Preparation of metal chalcogenides

Abstract

A method embodiment involves preparing single metal or mixed transition metal chalcogenide using exfoliation of two or more different bulk transition metal dichalcogenides in a manner to form an intermediate hetero-layered transition metal chalcogenide structure, which can be treated to provide a single-phase transition metal chalcogenide.

Claims

1. A method for preparing a transition metal chalcogenide, comprising the step of exfoliating and concurrently self-combining two or more starting transition metal chalcogenides having compositions that differ with respect to at least one of a transition metal constituent and a chalcogen constituent to produce a hetero-layered structure having a mix of different layers with different compositions.

2. The method of claim 1 wherein exfoliating is conducted by mechanical processing of the starting transition metal chalcogenides together.

3. The method of claim 2 wherein the exfoliating is conducted by dry mechanical processing of the two or more starting transition metal chalcogenides together.

4. The method of claim 2 wherein dry mechanical processing is carried out in an inert gaseous atmosphere or gaseous atmosphere that is non-reactive towards the two or more starting transition metal chalcogenides and the produced hetero-layered structure.

5. The method of claim 2 wherein the exfoliating and self-combining are conducted by mechanical processing in the presence of a liquid medium.

6. The method of claim 5 wherein the liquid medium comprises at least one of isopropanol, water, dimethylsulphoxide, N-vinyl-pyrrolidinonc, N-methyl-pyrrolidinone, benzonitrile or any solvent that does not react with exfoliated chalcogenide materials under the processing conditions.

7. The method of claim 2 wherein mechanical processing is carried out using pestle and mortar, shaker ball mills of any configuration, planetary ball mills of any configurations, any type of laboratory or industrial grinders, sonication, or other milling, or grinding equipment.

8. The method of claim 1 wherein the exfoliating and sell-combining form the hetero-layered structure which is three dimensional.

9. The method of claim 1 wherein the exfoliated starting transition metal chalcogenides are concurrently mixed as they are exfoliated to self-combine to form the hetero-layered structure.

10. The method of claim 9 where the hetero-layered structure is converted into single-phase, chalcogenide material by subjecting it to thermal annealing treatment or mechanical processing including at least one of milling, grinding, cold or hot rolling, or extrusion, high hydrostatic pressure, combined with thermal annealing treatment.

11. The method of claim 10 wherein the thermal treatment is carried out by heating in the temperature range between 100° C. and 1500° C.

12. The method of claim 1 wherein the exfoliating and concurrent self-combing are carried out by ultrasonic irradiation.

13. The method of claim 1 including the further step of treating the hetero-layered structure to form a substantially single-phase, chalcogenide structure.

14. The method of claim 13 wherein the hetero-layered structure is substantially devoid of separate phases of the two or more starting transition metal chalcogenides.

15. The method of claim 13 wherein a substantially homogenous solid solution of the two or more starting transition metal chalcogenides is produced.

16. The method of claim 13 wherein the hetero-layered structure is treated by heat treating at a temperature for a time to achieve a substantially single-phase chalcogenide structure.

17. The method of claim 16 wherein heat treating is conducted at elevated temperatures between 100 and 1500 degrees C. in an inert or non-reactive gaseous atmosphere to produce a single-phase transition metal chalcogenide.

18. The method of claim 16 wherein the heat treating time is between 1 minute to 72 hours or longer.

19. The method of claim 16 wherein heat treating is conducted in an atmosphere comprising at least one of helium, argon, krypton, xenon, nitrogen, and any other gas, which shows no reactivity towards the starting transition metal chalcogenides or the hetero-layered structure.

20. The method of claim 13 including the further step of exfoliating the substantially single phase, chalcogenide structure.

21. The method of claim 1 wherein the starting transition metal chalcogenides comprise transition metal dichalcogenides selected from the group consisting of the group 4 transition metal dichalcogenides (M=Ti, Zr, Hf), group 5 transition metal dichalcogenides (M=V, Nb, Ta) or group 6 transition metal dichalcogenides (M=Cr, Mo, W), group 7 transition metal dichalcogenides (M=Mn, Re), group 10 transition metal dichalcogenides (M=Pd, Pt)J, group 11 transition metal dichalcogenides (Cu, Ag), group 12 transition metal dichalcogenides (Zn, Cd), group 13 transition metal dichalcogenides (e.g., M=1n, Ga) as well as lanthanum group metals chalcogenides (Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu).

22. The method of claim 1 that produce a hetero-layered transition metal chalcogenide having a chemical composition represented by (M.sub.aM.sup.2.sub.bM.sup.3.sub.c. . . n)(X.sub.dX.sup.2.sub.eX.sup.3.sub.f), where the formula unit includes two or more different metals (M), and X, X.sup.2 and X.sup.3 represent S, Se, or Te, whereby the sum of a+b+c+. . . n is between 1 and 3 and the sum of d+e+f is between 1 and 6.

23. The method of claim 1 where the hetero-layered structure comprises at least two or more of a mixed metal dichalcogenide material, a mixed metal tricbalcogenide material, a same metal dichalcogenide material, or a same metal trichalcogenide material.

24. The method of claim 23 the metal is selected from the group consisting of Ti, Zr, Hf, Nb, Ta, Mo, W, Re, Pd, Pt, In, Ga and Sn.

25. The method of claim 1 wherein the exfoliating and self-combining occur in the presence of at least one of graphite, black phosphorus, and boron nitride.

26. The method of claim 1 wherein exfoliating is conducted using at least one of ultrasonic irradiation, liquid-assisted mechanical processing that includes grinding or milling, electrical force liquid-phase electrochemical exfoliation, or chemical exfoliation.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIGS. 1a and 1b show powder X-ray diffraction patterns for the stoichiometric 1:1 (molar) mixture of MoS.sub.2 and WS.sub.2 milled for various periods of time in a planetary mill (FIG. 1a) and a mixer mill (FIG. 1b).

(2) FIGS. 2a-2d are SEM secondary (SEI) and backscattering (BEI) images of the 1:1 (molar) MoS.sub.2 and WS.sub.2 samples milled for 15 hours in the planetary mill (FIGS. 2a, 2c) and the mixer mill (FIGS. 2b, 2d).

(3) FIG. 3 shows EDS elemental mapping of the 1:1 (molar) MoS.sub.2 and WS.sub.2 sample milled in the planetary mill for 15 hours where view “a” shows the analyzed area, view “b” shows sulfur distribution, view “c” shows tungsten distribution, and view “d” shows molybdenum distribution.

(4) FIGS. 4a and 4b are TEM images of the 1:1 (molar) MoS.sub.2 and WS.sub.2 samples milled for 15 hours in the planetary mill (FIG. 4a) and the mixer mill (FIG. 4b).

(5) FIGS. 5a and 5b are HAADF-TEM images of the 1:1 (molar) MoS.sub.2 and WS.sub.2 samples milled for 15 hours in the planetary mill (FIG. 5a) and the mixer mill (FIG. 5b). HAADF-TEM is high-angle annular dark-filed transmission electron microscopy.

(6) FIG. 6 shows Raman spectra of the 1:1 (molar) MoS.sub.2 and WS.sub.2 samples milled for 15 hours in the planetary mill (curve a) and in the mixer mill (curve b).

(7) FIG. 7 is the DSC/TGA curve of the 1:1 (molar) MoS.sub.2 and WS.sub.2 samples milled for 15 hours in the planetary mill.

(8) FIG. 8 shows powder X-ray diffraction patterns of the 1:1 (molar) mixture of MoS.sub.2 and WS.sub.2 milled for 15 hours in a planetary mill (curve a—as-milled) and then heat treated at 950 degrees C. in argon for 16 hours (curve b—annealed).

(9) FIGS. 9a and 9b are HAADF-TEM images of the 1:1 (molar) MoS.sub.2 and WS.sub.2 samples milled for 15 hours in the planetary mill and then heat treated at 950 degrees C. in argon for 16 hours.

(10) FIGS. 10a and 10b are powder X-ray diffraction patterns of the 1:1 (molar) mixture of MoS.sub.2 and WSe.sub.2 (FIG. 10a) and MoSe.sub.2 and WS.sub.2 (FIG. 10b). Both materials were ball milled for 15 hours in a planetary mill and then heat treated at 1000 degrees C. in argon for 16 hours.

(11) FIG. 11 is Raman spectra of the 1:1 (molar) MoS.sub.2—WSe.sub.2 samples milled for 30 hours in the planetary mill and then heat treated at 1000 degrees C. in argon for 16 hours.

(12) FIG. 12 shows powder X-ray diffraction patterns of the starting MoS.sub.2 and WSe.sub.2, and the 1:1 (molar) MoS.sub.2—WSe.sub.2 sample milled for 30 hours in a planetary mill at 600 rpm.

(13) FIG. 13 is HAADF-TEM and HAADF-EDS images of the 1:1 (molar) MoS.sub.2 and WSe.sub.2 samples milled for 30 hours in the planetary mill.

(14) FIG. 14 is the high-resolution XPS spectra of Mo 3d, S 2p, Se 3d and W 4f for the 1:1 (molar) MoS.sub.2 and WSe.sub.2 sample milled for 30 hours in the planetary mill and then heat treated at 1000 degrees C. in argon for 16 hours.

(15) FIG. 15 shows powder X-ray diffraction patterns of the starting MoS.sub.2 and WSe.sub.2, and the 1:1 (molar) MoS.sub.2—WSe.sub.2 samples milled for 1 and 4 hours in the mixer mill.

(16) FIG. 16 is powder X-ray diffraction patterns of the starting MoS.sub.2 and MoSe.sub.2, and the 1:1 (molar) MoS.sub.2—MoSe.sub.2 samples milled for 30 hours in the planetary mill and then heat treated at 1000 degrees C. in argon for 16 hours.

(17) FIG. 17 is Raman spectra of the starting MoS.sub.2 and MoSe.sub.2, and the 1:1 (molar) MoS.sub.2—MoSe.sub.2 samples milled for 30 hours in the planetary mill and then heat treated at 1000 degrees C. in argon for 16 hours.

(18) FIGS. 18a-18b; 19a-19b, and 20a-20b relate to five- and six-principal element TMDCs, wherein FIG. 18a shows XRD pattern and FIG. 18b shows Raman spectra of (Mo.sub.0.4W.sub.0.2Nb.sub.0.4)S.sub.0.8Se.sub.1.2. Corresponding data for (Mo.sub.0.6W.sub.0.2Ta.sub.0.2)S.sub.0.8Se.sub.1.2 is shown in FIG. 19a and FIG. 19b, and for (Mo.sub.0.25W.sub.0.25Nb.sub.0.25Ta.sub.0.25)SSe is shown in FIG. 20a and FIG. 20b. Diffraction patterns and Raman spectra of starting materials are shown as references.

(19) FIG. 21 shows powder X-ray diffraction patterns of the 1:1 (molar) MoS.sub.2—WSe.sub.2 samples milled for 1, 10 and 30 hours in the planetary mill at 300 rpm.

(20) FIGS. 22a-22e show HAADF-STEM and STEM-EDS images of the as-milled equimolar mixture of MoS.sub.2 and WSe.sub.2; wherein FIG. 22a shows an example of a “compositionally uniform” particle and FIG. 22b shows a heterostructured particle. A side view of a large particle is shown in FIG. 22c and FIG. 22d, and a “reshuffled” fragment of the same material is shown in FIG. 22e. Due to the higher Z-factor, WSe.sub.2 fragments produce brighter image than the MoS.sub.2 layer

(21) FIG. 23 is powder X-ray diffraction patterns of the 1:1 (molar) MoS.sub.2—WSe.sub.2 samples milled for 30 hours in the planetary mill at 300 and 600 rpm and then heat treated at 1000 degrees C. in argon for 16 hours.

(22) FIG. 24 is a schematic diagram of liquid-phase preparation of single-phase, bulk TMDC materials according to an embodiment of the invention.

(23) FIG. 25 are powder X-ray diffraction patterns of the 1:1 (molar) MoS.sub.2—WSe.sub.2 sample processed as described in Example 4 before heating.

(24) FIG. 26 are powder X-ray diffraction patterns of the 1:1 (molar) MoS.sub.2—WSe.sub.2 sample processed as described in Example 4 after heating at 1000 degrees C. in argon for 16 hours.

(25) FIG. 27 are powder X-ray diffraction patterns of the 1:1 (molar) MoS.sub.2—WSe.sub.2 sample processed as described in Example 5 before heating.

(26) FIG. 28 are powder X-ray diffraction patterns of the 1:1 (molar) MoS.sub.2—WSe.sub.2 sample processed as described in Example 6 before heating.

(27) FIG. 29 are powder X-ray diffraction patterns of the 1:1 (molar) MoS.sub.2—WSe.sub.2 sample processed as described in Example 6 after heating at 1000 degrees C. in argon for 16 hours.

DETAILED DESCRIPTION OF THE INVENTION

(28) The present invention provides method embodiments for preparing a transition metal chalcogenide material, such as a TMDC, by exfoliating two or more different starting TMDCs separately or together and combining the exfoliated products to form a transition metal chalcogenide structure having layers of different composition. The combining of the exfoliated products can be achieved in a passive manner by self-assembly in the event the TMDCs are exfoliated together and/or in an active manner by mixing the products together in the event the TMDCs are exfoliated separately.

(29) The present invention involves preparing a transition metal chalcogenide material starting for example from different, bulk, starting TMDCs wherein the method includes one or more solid-state or liquid-assisted exfoliation steps. For purposes of illustration and not limitation, Examples 1-3 set forth below describe dry mechanical exfoliation by mechanical processing to this end. For purposes of illustration and not limitation, Examples 4-7 describe liquid-assisted mechanical exfoliation by mechanical processing, which can be followed by liquid phase sonication, to this same end.

(30) In practice of embodiments of the present invention, the bulk TMDCs that are subjected to processing pursuant to the present invention can include the TMDCs selected from the group consisting of the group 4 TMDCs (M=Ti, Zr, Hf), group 5 TMDCs (M=V, Nb, Ta) or group 6 TMDCs (M=Cr, Mo, W), group 7 TMDCs (M=Mn, Re), group 10 TMDCs (M=Pd, Pt)], group 11 TMDCs (Cu, Ag), group 12 TMDCs (Zn, Cd), group 13 TMDCs (e.g., M=In, Ga) as well as lanthanum group metals chalcogenides (Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu).

(31) Practice of embodiments of the invention can produce mixed transition metal dichalcogenide materials that include two or more metals selected from the group consisting of metal is selected from the group consisting of Ti, Zr, Hf, Nb, Ta, Mo, W, Re, Pd, Pt, In, Ga and Cr and two or more chalcogen elements, namely, two or more of S, Se, and Te. Bulk layered chalcogenide materials that can be processed pursuant to the method embodiments can include, but are not limited to two or more bulk single-phase commercially available TMDCs as well as optional graphene, boron nitride, black phosphorus and other related layered materials that additionally and optionally may be incorporated into the composition of a final metal multi-chalcogenide composite product by exfoliation with the TMDCs wherein the composite structure is built-up of 2D exfoliated layers of the different materials.

(32) Examples 1-3 describe illustrative embodiments involving solid-state mechanical processing which can be conducted using pestle and mortar, shaker ball mills of any configuration, planetary ball mills of any configurations, any type of laboratory or industrial grinders, or other milling, or grinding equipment that can produce plastic, shear and other irreversible deformation as well as partial or complete exfoliation of the bulk TMDCs to an extent that achieves the results described below. The mechanical processing can be conducted under an inert or non-reactive gas atmosphere and at any temperature including below room temperature, at room temperature, and/or at elevated temperatures above room temperature such as to 100-1500° C. for appropriate times such as including, but not limited to, 1 minute to 72 hours or longer. The mechanical processing can be followed by heat treatment at elevated temperatures above room temperature such as 100-1500° C. A TMDC having a disordered, heterogeneous-layered structure or ordered, single-phase structure can be produced depending upon processing temperature and processing time. The ordered, single-phase TMDC can be a substantially homogenous solid solution of two or more different TMDCs.

(33) Examples 4-7 describe illustrative embodiments involving (1) mechanochemical exfoliation of two or more different TMDC materials in the same or different appropriate liquid environment using any exfoliation technique, step (2) subsequent generation of mixed hierarchical (layered) heterostructures, either by a spontaneous assembly in solution (e.g. mixing together of the dispersions formed in step (1)) or by using an additive assembly technique (e.g. layer-by-layer deposition, spin coating, ink jet printing etc. of the dispersions formed in step (1), and then step (3) reactive interlayer mixing and conversion of the hierarchical (layered) heterostructures obtained in step (2) into a single phase material, wherein reactive intermixing is effected by means of heat treatment, or mechanical working/processing, or high uniaxial external pressure, or a combination of external pressure and shear stress, or by cold or hot rolling or by combination of thereof. The invention envisions preparing a TMDC material using steps (1) to (3). The material so formed can include a mixed metal component.

(34) In illustrative embodiments, the exfoliating step is conducted by mechanical processing in the same or different liquid(s) to form dispersion(s) and the combining step involves spontaneous self-assembly (e.g. by mixing the dispersions together) or additive assembly (e.g. layer-by-layer deposition, spin coating, ink jet printing, etc. of the dispersions) of the exfoliated products of the dispersions.

(35) The intermediate 3D heterostructured TMDC material having hetero-layers (heterogeneous layers) can be converted to a single phase by subjecting the material to further processing including, but not limited to, thermal heat treatment (annealing), milling, grinding, cold or hot rolling, extrusion, high hydrostatic external pressure or combination thereof to obtain an ordered single-phase material.

(36) Practice of illustrative method embodiments enables simple, inexpensive, and scalable way of industrial production of single-phase materials described above. The liquid media employed for the liquid-assisted embodiment described above can be selected from the list of inexpensive, mass-produced organic solvents (e.g. isopropanol and other alcohols).

(37) The following Examples are offered to further illustrate embodiments of the invention without limiting the scope of method embodiments.

(38) Preparation of Three and Four Principal Element (Mixed Metal) TMDCs by Solid-State Mechanical Exfoliation and Annealing:

(39) Materials and Analytical Techniques.

(40) Ultra-high purity Ar (Matheson, 99.999%), ultra-high purity He (Matheson, 99.999%), MoS.sub.2 (Sigma-Alrdich, 99% purity), WS.sub.2 (Sigma-Alrdich, 99% purity), MoSe.sub.2 (Alfa Aesar, 99.9% purity), WSe.sub.2 (Alfa Aesar, 99.8% purity), and NbSe.sub.2 (Alfa Aesar, 99.8% purity) were used. As-received commercially available transition metal dichalcogenides, MoS.sub.2, WS.sub.2, MoSe.sub.2, WSe.sub.2 and NbSe.sub.2, were used as starting materials without further purification. TaS.sub.2 was prepared from Ta powder (99.99% purity) and S (Alfa Aesar, 99.9995% purity). In particular, TaS.sub.2 was prepared by ball milling a nearly stoichiometric mixture of tantalum and sulfur (5% excess). The milling was performed for 4 hours in a Fritsch, Pulverisette 7 milling machine, then followed by heat treatment of the resulting powder in a quartz tube sealed under 0.75 bar pressure of high purity helium for 5 days.

(41) Powder X-Ray Diffraction (XRD):

(42) The measurements were carried out using a PANalytical X'PERT powder diffractometer with an Xcelerator detector in the 20 range from 10° to 80° with 0.020 step size employing Cu-K.sub.α1 radiation (λ=0.15406 nm).

(43) Thermogravimetric Analysis (TGA):

(44) TGA data were collected using Netzsch Luxx STA 409 PG. About 10 mg of the investigated materials were placed in alumina crucibles and heated up under argon from room temperature to 1450° C. with a ramping rate of 10° C./min.

(45) HAADF-STEM and STEM-EDS Measurements:

(46) TEM experiments were performed on a Titan Themis (FEI) probe Cs-corrected TEM. High-resolution HAADF-STEM images were collected by the convergence semi-angle of 18 mrad and a collection semi-angle of 99-200 mrad at 200 kV. STEM-EDS analysis was carried out using a Super-X EDS detector attached to the Titan Themis. Focused Ion Beam (FIB) cross-sectioning was performed on a Helios Nanolab G3 UC dual-beam instrument (FEI). A liftout for TEM was carried out using standard in-situ TEM liftout procedures by means of the EZLift micromanipulator and Multi-Chem gas injection system [38, 39]. For the FIB cross-sectioning, a large agglomerate of particles was selected and covered with a protective layer of carbon that prevented the sputtering of the top surface of the sample during the experiment. Next, a trench was sputtered from both sides of the particle, resulting in a rectangular shape specimen, which afterwards was attached to a tungsten needle and thinned to electron transparency.

(47) Raman Spectroscopy: Powdered samples were spread on glass cover slips and analysed with a Horiba XploRA Raman microscope (HORIBA Scientific, Edison, N.J.) using 532-nm excitation (8.3.Math.10.sup.3 W/cm.sup.2) and a 100×(0.90 NA) objective. The detector was a front-illuminated Horiba Synapse EMCCD camera, and the acquisition time was 60 seconds. For each sample, the displayed spectrum was an average of 10 locations.

(48) High-Resolution X-Ray Photoelectron Spectra (XPS):

(49) Measurements were carried out for compositional analysis. A few milligrams of powder samples were mounted on a double-sided Scotch tape. XPS spectra for S 2p, Se 3d, Mo 3d and W 4f were acquired using physical electronic 5500 multi technique system with an Al-K.sub.α source. To compensate the charging effects, the binding energies of all peaks were corrected using standard carbon peak at 285 eV.

Example 1.—MoS.SUB.2.—WS.SUB.2 .System

(50) In a typical experiment, a total 1 g of the stoichiometric mixture of MoS.sub.2 powder and WS.sub.2 powder in the 1:1 molar ratio was transferred to a milling container together with eight 12 mm stainless steel balls (about 7 g each) so that ball-to-sample ratio was close to 56:1. After sealing the container under argon, ball milling was carried out for various time intervals at 600 rpm in a horizontal planetary mill Fritsch, Pulverisette 7. To facilitate the uniform milling and prevent caking of the powder during the processing, the milling mode was alternated between forward and reverse (30 min each) with an intermittent pause of 5 min. To investigate the effect of milling regime, the same amount of the sample was also processed in a high-energy mixer mill (SPEX, 8000M mill) in a stainless steel container with two 12.7 mm and four 6.35 mm grinding balls (ball-to-sample ratio=18:1). Ball milled powders were characterized using powder X-ray diffraction (XRD), differential scanning calorimetry and the thermogravimetric analysis (DSC/TGA), Raman spectroscopy, high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), scanning transmission electron microscopy energy dispersive spectrometry (STEM-EDS), scanning electron microscopy (SEM), scanning electron microscopy energy dispersive spectrometry (SEM-EDS) and scanning and transmission electron microscopies (SEM and TEM) as appropriate. In each example, milling was conducted at ambient temperature.

(51) XRD for the samples processed for different periods of time in planetary and mixer mills are shown in FIGS. 1a and 1b, respectively. Due to identical crystal structure and very close cell parameters for MoS.sub.2 and WS.sub.2, no shift in the Bragg peak positions could be observed even after a prolonged milling. However, strong peak broadening that becomes more apparent with the increasing milling time, which is a typical signature of disordering in the sample is clearly observed.

(52) SEM evaluation of two samples milled for 15 hours in the planetary mill and the mixer mill are shown in FIG. 2a, 2b. They revealed particle agglomeration on a microscopic scale. The particle morphology is highly irregular, with a broad particle size distribution. The distribution of constituting elements within the particles was analyzed using the backscattering electron imaging (BEI) combined with EDS. Backscattering analysis suggests uniform composition; i.e. no separate particles or regions of high concentrations of MoS.sub.2 or WS.sub.2 were present (FIG. 2c, 2d). Both samples on the micrometer-size scale appeared homogeneous.

(53) Analysis by SEM-EDS showed the characteristic peaks for tungsten, molybdenum, sulfur and carbon. The latter coming from the sample holder grid. As can be seen in FIG. 3, SEM-EDS confirms an even distribution of W, Mo, and S throughout the particle(s). Unfortunately, some overlapping peaks of S K- and Mo L-series in the SEM-EDS spectrum made the analysis qualitative. Therefore, the signal coming from W appears to be stronger compared to Mo. Similar results were obtained for the samples processed in the mixer mill (not shown).

(54) For samples processed either in the planetary or mixer mills, TEM (FIG. 4a, 4b) reveals disordered layered structures, which are consistent with the broadening of Bragg peaks in their XRD patterns (FIGS. 1a, 1b). Again, the uniform layer spacing of about 0.6 nm, characteristic for both MoS.sub.2 and WS.sub.2 (002) basal plane, cannot be indicative of a solid solution or layered hetero-structures due to the similarity of the MoS.sub.2 and WS.sub.2 cell parameters.

(55) The HAADF-STEM studies confirm disordering in both milled samples (FIG. 5a, 5b). The images clearly show high degrees of distortion and poor crystallinity of the as-milled materials. The Z-dependence visualizes W-rich sites as white to light-grey zones, and Mo-rich—as grey to dark-grey zones. Based on the Z-contrast images, in both cases a solid solution of MoS.sub.2 and WS.sub.2 may be suggested.

(56) However, the Raman spectrum of the sample (FIG. 6) does not agree with that published for a single-phase (Mo.sub.1-xW.sub.x)S.sub.2 [40] On the contrary, it contains a set of broad peaks at 352, 380, 407 and 418 cm.sup.−1 that resemble those of the individual MoS.sub.2 and WS.sub.2 phases in laminar MoS.sub.2/WS.sub.2 heterostructures. [41] Annealing the ball-milled powders at 1000° C. for 16 hours under helium produces a fused single-phase material, whose Raman spectrum (FIG. 6) matches that of (Mo.sub.0.5W.sub.0.5)S.sub.2.

(57) In order to obtain a crystalline material, the sample milled in a planetary ball mill for 15 hours was heat treated at 950 degrees C. The annealing temperature of 950 degrees C. was selected based on the results of DCS/TGA analysis for pure binary TMDCs (FIG. 7) and analytical data published in open literature. At ambient pressure, bulk MoS.sub.2, WS.sub.2 and WSe.sub.2 are fairly stable up to ˜1100 degrees C., but they slowly release chalcogens between 800-1000 degrees C. in high vacuum [42,43]. This suggests that all three binary TMDCs are approaching the edge of their stability at T˜950-1000 degrees C., where mobile reactive {MX.sub.Y} species formed can drive their chemical conversion.

(58) The powder XRD pattern of the material heat treated for 16 hours in an argon atmosphere consisted of sharp crystalline peaks (FIG. 8). Significantly improved crystallinity of the material was also confirmed by the HAADF-STEM measurements (FIGS. 9a, 9b). The heat treated sample consists of a 2H polymorph. Both HAADF- and EDS-STEM indicated a uniform distribution of Mo and W throughout the lattice.

Example 2.—MoSe.SUB.2.—WS.SUB.2 .and MoS.SUB.2.—WSe.SUB.2 .Systems

(59) Processing of both MoS.sub.2—WSe.sub.2 and MoSe.sub.2—WS.sub.2 systems was performed in a planetary mill. For this purpose, 2 g of corresponding equimolar mixture was ball milled at 600 rpm in a planetary mill for 30 hours with eight 12 mm stainless steel balls. The XRD traces of the samples obtained (FIGS. 10a, 10b) showed a significant Bragg peak broadening indicative of disordering in the starting materials. Partially incomplete homogenization of the as-milled samples can be concluded from the enhanced Bragg scattering corresponding to the individual chalcogenides. The 1:1 (molar) MoS.sub.2—WSe.sub.2 is clearly more homogeneous when compared to the 1:1 (molar) MoSe.sub.2—WS.sub.2 system.

(60) After the heat treatment at 1000 degrees C. for 16 hours in argon, both of the investigated materials crystalized into mixed TMDC systems with characteristic Bragg peaks (FIG. 10a for MoS.sub.2—WSe.sub.2 and FIG. 10b for MoSe.sub.2—WS.sub.2) that correspond to Mo.sub.05W.sub.0.5S.sub.05Se.sub.0.5. In the case of MoSe.sub.2—WS.sub.2 system, both the formation of the solid solution and the crystallization were incomplete as evidenced by the high-angle shoulder of the Bragg peak at 2θ ≈15 degrees and overall broader Bragg peaks when compared to the MoS.sub.2—WSe.sub.2 sample.

(61) The Raman spectrum of the heat treated material confirms the XRD results (FIG. 11). In the case of MoS.sub.2—WSe.sub.2 system, it consists of three characteristic broad bands at about 265, 355 and 400 cm.sup.−1, clearly deviating from those observed in the starting MoS.sub.2, WSe.sub.2 and the as-milled sample. The XRD pattern of the latter indicates the presence of both MoS.sub.2 and WSe.sub.2 phases in the material even after 30 hours of ball milling (FIG. 12). Once again, STEM-EDS suggests compositional homogeneity of heat treated samples (FIG. 13).

(62) The high-resolution X-ray photoelectron spectroscopy (XPS) (FIG. 14) reveals the presence of all four-principal elements, Mo, W, S and Se, on the surface of the heat treated material. The XPS spectrum of the annealed (Mo.sub.0.5W.sub.0.5)SSe contains peaks at 229.5 and 232.6 eV corresponding to Mo.sup.4+(3d.sub.5/2) and Mo.sup.4+(3d.sub.3/2) ions and the signal at 227 eV agrees with the position characteristic for S.sup.2−(2s) ion [44, 45]. The peaks at 32.9 and 35.1 eV are indicative of W.sup.4+(4f.sub.7/2 and 4f.sub.5/2) in TMDCs [46] while the weak signal at 38 eV suggests the presence of a minor W.sup.6+ (WO.sub.3) contamination [44]. Finally, the peak around 162.5 eV corresponds to the unresolved signals by S.sup.2−(2p.sub.3/2)/S.sup.2−(2p.sub.1/2). The additional peaks at ˜161 and ˜167 eV belong to Se.sup.2−(3p.sub.3/2) and Se.sup.2−(3p.sub.1/2), respectively [47]. The signal at ˜55 eV can be assigned to overlapping 3d.sub.5/2 and 3d.sub.3/2 peaks of Se.sup.2−.

(63) It is worth noting that the frequency of milling has a distinct effect on its result. Thus, the XRD pattern of the materials processed for 30 hours in the planetary mill at 300 rpm (processing frequency of 5 Hz) is quite similar to that obtained after one hour of milling of the MoS.sub.2 and WSe.sub.2 mixture in a SPEX 8000M unit (processing frequency of ˜18 Hz.sup.1), and the XRD pattern of the sample processed for 4 hours in the SPEX 8000M mill closely resembles that of the powder generated in the Fritsch Pulverisette 7 planetary mill at 600 rpm (the processing frequency of 10 Hz) for 30 hours (FIG. 15).

(64) The material of the milling equipment does not seem to affect the overall outcome of the synthetic process and a single-phase (Mo.sub.0.5W.sub.0.5)SSe could be successfully prepared in both silicon nitride and hardened steel vials after heat treatment. In the latter case, processed material contained up to 0.4 at. % of iron contamination after 30 hours of milling as determined by the X-ray fluorescence spectrometry (XRF). Similar amount of iron was also discovered in other TMDC samples prepared using the hardened steel milling sets.

(65) (Mo.sub.0.5W.sub.0.5)SSe crystallizes in space group P6.sub.3/mmc where Mo and W atoms randomly occupy the 2c position (⅓, ⅔, ¼) in the crystal lattice. The 4f site (⅓, ⅔, z) is filled randomly with S and Se. Shapes of Bragg reflections in the XRD pattern are highly anisotropic owing to distinctly plate-shaped particles and a nonrandom distribution of their orientations, which causes texturing and asymmetric broadening of the (h 0 l) Bragg peaks. Correcting for these effects requires spherical harmonics expansion to approximate crystallite shapes for Rietveld-based refinements. Results of which for this and other compounds described in this work are listed in Table 1.

(66) TABLE-US-00001 TABLE 1 Structural parameters of TMDCs derived from Rietveld refinements. The space group is P6.sub.3/mmc (#194). Metal atoms (Mo, W, Nb or Ta) occupy 2c (⅓, ⅔, ¼) site and chalcogens occupy 4f (⅓, ⅔, z) site. Standard deviations are given in parentheses. Column labelled R.sub.p lists profile residuals. Lattice parameters Phase Composition a, Å c, Å Chalcogen z/c R.sub.p Mo.sub.0.5W.sub.0.5S.sub.2 3.1628(1) 12.3581(4) 0.6229(2) 6.77 Mo.sub.0.5W.sub.0.5SSe 3.2239(5) 12.7348(3) 0.6169(2) 6.99 MoSSe 3.2246(4) 12.7069(2) 0.6168(1) 9.10 Mo.sub.0.4W.sub.0.2Nb.sub.0.4S.sub.0.8Se.sub.1.2 3.3073(2) 12.5718(9) 0.6151(2) 8.86 Mo.sub.0.6W.sub.0.2Ta.sub.0.2S.sub.0.8Se.sub.1.2 3.1754(1) 12.4158(2) 0.6186(3) 9.01 Mo.sub.0.25W.sub.0.25Nb.sub.0.25Ta.sub.0.25SSe 3.3015(2) 12.5189(9) 0.6223(3) 8.82

Example 3.—Three to Six Principal Element (Mixed Metal) TMDC Systems

(67) In a typical experiment, a 1 or 2 g sample of a physical mixture of two or more different binary TMDCs, taken in an appropriate stoichiometric proportion, was milled in either stainless steel milling container with eight 11.9 mm stainless steel balls, or in a silicon nitride vial with three 12.7 mm silicon nitride grinding balls using a two-station horizontal planetary mill (Fritsch, Pulverisette 7), or a shaker mill (SPEX 8000M) for various periods of time (1-30 hours). The milling containers were loaded and sealed under ultra-high purity argon in a glove box. To facilitate uniform milling and to prevent kinking of the powder during the processing, the milling mode of the planetary mill was alternated between forward and reverse rotations (30 min each) with an intermittent pause of 5 min. Subsequently, as-milled powders were pressed into pellets under argon in a glove box, placed in a quartz tube, which was further sealed under 0.75 bar of ultra-high purity helium. Typically, the heat treatment was conducted by ramping the temperature to 1000° C. and annealing the material for 16 hours or longer. Afterwards, samples were allowed to cool down to room temperature in the furnace. For analytical characterization, prepared materials were crushed in a mortar with a pestle and stored in a glove box under high-purity argon. The material of the milling equipment does not affect the overall outcome of the synthetic process. Also, according to X-ray fluorescence spectrometry (XRF), samples prepared using the hardened steel setup contained up to 0.4 at. % of iron contamination.

(68) Ball milling of the equimolar mixture of bulk MoS.sub.2 and MoSe.sub.2, followed by heat treatment of the resulting powder, reliably and reproducibly yields the known three-element chalcogenide, MoSSe. In this case, the presence of the starting materials in the as-milled powder was confirmed by both XRD and Raman spectroscopy, while a single-phase MoSSe forms after annealing at 1000° C. (FIG. 16, 17).

(69) Starting from bulk MoS.sub.2, WSe.sub.2 and NbSe.sub.2, a five-element compound with the nominal composition of (Mo.sub.0.4W.sub.0.2Nb.sub.0.4)S.sub.0.8Se.sub.1.2 (FIG. 18a, 18b) was prepared. Similar to other discussed cases, after ball-milling for 30 h, the material emerges as a highly disordered multi-phase powder. Its Raman spectrum (FIG. 18b) contains two prominent peaks at 378 and 404 cm.sup.−1, matching MoS.sub.2, and the very broad signal at ˜250 cm.sup.−1 that combines characteristic peaks of NbSe.sub.2 and WSe.sub.2 at 228, 236 and 248 cm.sup.−1. Subsequent annealing at 1000° C. converts the as-milled powder into a fused single-phase (Mo.sub.0.4W.sub.0.2Nb.sub.0.4)S.sub.0.8Se.sub.1.2.

(70) Further, (Mo.sub.0.6W.sub.0.2Ta.sub.0.2)S.sub.0.8Se.sub.1.2(FIG. 19a, 19b) was prepared from a stoichiometric mixture of MoSe.sub.2, WS.sub.2 and TaS.sub.2 using the same procedure. However, in this instance, an extended annealing time of 72 hours was necessary to obtain a crystalline material suitable for Rietveld refinement.

(71) Finally, the six-component compound, (Mo.sub.0.25W.sub.0.25Nb.sub.0.25Ta.sub.0.25)SSe (FIG. 20a, 20b) has been prepared by ball milling and subsequent annealing of an equimolar (1:1:1:1) mixture of MoS.sub.2, WSe.sub.2, NbSe.sub.2 and TaS.sub.2.

(72) The Bragg peaks in the XRD patterns of all five- and six-principal element (mixed metal TMDCs remain substantially broadened even after a prolonged annealing, and a minor oxide impurity was detected in both Ta-containing samples. Reasonably assuming similarity of particle sizes and shapes in all three materials prepared from similar precursors, the observed Bragg peak broadening can be attributed to reduced crystallinity due to built-in strain. Since both Nb and Ta are larger than Mo and W, combining them in the same metallic layer of a multi-element TMDC should cause distinct distortion of the layers that propagates into the entire 3D-lattice.

(73) In achieving the results described above, the tangential component of ball-milling, which is accountable for the shearing action, appears to enable mechanical exfoliation of bulk TMDCs. At the same time, the exfoliated TMDCs can easily restore their 3D-arrangements by restacking, which is used to construct vertical 3D-heterostructures from exfoliated two dimensional TMDCs, graphene, h-BN and similar single-layer nanomaterials [49, 50]. Hence, it is quite feasible that mechanical exfoliation and spontaneous restacking of different TMDCs in a way similar to reshuffling a deck of playing cards, can produce 3D hetero-assemblies that appear uniform for EDS but, in fact, are heterostructured materials. The latter can further transform into uniform single-phase materials during subsequent heat treatment. However, the inventors do not intend to be bound by any above theory or above explanation.

(74) Experiments using lower-speed (300 rpm) ball milling of bulk MoS.sub.2 and WSe.sub.2 shed some additional light upon layer-reshuffling during ball-milling. Contrary to the more intense (600 rpm) processing, both MoS.sub.2 and WSe.sub.2 phases remain clearly distinguishable in the XRD patterns of the as-milled powders even after 30 hours of milling (FIG. 21), and the STEM-EDS analysis now clearly reveals the presence of two different types of particles in this material (FIG. 22a-22e). The first kind of particles looks compositionally uniform (FIG. 22a) resembling particles in the as-milled samples discussed above. The second group consists of hetero-assemblies, where the “reshuffling” remains incomplete, and individual MoS.sub.2 and WSe.sub.2 segments can be distinguished around the areas of their overlap (FIG. 22b). The Focused Ion Beam (FIB) cross-sectioning experiment performed on a large agglomerate of the particles, which was cut by a Ga-ion beam, attached to a tungsten needle and rotated in the TEM chamber to produce a side view, clearly demonstrates its heterogeneous layered structure (FIG. 22c, 22d). Heating the as-milled, incompletely reshuffled powder at 1000 degrees C. for 16 hours produces a fused single-phase (Mo.sub.0.5W.sub.0.5)SSe identical to the material obtained in other experiments. (FIG. 23) Thus, available experimental data strongly suggest that mechanical milling of MoS.sub.2 with WSe.sub.2 leads to stochastic rearrangement of both individual layers and incompletely exfoliated slabs into 3D hetero-assemblies where both kinds of building blocks retain their compositional individuality (FIG. 22d, 22e).

(75) The above examples demonstrate that the method embodiments of the invention described above enable easy and reliable preparation of diverse multi-principal element (mixed metal) TMDCs that were either unknown or barely accessible via conventional materials fabrication routes.

