtained by the method was in the form of powder (the powder was similar to that of comparative example 1) and was not single crystal. Therefore, it was confirmed that when the molar ratio of tantalum powder, chromium powder, tellurium powder was 0.5:1.5:4, it was impossible to synthesize a single crystal material.
Comparative example 4
A process for preparing telluride, which is substantially the same as the process of example 1, except that: in the step S2, the temperatures of the low temperature region and the high temperature region are 400±25 ℃.
The product prepared by the method of comparative example 4 is subjected to analysis characterization of morphology, structure and chemical composition by an optical microscope, an X-ray diffractometer and a scanning electron microscope, and the material prepared by the method is determined to be not single crystal.
Comparative example 5
A process for preparing telluride, which is substantially the same as the process of example 1, except that: in the step S2, the temperatures of the low temperature region and the high temperature region are 800±25 ℃.
The product prepared by the method of comparative example 5 is subjected to analysis characterization of morphology, structure and chemical composition by an optical microscope, an X-ray diffractometer and a scanning electron microscope, and the material prepared by the method is determined to be not single crystal.
In examples 1 to 4 and comparative examples 1 to 5, the purity of the tantalum powder, the purity of the chromium powder, and the purity of the tellurium powder were all not less than 99.99%.
As is clear from the above examples and comparative examples, the ternary layered Ta having a large size and high quality can be obtained only by chemical vapor transport and controlling the ratio of reactants, reaction temperature and reaction time 1-x Cr 1+x Te 4 The telluride has high quality, large particle and chemical general formula Ta, and is difficult to obtain when the temperature is too high or too low, or the molar ratio of elements is not (1-x): (1+x): 4 and x is more than or equal to-0.1 and less than or equal to 0.3 1-x Cr 1+x Te 4 Is a ternary layered telluride crystal of (a).
It will be understood that equivalents and modifications will occur to those skilled in the art in light of the present invention and their spirit, and all such modifications and substitutions are intended to be included within the scope of the present invention as defined in the following claims.
Claims (10)
1. A ternary layered telluride, characterized by the chemical formula:
Ta 1-x Cr 1+x Te 4 wherein, -0.1 is less than or equal to x is less than or equal to 0.3.
2. The ternary layered telluride of claim 1, wherein the Ta 1-x Cr 1+x Te 4 Is of rhombic structure, and the space group is
3. A method for producing a ternary layered telluride single crystal, for producing a ternary layered telluride according to claim 1 or 2, characterized in that the method comprises the steps of:
step S1, batching and packaging: mixing tantalum powder, chromium powder and tellurium powder according to a proportion, placing the mixture into a quartz tube, adding iodine particles, vacuumizing, and sealing the quartz tube;
step S2, firing: placing the sealed quartz tube in a double-temperature-zone tube furnace, positioning one end with materials at the high-temperature-zone end of the double-temperature-zone tube furnace, positioning one end without materials at the low-temperature-zone end of the double-temperature-zone tube furnace, heating at a speed of 2-5 ℃/min, enabling the temperature of the low-temperature-zone end to be 575-625 ℃, enabling the temperature of the high-temperature-zone end to be 675-725 ℃, and preserving heat for 7-10 days; after the heat preservation is finished, cooling to room temperature, and cleaning and drying to obtain ternary lamellar telluride Ta 1-x Cr 1+x Te 4 。
4. The method for producing a ternary layered telluride single crystal according to claim 3, wherein the molar ratio of tantalum powder, chromium powder and tellurium powder is (1-x): (1+x): 4.
5. The method for producing a ternary layered telluride single crystal according to claim 4, wherein the purity of the tantalum powder, chromium powder and tellurium powder is not less than 99.99%.
6. The method for preparing a ternary layered telluride single crystal according to claim 5, wherein the molar ratio of tantalum powder, chromium powder and tellurium powder is 1:1:4, and the molecular formula of the ternary layered telluride prepared is TaCrTe 4 。
7. A method for producing a ternary layered telluride single crystal as defined in claim 3, wherein the holding time is 7 days.
8. The method for producing a ternary layered telluride single crystal according to claim 3, wherein the iodine particles are added in an amount of 5mg/mL.
9. The method for producing a ternary layered telluride single crystal according to claim 3, wherein the washing step is washing with alcohol.
10. The method for producing a ternary layered telluride single crystal according to claim 3, wherein the vacuum degree in the tube after the vacuum is applied to the quartz tube is 1Pa or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311397754.0A CN117468095A (en) | 2023-10-25 | 2023-10-25 | Ternary layered telluride and preparation method of single crystal thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311397754.0A CN117468095A (en) | 2023-10-25 | 2023-10-25 | Ternary layered telluride and preparation method of single crystal thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117468095A true CN117468095A (en) | 2024-01-30 |
Family
ID=89623146
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311397754.0A Pending CN117468095A (en) | 2023-10-25 | 2023-10-25 | Ternary layered telluride and preparation method of single crystal thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117468095A (en) |
-
2023
- 2023-10-25 CN CN202311397754.0A patent/CN117468095A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Galazka | β-Ga2O3 for wide-bandgap electronics and optoelectronics | |
| CN108039403B (en) | Batch preparation method of high-quality wafer-level bismuth selenide semiconductor single-crystal film | |
| CN107287578B (en) | A kind of chemical gas-phase deposition process for preparing of a wide range of uniformly double-deck molybdenum disulfide film | |
| CN110184654B (en) | Bi2O2Se crystal and preparation method thereof | |
| CN109437124B (en) | Method for synthesizing single-layer transition metal chalcogenide | |
| Filippo et al. | Single crystalline β-Ga2O3 nanowires synthesized by thermal oxidation of GaSe layer | |
| CN111139519A (en) | Preparation method of flaky SnSe monocrystal | |
| CN110438567A (en) | A kind of preparation method of semiconductor selenium bismuth oxide single crystal thin-film material | |
| CN110980659A (en) | Tungsten ditelluride grown by using new raw material and preparation method thereof | |
| Sun et al. | ε-InSe single crystals grown by a horizontal gradient freeze method | |
| TWI566274B (en) | Feed materials for single crystal silicon carbide epitaxial growth and method for epitaxial growth of single crystal silicon carbide | |
| CN111115590A (en) | Two-dimensional indium telluride nanosheet and polarized light detector prepared from same | |
| KR101830524B1 (en) | Two-dimensional large-area metal chalcogenide single crystals and method for manufactruing the same | |
| CN117468095A (en) | Ternary layered telluride and preparation method of single crystal thereof | |
| CN114686986B (en) | SnSe 2 Method for producing single crystal | |
| Zhai et al. | Growth of single crystalline ZnxCd1− xS nanocombs by metallo-organic chemical vapor deposition | |
| US20050115489A1 (en) | Method of obtaining a cdte or cdznte single crystal and the single crystal thus obtained | |
| CN113186590A (en) | Preparation method of centimeter-level molybdenum trioxide single crystal | |
| Jalilian et al. | Crystalline nano-structures of Ga2O3 with herringbone morphology | |
| Li et al. | Controlled growth of 2D ultrathin Ga 2 O 3 crystals on liquid metal | |
| JP2021511279A (en) | Plastic semiconductor materials and their manufacturing methods | |
| KR102250674B1 (en) | Layered compound, nanosheet and preparing method thereof | |
| Zhang et al. | Growth of submillimeter-scale single crystal 2D BiI3 by the cooling-induced growth method in a confined space | |
| CN117468090B (en) | Tantalum (IV) oxyhalide compound crystal material and preparation method and application thereof | |
| Wang et al. | Growth of Bi2S3 skeleton crystals with three-dimensional network morphologies |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |