Substrate-free crystalline 2D nanomaterials

Abstract

The present disclosure generally relates to compositions comprising substrate-free 2D crystalline nanomaterials of binary compounds of formula (M).sub.x(Te).sub.y, and the method of making and using the substrate-free crystalline 2D crystalline nanomaterial.

Claims

1. A composition comprising a substrate-free 2D crystalline nanomaterial of a binary compound of formula (M).sub.x(Te).sub.y, wherein said M is Ag, and the formula is Ag.sub.4.53Te.sub.3, the 2D crystalline nanomaterial is characterized by a non-symmetric structure.

2. The composition of claim 1, wherein the 2D crystalline nanomaterial has a monolayer or a multilayer structure with a thickness of 0.1-30 nm.

3. The composition of claim 1, wherein said M is Ag, and the formula is Ag.sub.4.53Te.sub.3, the 2D crystalline nanomaterial is characterized by an X-ray diffraction pattern (CuKα radiation, λ=1.54056 A) comprising peaks at 25.23°, 29.27°, 34.94°, and 41.42°.

4. The composition of claim 1, wherein the 2D crystalline nanomaterial is thermally stable having substantially no mass change up to eight- hundred degrees Celsius.

5. A method of preparing substrate-free 2D crystalline nanomaterial of claim 1, wherein the method comprises: providing a substrate-free 2D Tellurene crystalline nanomaterial; preparing a suspension of the substrate-free 2D Tellurene crystalline nanomaterial in a first solvent; providing a salt of a formula M.sub.mX.sub.n, wherein 1≤m≤6, 1≤n≤6, X is an acid radical; preparing a suspension of the salt of the formula M.sub.mX.sub.n in a second solvent, wherein the first solvent and the second solvent may be same of different solvent; mixing the suspension of the substrate-free 2D Tellurene and the suspension of the salt and allowing the reaction between the substrate-free 2D Tellurene and the salt; and forming the substrate-free 2D crystalline nanomaterial having the binary compound of formula (M).sub.x(Te).sub.y, wherein said M is Ag, and the formula is Ag.sub.4.53Te.sub.3, the 2D crystalline nanomaterial is characterized by a non-symmetric structure.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIGS. 1A-1E are in FIG. 1 characterizations for Example 1. 1A. The optical image of the 2D PdTe.sub.2 nanoflake. 1B. SEM-EDS result of the 2D PdTe.sub.2 nanoflake. 1C. Hight-resolution TEM image of the as-synthesized 2D PdTe.sub.2 nanoflake. 1D. Atomic force microscope (AFM) image of a 12.9 nm 2D PdTe.sub.2 flake. 1E. A hexagonal basis per unit cell in PdTe.sub.2. 1F. XRD pattern of the as-synthesized 2D PdTe.sub.2 flake.

(2) FIGS. 2A-2B in FIG. 2 are different behaviors of Example 1 and 2D tellurene. 2A. Thermal gravimetric analysis of the 2D tellurene and 2D PdTe.sub.2 nanoflake. 2B, UV-vis spectra of the 2D tellurene and PdTe.sub.2 nanoflakes.

(3) FIGS. 3A-3F in FIG. 3 are characterizations for Example 2. 3A. unit cell of the Ag.sub.4.53Te.sub.3 crystal structure. 3B-3E. High resolution TEM, Optical image, AFM and EDS results of the as-synthesized 2D Ag.sub.4.53Te.sub.3, respectively. 3F. XRD pattern of the as-synthesized 1D and 2D silver telluride.

(4) FIGS. 4A-4D in FIG. 4 are second harmonic generation (SHG) results for Example 2. FIG. 4A shows SHG results of the 2D Ag.sub.4.53Te.sub.3. FIG. 4B shows angle dependent Raman spectra of the 2D Ag.sub.4.53Te.sub.3. FIG. 4C shows standard contact PFM investigation for 2D Ag.sub.4.53Te.sub.3. FIG. 4D shows average amplitude variations versus applied voltages.

(5) FIG. 5A in FIG. 5 shows sketch of the nanogenerator's structure. FIG. 5B in FIG. 5 shows the open voltage of the generators comprising 1D Ag.sub.2Te nanowire and 2D Ag.sub.4.53Te.sub.3.

DETAILED DESCRIPTION

(6) For the purposes of promoting an understanding of the principles of the present disclosure, reference will now be made to the embodiments illustrated in the drawings, and specific language will be used to describe the same. It will nevertheless be understood that no limitation of the scope of this disclosure is thereby intended.

(7) In the present disclosure the term “about” can allow for a degree of variability in a value or range, for example, within 10%, within 5%, or within 1% of a stated value or of a stated limit of a range.

(8) In the present disclosure the term “substantially” can allow for a degree of variability in a value or range, for example, within 90%, within 95%, or within 99% of a stated value or of a stated limit of a range.

(9) In the present disclosure, the term “2D material” refers to an allotrope of the materila. One well-known 2D material is graphene, which is an allotrope of carbon.

(10) In the present disclosure, the term “substrate-free 2D material” refers to 2D material that are prepared through a solution condition instead of being deposited on a substrate. The disadvantage of a 2D material on a substrate is that such material cannot be easily used and is not available as standalone 2D material. Therefore, the substrate-free 2D material disclosed in the present disclosure provides a standalone, stable and convenient source of pure 2D material. A skilled artisan will appreciate that “substrate-free 2D material” refers to “substrate-free 2D material” as made. The later prepared composition by any other physical and/or chemical mixing or combining the as made “substrate-free 2D material” with another material, even could be named as “substrate”, should still be within the definition of “substrate-free 2D material” as defined here.

(11) In the present disclosure, the term “acid radical” refers to any organic or inorganic ion formed after removal of hydrogen ion (H.sup.+ ion) from an acid. A representative acid radical for the present disclosure may be but is not limited to F.sup.−, Cl.sup.−, Br.sup.−, I.sup.−, NO.sub.3.sup.−, SO.sub.4.sup.2−, HCOO.sup.−, or CH.sub.3COO.sup.−.

(12) In one embodiment, the present disclosure provides a substrate-free 2D crystalline nanomaterial of a binary compound of formula (M).sub.x(Te).sub.y, wherein M is selected from the group consisting of Cd, Pb, Cu, Co, Ni, Ta, Mo, W, Pd, Pt, Zn, Bi, Sb, Ga, Ge, Fe, Sn, and Zr, and wherein 1≤x≤6, 1≤y≤6.

(13) In one embodiment, the present disclosure provides a substrate-free 2D crystalline nanomaterial of a binary compound of formula (M).sub.x(Te).sub.y, wherein the 2D crystalline nanomaterial has single crystalline nature.

(14) In one embodiment, the present disclosure provides a substrate-free 2D crystalline nanomaterial of a binary compound of formula (M).sub.x(Te).sub.y, wherein the 2D crystalline nanomaterial has a monolayer or a multilayer structure with a thickness of 0.1-30 nm, 0.1-20 nm, 0.1-10 nm, 0.1-5 nm, 0.1-3 nm, 1-30 nm, 1-20 nm, 1-10 nm, 1-5 nm, 1-3 nm, or any combination thereof.

(15) In one embodiment, the present disclosure provides a substrate-free 2D crystalline nanomaterial of a binary compound of formula (M).sub.x(Te).sub.y, wherein said M is Pd, the formula is PdTe.sub.2, the 2D crystalline nanomaterial is characterized by an X-ray diffraction pattern (CuKα radiation, λ=1.54056 A) comprising peaks at 30.02°, 43.31°, 43.64°, 55.23° and 56.89°. The five peaks are corresponded to (011), (012), (101), (201) and (112), respectively.

(16) In one embodiment, the present disclosure provides a substrate-free 2D crystalline nanomaterial of a binary compound of formula (M).sub.x(Te).sub.y, wherein said M is Ag, and the formula is Ag.sub.4.53Te.sub.3, the 2D crystalline nanomaterial are characterized by an X-ray diffraction pattern (CuKα radiation, λ=1.54056 A) comprising peaks at 25.23°, 29.27°, 34.94°, and 41.42°. The four peaks are corresponded to (302), (3-14), (4-14) and (5-14), respectively.

