CN116924352A - Method for adjusting transition metal chalcogenide broad spectrum detection by utilizing vacancy defects - Google Patents
Method for adjusting transition metal chalcogenide broad spectrum detection by utilizing vacancy defects Download PDFInfo
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- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 48
- -1 transition metal chalcogenide Chemical class 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 35
- 230000007547 defect Effects 0.000 title claims abstract description 30
- 238000001514 detection method Methods 0.000 title claims abstract description 13
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 35
- 239000000956 alloy Substances 0.000 claims abstract description 35
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- 238000000137 annealing Methods 0.000 claims abstract description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052798 chalcogen Inorganic materials 0.000 claims abstract description 14
- 150000001787 chalcogens Chemical class 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 10
- 150000004770 chalcogenides Chemical class 0.000 claims abstract description 8
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 238000001228 spectrum Methods 0.000 claims abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 3
- 230000008569 process Effects 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- 239000011593 sulfur Substances 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 61
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 29
- 235000012239 silicon dioxide Nutrition 0.000 claims description 25
- 239000010453 quartz Substances 0.000 claims description 21
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 20
- 239000010431 corundum Substances 0.000 claims description 18
- 229910052593 corundum Inorganic materials 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 17
- 229910052786 argon Inorganic materials 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 16
- 239000012159 carrier gas Substances 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000011780 sodium chloride Substances 0.000 claims description 10
- 150000003624 transition metals Chemical class 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- 239000011812 mixed powder Substances 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000012512 characterization method Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 6
- 238000011144 upstream manufacturing Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001069 Raman spectroscopy Methods 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- 229910002058 ternary alloy Inorganic materials 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000004570 mortar (masonry) Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000005498 polishing Methods 0.000 claims description 2
- 229910052594 sapphire Inorganic materials 0.000 claims description 2
- 239000010980 sapphire Substances 0.000 claims description 2
- 230000003595 spectral effect Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 230000002950 deficient Effects 0.000 claims 3
- 239000000463 material Substances 0.000 abstract description 12
- 239000002356 single layer Substances 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000005424 photoluminescence Methods 0.000 abstract description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 abstract 1
- 238000001237 Raman spectrum Methods 0.000 description 9
- 238000000103 photoluminescence spectrum Methods 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000005275 alloying Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000009812 interlayer coupling reaction Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000004549 pulsed laser deposition Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229910016001 MoSe Inorganic materials 0.000 description 1
- 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 1
- 238000001505 atmospheric-pressure chemical vapour deposition Methods 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
- G01J3/28—Investigating the spectrum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/305—Sulfides, selenides, or tellurides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Abstract
A method for adjusting transition metal chalcogenide broad spectrum detection by utilizing vacancy defects belongs to the field of two-dimensional materials. The method adopts transition metal oxide as a metal source, two different chalcogenides as a sulfur source, and a chemical vapor deposition method is used for growing single-layer ternary transition metal chalcogenides with uniformly distributed elements. By utilizing the stability difference of chemical bonds between alloy elements, unstable chemical bonds are broken through a hydrogen auxiliary annealing mode, and the generated chalcogen element vacancy defects are uniformly distributed in the ternary transition metal chalcogenide. The chalcogen element vacancy defect introduces a defect energy level between a conduction band and a valence band of the transition metal chalcogenide, generates a new photoluminescence peak, and widens the spectrum detection range. The experimental method has the advantages of simple process and good repeatability, can accurately regulate and control the types, distribution and quantity of defects, and is suitable for large-scale production.
Description
Technical Field
The invention belongs to the field of two-dimensional materials, and relates to a method for adjusting wide spectrum detection of transition metal chalcogenide by utilizing vacancy defects.
Technical Field
Two-dimensional transition metal chalcogenides (TMDs) have the characteristics of atomic layer thickness, adjustable band gap, high carrier mobility and the like, and are electrically, photoelectrically and optically usedThe method has wide application in the fields of the like. To further regulate and broaden the spectral response range of TMDs materials, methods of band tuning have been developed to apply stress, alloying, interlayer coupling, defect engineering, and the like. However, the band gap of the TMDs material can be adjusted to a certain extent by a stress and alloying method, but the adjustment range is limited due to the limitation of the intrinsic band gap of the material. Although the band gap of TMDs materials can be widely adjusted by means of interlayer coupling, there is a problem of low photo-responsivity, which is mainly that two different TMDs materials are stacked together, and electrons of conduction band and holes of valence band are not in the same position of K space. Defect engineering is a method for relatively effectively adjusting energy bands by introducing defect energy levels between conduction and valence bands of a material, thereby adjusting the band gap thereof. There have been articles describing the preparation of MoS by pulsed laser deposition 1.89 The detection wavelength of the material can reach 2.7 mu m. By means of MoS 2 ，WS 2 ，MoSe 2 ，WSe 2 The materials can be irradiated by proton beams, and can introduce sub-band gap photoluminescence peaks 100-200meV below neutral exciton peaks. In addition, WSe can be realized by annealing 2 The bandgap of (2) varies from 1.6eV to 1.3eV. Methods by pulsed laser deposition or proton/ion beam irradiation face time consuming and costly problems; and the type and the number of defects are difficult to control by plasma irradiation, heating and other methods.
Disclosure of Invention
In view of the above, the present invention provides a method for adjusting the bandgap of a material using alloys and defects. Firstly, synthesizing ternary transition metal chalcogenide with uniformly distributed elements by a chemical vapor deposition method, and adjusting the band gap of the material to a certain extent; and secondly, utilizing the stability difference of chemical bonds between alloy elements, and breaking unstable chemical bonds in a hydrogen-assisted annealing mode to prepare the ternary transition metal chalcogenide with uniformly distributed chalcogen vacancy defects. A defect level is introduced between the conduction band and the valence band of the ternary transition metal chalcogenide, thereby adjusting the band gap thereof.
In order to solve the problems, the invention adopts the following technical scheme:
a method for adjusting broad spectrum detection of transition metal chalcogenide by utilizing defect engineering is characterized in that salt is used as an accelerator, added into transition metal oxide, and the growth temperature is controlled to be 750-850 ℃ to prepare large-area ternary transition metal chalcogenide (consisting of two chalcogen elements and metal elements Mo or/and W); and then annealing the ternary transition metal chalcogenide by a hydrogen auxiliary annealing mode, thereby preparing the ternary transition metal chalcogenide with certain defect concentration.
The method specifically comprises the following steps:
(1) Cleaning the surface of the growth substrate;
(2) Preparing salt, grinding large-particle salt into powder by using a mortar, and weighing salt with a certain mass; weighing transition metal source powder with certain mass as a metal source;
(3) Weighing two chalcogen element powders with certain mass, pouring the chalcogen element powders into a centrifuge tube according to a certain proportion, uniformly stirring, and weighing chalcogen element mixed powder with certain mass as a sulfur source;
(4) Transferring the weighed transition metal source powder and salt powder into a corundum boat, mixing, placing a growth substrate above the transition metal source with a polishing surface facing downwards for growing ternary alloy, and pushing the corundum boat to the central temperature zone position of a tube furnace by using a furnace hook; pouring the weighed chalcogen element mixed powder into a glass boat, and placing the glass boat in a low-temperature area upstream of a carrier gas flow, wherein the distance is a certain distance from the center of a tube furnace; the carrier gas enters from one end of the tube furnace and is discharged from the other end;
(5) In the chemical vapor deposition reaction process, inert gas is used as carrier gas, and the temperature of the center of the tube furnace is set as follows according to time periods: the temperature is divided into three stages, wherein the first stage is a stage of exhausting gas in a tube furnace by introducing carrier gas, the second stage is a growth stage of ternary alloy, namely, heating up according to a certain heating rate under the condition of introducing carrier gas, then, reaching a certain temperature T2, preserving heat for a period of time at the temperature, and starting to introduce hydrogen until the growth is finished when the heating up process reaches the temperature T1; the third stage is a natural cooling stage;
(6) Annealing of the sample. Taking out the sample for Raman and PL characterization, after the characterization is finished, placing the surface with the sample growing upwards in a clean corundum boat in an inclined mode, and placing the corundum boat in a clean quartz tube.
(7) And (3) sequentially washing the quartz tube, introducing inert gas and hydrogen, heating the quartz tube by a furnace, and naturally cooling after keeping the temperature for a period of time.
Wherein, preferably, in the step (1), the cleaning is sequentially carried out by using acetone, alcohol and deionized water, the ultrasonic time is 5-15min, and the power is set to be 40-100W.
Wherein preferably, the salt in the step (2) comprises sodium chloride, potassium iodide and the like;
wherein preferably, the transition metal source in step (2) comprises: moO (MoO) 3 、WO 3 One or more of them;
wherein preferably, the two chalcogenides in the step (3) are S powder and Te powder or Se powder and Te powder; wherein, preferably, the mass ratio of the S powder to the Te powder or Se powder to the Te powder is 3:100-8:100;
wherein preferably, the growth substrate in step (4) comprises a silicon/silicon dioxide substrate, sapphire, mica, etc., preferably a silicon/silicon dioxide substrate;
wherein, preferably, the mass ratio of the transition metal source powder, the salt powder and the two chalcogenides in the step (4) is (1-10): (0.5-4): (200-400), preferably 1-10mg, 0.5-4mg and 200-400mg respectively.
Wherein preferably, in the step (4), the distance from the glass boat to the central position of the furnace is 13.5-16cm, and the temperature is kept between 250-600 ℃.
Wherein the carrier gas in the step (5) is preferably an inert gas, ar gas or N 2 Gas, preferably Ar gas; the flow rate of the inert gas in the first stage is 200-400sccm, and the gas washing time is 10-30min;
wherein preferably, the flow rate of the carrier gas in the second stage in the step (5) is 45-60sccm;
preferably, the hydrogen in the step (5) is introduced when the furnace temperature T1 reaches 600 ℃; wherein preferably the flow of hydrogen in the second stage of step (5) is from 5 to 10sccm, preferably 5sccm;
wherein preferably, the second stage T2 growth temperature in step (5) is 750-850 ℃, preferably 750 ℃;
wherein preferably, the second stage growth time in the step (5) is that of keeping the temperature at the T2 temperature for 3-15min, preferably 3-5min;
wherein, preferably, the annealing temperature in the step (7) is 200-350 ℃, and the annealing heat preservation time is 10-60min; the flow rate of the introduced argon is 40-60sccm, and the flow rate of the hydrogen is 5-15sccm.
The invention has the following advantages:
the invention adopts the atmospheric pressure chemical vapor deposition method to prepare the growth and defect of ternary transition metal chalcogenide;
the invention adopts a chemical vapor deposition mode to prepare a single-layer ternary transition metal chalcogenide, wherein elements are uniformly distributed in the ternary transition metal chalcogenide;
the chemical bonds with poor stability are broken by utilizing the difference of chemical bond stability among elements in the ternary transition metal chalcogenide, and the ternary transition metal chalcogenide with uniformly distributed chalcogen vacancy defects is prepared by hydrogen-assisted annealing;
because Se atoms or S atoms and a part of Te atoms are reserved, the framework structure of the ternary transition metal chalcogenide is maintained, and the stability of the alloy structure is ensured.
Firstly, the band gap of the ternary transition metal chalcogenide is regulated by an alloy method, so that the band gap is reduced to a certain extent; and secondly, introducing a defect energy level into the ternary transition metal chalcogenide by a defect introducing method in the step (7), and generating a new PL peak so as to enable broad spectrum detection (broad spectrum relative to the spectrum without entering the defect).
The method is simple, has good repeatability, can accurately regulate and control the types, distribution and quantity of defects, and is suitable for large-scale production.
Drawings
FIG. 1 shows the present inventionChemical vapor deposition growth of WSe in the light 2(1-x) Te 2x Schematic diagram of experimental device of alloy;
FIG. 2 is a WSe of example 1 2 Raman and PL spectra of (a);
FIG. 3 is WSe in example 2 1.7 Te 0.3 An optical lens and an atomic force microscope image of the alloy;
FIG. 4 is a WSe in example 2 1.7 Te 0.3 Raman and PL spectra of the alloy;
FIG. 5 is a WSe after annealing in example 2 1.7 Te 0.3 Raman and PL spectra of the alloy;
FIG. 6 is a WSe after annealing in example 3 1.7 Te 0.3 Raman and PL spectra of the alloy;
FIG. 7 is a WSe after annealing in example 4 1.7 Te 0.3 Raman and PL spectra of the alloy;
FIG. 8 is a WSe after annealing in example 3 1.7 Te 0.3 Photo-response diagram of alloy to different wavelengths
Detailed Description
The invention is further illustrated by the following figures and examples, which are not intended to limit the invention.
Example 1:
with SiO thickness of 400 μm 2 Si (wherein SiO) 2 285 nm) as a growth substrate, cutting a 4-inch silicon wafer into 1cm x 1cm squares, and respectively performing ultrasonic treatment for 15min by using acetone, alcohol and deionized water, wherein the power is set to be 100W; weigh 8mg of WO 3 The powder and 1mg of NaCl powder were poured into a corundum boat, and Si/SiO was deposited 2 The substrate is obliquely placed to WO 3 And NaCl powder and pushing the powder to the central position of the tube furnace; 300mg of Se powder was weighed and placed in a quartz boat, and the quartz boat was placed in the upstream region of the tube furnace at a distance of 14cm from the central temperature zone of the tube furnace. WSe (Wireless sensor set) 2(1-x) Te 2x The schematic diagram of the experimental device for alloy growth is shown in fig. 1.
Washing with 200sccm argon for 15-20min; after the gas washing is completed, the flow rate of argon is adjusted to 45sccm to carry out WSe 2 The alloy was grown, and the furnace was warmed to 750 ℃ at a ramp rate of 50 ℃/min and incubated at this temperature for 3min. When the furnace temperature was raised to 600 ℃, 5sccm of hydrogen was introduced. After the growth is finished, when the temperature of the furnace is reduced to 600 ℃, closing hydrogen, opening the furnace, and naturally cooling to room temperature. The obtained WSe 2 The Raman and PL spectra of (c) are shown in figure 2. From the figure, we can see WSe 2 The PL peak of (C) is at 765 nm.
Example 2:
with SiO thickness of 400 μm 2 Si (wherein SiO) 2 285 nm) as a growth substrate, cutting a 4-inch silicon wafer into 1cm x 1cm squares, and respectively performing ultrasonic treatment for 15min by using acetone, alcohol and deionized water, wherein the power is set to be 100W; weigh 8mg of WO 3 The powder and 1mg of NaCl powder were poured into a corundum boat, and Si/SiO was deposited 2 The substrate is obliquely placed to WO 3 And NaCl powder and pushing the powder to the central position of the tube furnace; 300mg of mixed powder of Se powder and Te powder (the mass ratio of the Se powder to the Te powder is 5:100) is weighed and placed in a quartz boat, and the quartz boat is placed in the upstream area of a tube furnace, and the distance from the central temperature area of the tube furnace is 14cm.
Washing with 200sccm argon for 15-20min; after the gas washing is completed, the flow rate of argon is adjusted to 45sccm to carry out WSe 2(1-x) Te 2x The alloy was grown, and the furnace was warmed to 750 ℃ at a ramp rate of 50 ℃/min and incubated at this temperature for 3min. When the furnace temperature was raised to 600 ℃, 5sccm of hydrogen was introduced. After the growth is finished, when the temperature of the furnace is reduced to 600 ℃, closing hydrogen, opening the furnace, and naturally cooling to room temperature. The obtained WSe 1.7 Te 0.3 The optical lens, AFM, raman and PL spectrograms of the alloy are shown in figures 3 and 4.AFM characterization, grown WSe 1.7 Te 0.3 The alloy thickness was 0.76nm, indicating that it was a monolayer. Raman characterization shows that WSe is grown 1.7 Te 0.3 Alloy, and WSe 1.7 Te 0.3 The PL peak of the alloy is 800nm, compared with WSe 2 The PL peak of (2) is shifted to the right by 25nm mainly due to the incorporation of Te element, which causes WSe to occur 1.7 Te 0.3 The band gap of the alloy decreases.
Placing the grown sample into a new oneThe corundum boat and a new quartz tube, and the corundum boat is placed in the center of the furnace. The quartz tube was purged with 200sccm argon for 15-20 minutes and air was removed therefrom. After the gas washing is completed, regulating the flow of argon to 45sccm; 5sccm of hydrogen was introduced. The furnace was started, the heating rate of the furnace was set to 30 ℃/min, heated to 250 ℃, and annealed at this temperature for 30min. After the annealing is completed, the hydrogen is closed, the furnace is opened, and the annealing furnace is naturally cooled to room temperature. Annealed WSe 1.7 Te 0.3 The Raman and PL spectra of the alloy are shown in figure 5; unannealed WSe 1.7 Te 0.3 The alloy had only one PL peak at 800nm (FIG. 4), whereas WSe was annealed at 250℃for 30min 1.7 Te 0.3 The PL peaks at 800nm and 876nm appear in the alloy, mainly due to the breakdown of the less stable W-Te bonds by annealing, introducing a defect level between the conduction and valence bands of the alloy, resulting in the appearance of a new 876nm peak.
Example 3:
with SiO thickness of 400 μm 2 Si (wherein SiO) 2 285 nm) as a growth substrate, cutting a 4-inch silicon wafer into 1cm x 1cm squares, and respectively performing ultrasonic treatment for 15min by using acetone, alcohol and deionized water, wherein the power is set to be 100W; weigh 8mg of WO 3 The powder and 1mg of NaCl powder were poured into a corundum boat, and Si/SiO was deposited 2 The substrate is obliquely placed to WO 3 And NaCl powder and pushing the powder to the central position of the tube furnace; weighing 300mg of mixed powder of Te powder and Se powder (the mass ratio of the Te powder to the Se powder is 5:100), placing the mixed powder into a quartz boat, and placing the quartz boat in an upstream area of a tube furnace, wherein the distance from the quartz boat to a central temperature area of the tube furnace is 14cm;
washing with 200sccm argon for 15-20min; after the gas washing is completed, the flow rate of argon is adjusted to 45sccm to carry out WSe 2(1-x) Te 2x The alloy was grown, and the furnace was warmed to 750 ℃ at a ramp rate of 50 ℃/min and incubated at this temperature for 3min. When the furnace temperature was raised to 600 ℃, 5sccm of hydrogen was introduced. After the growth is finished, when the temperature of the furnace is reduced to 600 ℃, closing hydrogen, opening the furnace, and naturally cooling to room temperature.
Placing the grown sample into a new corundum boat,and the corundum boat was placed in the center of the furnace. The quartz tube was purged with 200sccm argon for 15-20 minutes and air was removed therefrom. After the gas washing is completed, regulating the flow of argon to 45sccm; 5sccm of hydrogen was introduced. The furnace was started, the heating rate of the furnace was set to 30 ℃/min, heated to 280 ℃, and annealed at this temperature for 30min. After the annealing is completed, the hydrogen is closed, the furnace is opened, and the annealing furnace is naturally cooled to room temperature. Annealed WSe 1.7 Te 0.3 The Raman and PL spectra of the alloy are shown in FIG. 6. FIG. 6 WSe after annealing 1.7 Te 0.3 A new PL peak at 910nm appears, whereas the annealed WSe of FIG. 5 1.7 Te 0.3 The PL peak at 876nm appears, and the wavelength of the newly appearing PL peak in fig. 6 is larger than that of the newly appearing PL peak in fig. 5, mainly due to the increase in annealing temperature, introducing more Te hole defects. FIG. 8 is a WSe 1.7 Te 0.3 The alloy is annealed at 280 ℃ to respond to light with different wavelengths, and the alloy can respond to light with 1000nm, so that the alloy can perform broad spectrum detection.
Example 4:
with SiO thickness of 400 μm 2 Si (wherein SiO) 2 285 nm) as a growth substrate, cutting a 4-inch silicon wafer into 1cm x 1cm squares, and respectively performing ultrasonic treatment for 15min by using acetone, alcohol and deionized water, wherein the power is set to be 100W; weigh 8mg of WO 3 The powder and 1mg of NaCl powder were poured into a corundum boat, and Si/SiO was deposited 2 The substrate is obliquely placed to WO 3 And NaCl powder and pushing the powder to the central position of the tube furnace; weighing 300mg of mixed powder of Te powder and Se powder (the mass ratio of the Te powder to the Se powder is 5:100), placing the mixed powder into a quartz boat, and placing the quartz boat in an upstream area of a tube furnace, wherein the distance from the quartz boat to a central temperature area of the tube furnace is 14cm;
washing with 200sccm argon for 15-20min; after the gas washing is completed, the flow rate of argon is adjusted to 45sccm to carry out WSe 2(1-x) Te 2x The alloy was grown, and the furnace was warmed to 750 ℃ at a ramp rate of 50 ℃/min and incubated at this temperature for 3min. When the furnace temperature was raised to 600 ℃, 5sccm of hydrogen was introduced. After the growth is finished, when the furnace temperature is reduced to 600 ℃, closing hydrogen, opening the furnace, and naturallyCooled to room temperature.
The grown samples were placed in a new corundum boat and a new quartz tube, and the corundum boat was placed in the center of the furnace. The quartz tube was purged with 200sccm argon for 15-20 minutes and air was removed therefrom. After the gas washing is completed, regulating the flow of argon to 45sccm; 5sccm of hydrogen was introduced. The furnace was started, the heating rate of the furnace was set to 30 ℃/min, heated to 280 ℃, and annealed at this temperature for 30min. After the annealing is completed, the hydrogen is closed, the furnace is opened, and the annealing furnace is naturally cooled to room temperature. Annealed WSe 1.7 Te 0.3 The Raman and PL spectra of the alloy are shown in FIG. 7.
The ternary transition metal chalcogenide with uniformly distributed elements grows through a chemical vapor deposition method, the ternary transition metal chalcogenide consists of two chalcogenides and metal elements Mo or/and W, and the ternary transition metal chalcogenide is formed by utilizing the stability difference of chemical bonds between the elements, and then the chemical bonds with poor stability are broken through a hydrogen auxiliary annealing mode to generate the ternary transition metal chalcogenide with uniformly distributed chalcogenides vacancy defects, and defect energy levels are introduced between a conduction band and a valence band of the ternary transition metal chalcogenide alloy, so that a new PL peak appears, and the ternary transition metal chalcogenide alloy can be subjected to relatively wider spectrum detection.
Claims (9)
1. A method for preparing transition metal chalcogenide capable of broad spectrum detection by utilizing defect engineering is characterized in that a ternary transition metal chalcogenide with uniformly distributed elements is grown by a chemical vapor deposition method, the ternary transition metal chalcogenide consists of two chalcogenides and metal elements Mo or/and W, the chemical bonds with poor stability are broken by utilizing the stability difference of the chemical bonds between the elements and by a hydrogen auxiliary annealing mode, the ternary transition metal chalcogenide with uniformly distributed chalcogen element vacancy defects is generated, defect energy levels are introduced between a conduction band and a valence band of the ternary transition metal chalcogenide alloy, and a new PL peak appears, so that the ternary transition metal chalcogenide alloy can be subjected to relatively wider spectrum detection.