(76) Mechanochemical exfoliation coupled with stochastic restacking of binary precursors enables the generation of layered 3D heterostructures, and annealing of the latter generates single-phase multi-metal element materials. It is quite feasible that similar or closely related protocols can be applied to the preparation of other classes of materials, which are inaccessible or hard-to-reach through conventional synthetic routes.

(77) Another important outcome of practice of method embodiments is that mechanochemical treatment facilitates the formation of 3D-heterostructures from bulk TMDCs that may provide a path to prepare to a broad range of unusual hetero-structured nanomaterials.

(78) Finally, multi-principal element (mixed metal) materials synthesized using the method embodiments, represent a unique group of high-entropy-like systems that can serve as precursors of new 2D nanomaterials and 3D-heterostructures with future applications in electronics, electrochemical water splitting, and advanced lubrication, to name a few.

(79) Preparation of Multi-Principal Element (Mixed Metal) TMDC's by Liquid-Assisted Exfoliation:

(80) FIG. 24 illustrates schematically liquid-phase preparation of single-phase, bulk TMDC materials according to other embodiments of the invention. After synthesis, the liquid medium can be removed by vacuum evaporation, boiling away, dry freezing or any other technique.

Example 4.—MoS.SUB.2.—WSe.SUB.2 .System

(81) Commercial MoS.sub.2 powder (Sigma-Alrdich, 99% purity) and WSe.sub.2 powder (Alfa Aesar, 99.8% purity) were used as starting materials. MoS.sub.2 and WSe.sub.2, 2 g of each powder, were separately ball milled in the presence of 1 ml of isopropanol for 30 hours using a Fritsch Pulverisette 7 planetary mill. The milling was carried out in separate milling vials sealed under argon with eight 12 mm stainless steel balls (about 7 g each) at 600 rpm. The milling mode was alternated between forward and reverse (30 min each) with an intermittent pause of 5 min to facilitate uniform shear milling.

(82) Obtained powders were dried under vacuum and corresponding amounts of the samples were weighed out to obtain stoichiometric molar ratio of 1MoS.sub.2:1 WSe.sub.2 with a total mass of 0.5 gram. Each sample was separately added to 40 grams of isopropanol and sonicated for 60 minutes in a FS20H Fisher Scientific sonicating machine. Thereafter, obtained suspensions were centrifuged at 3500 rpm for 15 min. Equal amounts of the obtained dispersions were mixed together, then the solvent was evaporated at 70° C., which led to the formation of a mixed solid assembly from exfoliated MoS.sub.2 and WSe.sub.2 phases as confirmed by XRD (FIG. 25).

(83) Next, the obtained mixed solid material was annealed at 1000 degrees C. in a quartz tube under inert gas atmosphere for 16 hours. The XRD pattern of the heat treated sample showed a highly crystalline single-phase solid combining four elements in its structure with the general chemical formula of Mo.sub.1-xW.sub.xS.sub.2-2xSe.sub.2x (FIG. 26)

Example 5.—MoS.SUB.2.—WSe.SUB.2 .System

(84) Starting MoS.sub.2 and WSe.sub.2 were prepared as described in Example 4. Subsequently, they were combined together in an equimolar ratio to obtain a 0.5 gram sample. The sample was suspended in 100 ml of isopropanol and sonicated for 10 hours in a FS20H Fisher Scientific sonicating machine. Next, 50 ml of isopropanol was added to the sonicated suspension, and it was centrifuged for 30 minutes at 3500 rpm. The liquid phase was separated and the precipitated material was dried in vacuum. The obtained dry solid material was annealed at 1000° C. for 16 hours in a quartz tube sealed under inert argon. FIG. 27 shows the XRD pattern of the material before annealing, indicating the presence of MoS.sub.2 and WSe.sub.2 phases in the sample. After annealing, an XRD pattern showed a highly crystalline solid solution of four component TMDC with the general chemical composition of Mo.sub.1-xW.sub.xS.sub.2-2xSe.sub.2x.

Example 6.—MoS.SUB.2.—WSe.SUB.2 .System

(85) A total 2 grams of the equimolar mixture of MoS.sub.2 powder and WSe.sub.2 powder was shear milled for 30 hours in 1 ml of isopropanol to facilitate their liquid-assisted exfoliation and restacking. The XRD pattern of the as-milled sample shown in FIG. 28 suggests that the product formed contains chemically unchanged but clearly disordered precursor phases. The absence of the characteristic peaks of (Mo.sub.0.5W.sub.0.5)SSe phase implies that only exfoliation and restacking processes may have occurred. After heat treatment at 1000° C. for 16 hours under argon, the material has transformed into a crystalline single-phase (Mo.sub.0.5W.sub.0.5)SSe as confirmed by XRD (FIG. 29).

(86) In practicing these and other embodiments of the present invention, heat treating of the disordered layered mixed TMDCs can be conducted at elevated temperatures between 100 and 1500 degrees C. in an inert or non-reactive gas atmosphere to produce the ordered layered mixed TMDC. For purposes of illustration and not limitation, the heat treating time can be between 1 minute to 72 hours or longer. Heat treating can be conducted in an inert atmosphere comprise helium, argon, krypton, xenon, nitrogen, methane and any other gas, which shows no reactivity towards the binary TMDCs and the produced disordered layered mixed TMDC.

(87) The present invention further envisions a subsequent method step that involves exfoliating the ordered layered mixed TMDC (crystalline material) to produce a single layer or multi-layer crystalline nanostructure. Exfoliation can be conducted using sonication in a liquid or any other appropriate exfoliation technique.

(88) Although the present invention has been described with respect to certain illustrative embodiments and examples for purposes of illustration and not limitation, those skilled in the art will understand that changes and modifications can be made therein within the scope of the present invention as set forth in the appended claims.

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