(17) In one embodiment, the present disclosure provides a method of preparing substrate-free 2D crystalline nanomaterial of the present disclosure, wherein the method comprises: providing a substrate-free 2D Tellurene crystalline nanomaterial; preparing a suspension of the substrate-free 2D Tellurene crystalline nanomaterial in a first solvent; providing a salt of a formula M.sub.mX.sub.n, wherein 1≤m≤6, 1≤n≤6, X is an acid radical; preparing a suspension of the salt of the formula M.sub.mX.sub.n in a second solvent, wherein the first solvent and the second solvent may be same of different solvent; mixing the suspension of the substrate-free 2D Tellurene and the suspension of the salt and allowing the reaction between the substrate-free 2D Tellurene and the salt; and providing the substrate-free 2D crystalline nanomaterial of the present disclosure.

(18) Example 1: Substrate-Free 2D Crystalline Palladium Ditelluride (PdTe.sub.2)

(19) Synthesis of Example 1:

(20) 2D tellurene, which is the starting material, is prepared by a method disclosed in Wang, Yixiu, et al., Large-area solution-grown 2D tellurene for air-stable, high-performance field-effect transistors, arXiv:1704.06202, Apr. 20, 2017. In a typical synthesis, 37 ml of freshly 2D tellurene nanoflake (0.4 mmol) was precipitated by adding about 100 ml of acetone. The precipitated tellurene nanoflakes were dispersed in 79 ml of deionized water to form a suspension under mild magnetic stirring at room temperature. Then, 0.1 g PdCl.sub.2 was dispersed in 30 mL of deionized water. After a short duration of sonication, 1 mL of the PdCl.sub.2 solvent was added drop-by-drop into the above 2D tellurene deionized water suspension. Silver grey 2D tellurene gradually turned black, which indicates the conversation from 2D tellurene to substrate-free crystalline 2D palladium ditelluride (PdTe.sub.2).

(21) Structure Characterization of Example 1

(22) FIG. 1A shows the optical image of the substrate-free of Example 1, which adopts the similar morphology and size with the template 2D tellurene with lengths ranging from 50 to 100 um. But the color of transformed 2D PdTe.sub.2 is purple, which is different from 2D tellurene. The Scanning electron microscopy energy-dispersive spectroscopy (SEM-EDS) element maps of fields of nanocrystals (FIG. 1B) further confirmed that Pd and Te are evenly distributed among the 2D nanocrystal. Next, high resolution TEM was employed to further confirm the crystal structure. The beam of electrons is transmitted vertically through the surface of the 2D crystal. As is shown in FIG. 1C, the structure shows periodic symmetry consisting of three atoms. The interplanar spacings are 0.51 nm and 0.23 nm, which corresponds to PdTe.sub.2 (0001) and (−12-10) planes, respectively. As is illustrated by the top-view 3D image overlaid on the TEM image, every periodic three atoms are made of two Pd atoms and one Te atom. Therefore, the 2D PdTe.sub.2 are growing in [0001] direction, and the width is [−12-10] direction. The atomic-thin nature and smooth surface of the PdTe.sub.2 flake is verified with the atomic force microscopy (AFM) characterization. As s shown in FIG. 1D, the thickness of this 2D PdTe.sub.2 is 12.9 nm. FIG. 1E suggests a hexagonal basis with one palladium and two tellurium atoms per unit cell having lattice parameters a=4.0365 A and c=5.1262 A. It is noted that the resultant c/a=1.27 is the smallest value amongst the isoelectronic, isostructural transition metal dichalcogenides (TMDC). FIG. 1F provided the XRD pattern of the as synthesized 2D PdTe.sub.2 flake.

(23) The thermal stability of the as-synthesized 2D PdTe.sub.2 and the template 2D tellurene was compared as shown in FIG. 2A. It is noticed that the 2D tellurene cannot withstand the temperature higher than 500° C. in the flow of the N.sub.2 gas. On the contrary, it was found that there is nearly no mass change when the temperature is raised up to 800° C. for the as-synthesized 2D PdTe.sub.2. This result not only illustrates the success of the chemical transformation process but also proving the high thermal stability of the 2D PdTe.sub.2. FIG. 2B indicates the UV-vis absorption spectrum of the 2D tellurene and 2D PdTe.sub.2. It is shown that 2D tellurene has two broad typical absorption peaks locates at 570 and 800 nm, respectively. However, the peak at 570 nm disappears when PdTe.sub.2 is examined.

(24) Potential Application of Example 1

(25) There have been extensive efforts to achieve materials which host topologically nontrivial states and are simultaneously robust superconductors for the practical deployment of topological and hybrid electronic quantum materials. Example 1 is a semimetal that would potentially meet this need. Example 1 is an intrinsic bulk superconductor (Tc≈1.7 K).

(26) Example 1 may also be a good candidate for diverse promising applications in electronics, optics, superconductivity, quantum electronics, quantum computing, etc.

(27) Example 2: Substrate-Free 2D Crystalline Ag.sub.4.53Te.sub.3

(28) Synthesis of Example 2:

(29) 2D tellurene, which is the starting material, is prepared by a method disclosed in Wang, Yixiu, et al., Large-area solution-grown 2D tellurene for air-stable, high-performance field-effect transistors, arXiv:1704.0620, 2017. In the synthesis of Example 2, Example 2 was obtained by using the chemical transformation with sacrificing 2D tellurene. Comparing to the reaction in one-dimension, the lateral dimension limitation and differential thermodynamic were introduced in the lateral direction of the flake. In a typical synthesis, 37 ml of freshly tellurene nanoflake (0.4 mmol) was precipitated by adding about 100 mL of acetone. The precipitated tellurene nanoflakes were dispersed in 79 mL of ethylene glycol to form a suspension under mild magnetic stirring at room temperature. Then, 0.1 g AgNO.sub.3 was dispersed in 20 mL of ethylene glycol. After a short duration of sonication, 1 mL of the AgNO.sub.3 solvent was added drop-by-drop into the above 2D tellurene suspension. The silver grey 2D tellurene gradually turned brown, which indicates the conversation from 2D tellurene to 2D Ag.sub.4.53Te.sub.3.

(30) Characterization of Example 2

(31) The optical image shown in FIG. 3C illustrates that Example 2 adopts the analogous morphology and size with 2D tellurene, which has edge lengths ranging from 50 to 100 um. The typical thickness of the flakes is characterized by atomic force microscopy (AFM) (FIG. 3D). The Scanning transmission electron microscopy energy-dispersive spectroscopy (STEM-EDS) element maps of fields of nanocrystals (FIG. 3E) further confirmed that Ag and Te are evenly distributed among the 2D nanocrystal. With the assistance of the EDS element percentage analysis, it can be found that Ag penetration into the matrix of 2D tellurene happens non-stoichiometrically. Then next, high resolution TEM was employed to further confirm the crystal structure. The beam of electrons is transmitted vertically through the surface of the 2D crystal. From the HR-TEM image, it was found the lattice space is different from the Te. See Wang, Y. et al. Field-effect transistors made from solution-grown two-dimensional tellurene. Nature Electronics 1, 228-236, 2018. Also, it does not match the lattice space of Ag.sub.2Te. See Moon, G. D., Ko, S., Xia, Y. & Jeong, U. Chemical Transformations in Ultrathin Chalcogenide Nanowires. ACS Nano 4, 2307-2319, 2010. Then the lattice parameters reported by the Walter etc. in 1996 were simulated. See Kahn, W. & Gunter, J. R. Preparation of Ag5-xTe3 Thin Films and Confirmation of Their Crystal Structure by High Resolution Electron Microscopy. Journal of Solid State Chemistry 123, 391-397, 1996. It is suggested that the simulated structure features (P-62 m) space group with a=b=1.34456 nm and c=1.6917 nm. The crystal structure can be described as a superstructure of tellurium. After measurement, it was found that the lattice distance of 1.63 nm and 0.67 nm match well with the interplanar spacing of (0001) and (2-1-10) in simulated Ag.sub.4.53Te.sub.3, respectively. Therefore, it can be concluded that the flake grows along [2-1-10] and the width direction is [0001].

(32) In Ag—Te system, it is well known that the Ag/Te ratio vary from 1:1 to 2:1. Three minerals are empressite AgTe, stuetizite and hessit Ag.sub.2Te. See Voronin, M. V., Osadchii, E. G. & Brichkina, E. A. Thermochemical properties of silver tellurides including empressite (AgTe) and phase diagrams for Ag—Te and Ag—Te—O. Physics and Chemistry of Minerals 44, 639-653, 2017. The high mobility of silver ion in this system result in the Ag—Te bonding starting from the not covalent bonding of AgTe to the only covalently bonded Ag.sub.2Te in the Te anion frame. See Peter, B. Tellurium-Rich Tellurides. Angewandte Chemie International Edition in English 27, 759-772, 1988. While in the present disclosure, Ag.sub.4.53Te.sub.3is located between two extremes, and it therefore consists of isolated Te ions, covalently bonded Te dumbbells (see Baumer, F. & Nilges, T. A Chemical, High-Temperature Way to Ag1.9Te via Quasi-Topotactic Reaction of Stuetzite-type Ag1.54Te: Structural and Thermoelectric Properties. Inorganic Chemistry 56, 13930-13937, 2017) and containing significant amount of covalently bonded tellurium. FIG. 3A indicates a unit cell of this structure. The general structure features the polyanion substructure like the honeycomb net of isolated Te ions, the distorted Kagome net of partially covalent-bonded Te and the order Te.sup.2− dumbbells. The left circle in FIG. 3B suggests one unit cell projected parallel to [01-10]. After turning over in [0001] for 90°, the typical dimension of the unit cell can be identified, where a=b=1.34 nm and c=0.85 nm. To further prove the crystal structure, the room temperature X-ray diffraction pattern of obtained 2-D Ag.sub.4.53Te.sub.3 was obtained by testing the dry powder. The XRD pattern of the Ag.sub.4.53Te.sub.3is simulated by theoretical lattice parameters that are in good agreement with the previous literature. See Zhang, X. et al. Promising Thermoelectric Ag5-δTe3 with Intrinsic Low Lattice Thermal Conductivity. ACS Energy Letters 2, 2470-2477, 2017. From FIG. 3F, it was found that the diffraction peaks of then two patterns are almost in the same position, which illustrated the formation of Ag.sub.4.53Te.sub.3 and also verified the purity of our products. On the contrary, XRD pattern of obtained 1D Ag.sub.2Te from the same chemical transformation method shows different peaks from 2D Ag.sub.4.53Te.sub.3 (FIG. 3F), which is consistent with the previous report. See Moon, G. D., Ko, S., Xia, Y. & Jeong, U. Chemical Transformations in Ultrathin Chalcogenide Nanowires. ACS Nano 4, 2307-2319, 2010.

(33) Second harmonic generation imaging was performed on the as-sythesized 2D Ag4.53Te.sub.3, which is shown in FIG. 4A. The samples are measured on a glass substrate. Bright field optical image in FIG. 4A (i) indicates the morphology of the 2D Ag.sub.4.53Te.sub.3 samples. FIG. 4A (ii) and (iv) illustrates the light introduced onto the 2D material with vertical, horizontal and horizontal minus vertical polarization. As a result, they all show up strong signal, which suggests the nature non-symmetric structure of the 2D Ag.sub.4.53Te.sub.3. The anisotropic optical properties of as-synthesized 2D Ag.sub.4.53Te.sub.3 was further characterized by angle-resolved polarized Raman spectroscopy at room temperature. By rotating the 2D Ag.sub.4.53Te.sub.3 flakes in steps of 15°, changes was observed in the angle-resolved Raman peak intensities. The peak intensities of different modes was extracted by fitting with a Lorentz function and plotted them into the corresponding polar figures. The two strong peaks at 80 and 140 cm.sup.−1 was found to exhibit angle dependent intensity change with the polarization angle, which is shown in FIG. 4B.

(34) Standard contact PFM technology was used to investigate the out of plane piezoelectricity of 2D Ag.sub.4.53Te.sub.3. As shown in FIG. 4C, the mechanical response of the sample was measured when the vertical electrical field was applied to its surface through conducting the PFM tip. A typical piezoelectric material is strained (or stressed) under a vertical electrical field, which is reflected in the amplitude change for PFM imaging. The vertical motion of PFM tip and the vertical electric field applied make PFM imaging a powerful tool to explore the electromechanical functionalities in a vertical direction, namely, quantify the piezoelectric constant of d.sub.33 for piezoelectric materials. Here, Tip voltages from 3 to 10 V were applied to study the vertical electromechanical response of 2D Ag.sub.4.53Te.sub.3. The amplitude images under different tip voltages are shown in FIG. 4C, and the corresponding topography and phase images are displayed in FIG. 4C. Surprisingly, significant amplitude change was observed in the amplitude images when different tip voltages were applied, indicating strong inverse piezoelectricity. From average amplitude variations versus applied voltages in FIG. 4D, the vertical piezoelectric constant of deff is ˜28.2 pm.Math.V.sup.−1.

(35) Next, to further prove the piezoelectric output of the 2D Ag.sub.4.53Te.sub.3, the integrated nanogenerator based on 1D Ag2Te and 2D Ag.sub.4.53Te.sub.3 were fabricated (FIG. 5A). The active layer material (1D Ag2Te or 2D AgTe) were assembled on an indium tin oxide/PET flexible substrate (surface resistivity 60 Ω/sq) coated with a 1 um-thick polydimethylsiloxane(PDMS). Subsequently, a 1 um thick PDMS was spin-coated to cover the nanowire layer. Finally, silver nanowire was applied with a screen printer for fabricating the top electrode. The results presented in FIG. 5B showed that the 2D Ag.sub.4.53Te.sub.3 based piezoelectric nanogenerator has a significant output, while there in no signal measured from the 1D Ag.sub.2Te nanowire NGs. This result again verified the non-symmetric structure of our 2D Ag.sub.4.53Te.sub.3 and promises its application for future nanoelectronics.

(36) XRD Patterns of the Crystals

(37) The XRD patterns of the crystals are obtained on a D8 Advance X-ray powder diffractometer, equipped with a CuKa source (λ=1.54056 A) and a Vantec detector, operating at 40 kV and 40 mA. Each sample is scanned between 20° and 65° in 2θ, with a step size of 0.0057° in 2θ and a scan rate of 11.41 seconds/step, and with 2.1 mm divergence and receiving slits and a 0.1 mm detector slit. A crystalline 2D nanomaterial is deposited on the Si wafer with smooth surface. The crystal form diffraction patterns are collected at ambient temperature and relative humidity. The background for the crystal is removed by Jade 6.5 prior to peak picking. Conformation of a crystal form may be made based on any unique combination of distinguishing peaks (in units of ° 2θ), typically the more prominent peaks. Thus, a prepared sample of crystalline 2D nanomaterial is characterized by an XRD pattern using CuKa radiation as having diffraction peaks (2-theta values).

(38) TABLE-US-00001 TABLE 1 X-Ray Crystal Diffraction Peaks of Example 1 Angel ° 2 θ Intensity Ratio Crystallographic plane 30.02 1.00 (/Intensity at 30.02°) (011) 43.31 0.26 (/Intensity at 30.02°) (012) 43.64 0.24 (/Intensity at 30.02°) (101) 55.23 0.23 (/Intensity at 30.02°) (201) 56.89 0.12 (/Intensity at 30.02°) (112)

(39) TABLE-US-00002 TABLE 2 X-Ray Crystal Diffraction Peaks of Example 2 Angel ° 2 θ Intensity Ratio Crystallographic plane 25.23 0.35 (/Intensity at 41.42°) (302) 29.27 0.56 (/Intensity at 41.42°) (3-14) 34.94 0.87 (/Intensity at 41.42°) (4-14) 41.42 1.00 (/Intensity at 41.42°) (5-14)

(40) In summary, a simple, low-cost, solution-based chemical pathway to the scalable synthesis and assembly of substrate-free 2D crystalline nanomaterial was developed. This approach has the potential to produce stable, high-quality, ultrathin semiconductors with a good control of composition, structure, and dimensions for applications in electronics, optoelectronics, energy conversion, energy storage, sensors, and quantum devices. The substrate-free 2D crystalline nanomaterial of the present disclosure therefore adds a new class of nanomaterials to the large family of 2D materials and enables possibilities for the further investigation of many exciting properties and intriguing applications.

(41) Substrate-free 2D crystalline nanomaterial of the present disclosure could be a good thermoelectric material, a photothermal material for potential photothermal treatment of cancer/tumor cells in vivo, exhibits diverse promising applications in electronics, optics, thermoelectricity, superconductivity, and as a candidate for a new high-temperature Quantum Spin Hall paradigm, etc. in quantum electronics.

(42) Those skilled in the art will recognize that numerous modifications can be made to the specific implementations described above. The implementations should not be limited to the particular limitations described. Other implementations may be possible.