2. The method as claimed in claim 1, characterized in that it comprises the following steps:
the method specifically comprises the following steps:
(1) Cleaning the surface of the growth substrate;
(2) Preparing salt, grinding large-particle salt into powder by using a mortar, and weighing salt with a certain mass; weighing transition metal source powder with certain mass as a metal source;
(3) Weighing two chalcogen element powders with certain mass, pouring the chalcogen element powders into a centrifuge tube according to a certain proportion, uniformly stirring, and weighing chalcogen element mixed powder with certain mass as a sulfur source;
(4) Transferring the weighed transition metal source powder and salt powder into a corundum boat, mixing, placing a growth substrate above the transition metal source with a polishing surface facing downwards for growing ternary alloy, and pushing the corundum boat to the central temperature zone position of a tube furnace by using a furnace hook; pouring the weighed chalcogen element mixed powder into a glass boat, and placing the glass boat in a low-temperature area upstream of a carrier gas flow, wherein the distance is a certain distance from the center of a tube furnace; the carrier gas enters from one end of the tube furnace and is discharged from the other end;
(5) In the chemical vapor deposition reaction process, inert gas is used as carrier gas, and the temperature of the center of the tube furnace is set as follows according to time periods: the temperature is divided into three stages, wherein the first stage is a stage of exhausting gas in a tube furnace by introducing carrier gas, the second stage is a growth stage of ternary alloy, namely, heating up according to a certain heating rate under the condition of introducing carrier gas, then, reaching a certain temperature T2, preserving heat for a period of time at the temperature, and starting to introduce hydrogen until the growth is finished when the heating up process reaches the temperature T1; the third stage is a natural cooling stage;
(6) Annealing of the sample. Taking out the sample for Raman and PL characterization, after the characterization is finished, placing the surface with the sample growing upwards in a clean corundum boat in an inclined mode, and placing the corundum boat in a clean quartz tube.
(7) And (3) sequentially washing the quartz tube, introducing inert gas and hydrogen, heating the quartz tube by a furnace, and naturally cooling after keeping the temperature for a period of time.
3. The method of claim 1, wherein the washing in step (1) is ultrasonic washing with acetone, alcohol and deionized water in sequence for 5-15min at a power setting of 40-100W.
4. The method of claim 1 wherein said salt in step (2) comprises sodium chloride, potassium iodide, and the like; the transition metal source described in step (2) includes: moO (MoO) 3 、WO 3 One or more of them; the two chalcogenides in the step (3) are S powder and Te powder, or Se powder and Te powder; wherein, the mass ratio of the S powder to the Te powder or Se powder to the Te powder is 3:100-8:100.
5. The method according to claim 1, wherein the growth substrate in step (4) comprises a silicon/silicon dioxide substrate, sapphire, mica, etc., preferably a silicon/silicon dioxide substrate; the mass ratio of the transition metal source powder to the salt powder to the two chalcogenides in the step (4) is (1-10): (0.5-4): (200-400), preferably the corresponding mass is 1-10mg, 0.5-4mg, 200-400mg respectively; the distance from the glass boat to the center of the furnace in the step (4) is 13.5-16cm, and the temperature is kept between 250-600 ℃.
6. The method of claim 1, wherein the carrier gas in step (5) is an inert gas, ar, N 2 Gas, preferably Ar gas; the flow rate of the inert gas in the first stage is 200-400sccm, and the gas washing time is 10-30min;
the flow rate of the carrier gas in the second stage in the step (5) is 45-60sccm;
the hydrogen gas in the step (5) is introduced when the furnace temperature T1 reaches 600 ℃; the flow rate of the hydrogen in the second stage in the step (5) is 5-10sccm, preferably 5sccm;
the second stage T2 growth temperature in step (5) is 750-850 ℃, preferably 750 ℃;
the second stage growth time in step (5) is 3-15min, preferably 3-5min, at T2 temperature.
7. The method according to claim 1, wherein the annealing temperature in step (7) is 200 to 350 ℃ and the annealing hold time is 10 to 60min; the flow rate of the introduced argon is 40-60sccm, and the flow rate of the hydrogen is 5-15sccm.
8. A defective transition metal chalcogenide prepared according to the method of any one of claims 1-7.
9. Use of a defective transition metal chalcogenide compound produced according to the method of any one of claims 1-7 for a broader spectral detection of a relatively defective transition metal chalcogenide compound.
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