Top-down synthesis of two-dimensional nanosheets

Abstract

A method for synthesizing two-dimensional (2D) nanosheets comprises heating a bulk material in a solvent. The process is scalable and can be used to produce solution-processable 2D nanosheets with uniform properties in large volumes.

Claims

1. A method of preparing two-dimensional (2D) nanosheets, the method comprising: heating a bulk material in an organic solvent under reflux conditions for a time sufficient to effect the conversion of the bulk material into a plurality of two-dimensional (2D) nanosheets, the 2D nanosheets having thicknesses of 1 to 10 monolayers and lateral dimensions between 1 and 100 nm, wherein the organic solvent is selected from the group consisting of alkyl amines, fatty acids, phosphines, phosphine oxides, alcohols, alkanes, and any combination thereof.

2. The method of claim 1, wherein the bulk material is a transition metal dichalcogenide (TMDC).

3. The method of claim 2, wherein the TMDC is MoS.sub.2.

4. The method of claim 2, wherein the TMDC is MoSe.sub.2.

5. The method of claim 2, wherein the TMDC is WS.sub.2.

6. The method of claim 2, wherein the TMDC is WSe.sub.2.

7. A method of preparing two-dimensional (2D) nanosheets, the method comprising: heating a bulk material in an organic non-coordinating solvent for a time sufficient to effect the conversion of the bulk material into a plurality of two-dimensional (2D) nanosheets, the 2D nanosheets having thicknesses of 1 to 10 monolayers and lateral dimensions between 1 and 100 nm.

8. The method of claim 7, wherein the bulk material is a transition metal dichalcogenide (TMDC).

9. The method of claim 8, wherein the TMDC is MoS.sub.2.

10. The method of claim 8, wherein the TMDC is MoSe.sub.2.

11. The method of claim 8, wherein the TMDC is WS.sub.2.

12. The method of claim 8, wherein the TMDC is WSe.sub.2.

13. The method of claim 7, wherein the heating is performed under reflux conditions.

Description

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING(S)

(1) FIG. 1 shows a photoluminescence contour map of MoS.sub.2 2D nanosheets prepared according to Example 1.

(2) FIG. 2 shows a photoluminescence contour map of MoS.sub.2 2D nanosheets prepared in hexadecanol.

(3) FIG. 3 shows a photoluminescence contour map of MoS.sub.2 2D nanosheets prepared in acetic acid.

(4) FIG. 4 shows a photoluminescence contour map of MoS.sub.2 2D nanosheets prepared according to Example 3.

(5) FIG. 5 shows another photoluminescence contour map of MoS.sub.2 2D nanosheets prepared and extracted according to Example 3.

(6) FIG. 6 shows yet another photoluminescence contour map of MoS.sub.2 2D nanosheets prepared and extracted according to Example 3.

DETAILED DESCRIPTION OF THE INVENTION

(7) The following description of the embodiments is merely exemplary in nature and is in no way intended to limit the subject matter of the present disclosure, their application, or uses.

(8) As used throughout, ranges are used as shorthand for describing each and every value that is within the range. Any value within the range can be selected as the terminus of the range. Unless otherwise specified, all percentages and amounts expressed herein and elsewhere in the specification should be understood to refer to percentages by weight.

(9) For the purposes of this specification and appended claims, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, and other numerical values used in the specification and claims, are to be understood as being modified in all instances by the term “about.” The use of the term “about” applies to all numeric values, whether or not explicitly indicated. Also, the use of “˜” is throughout the disclosure is understood to be a symbolic representation the term “about.” This term generally refers to a range of numbers that one of ordinary skill in the art would consider as a reasonable amount of deviation to the recited numeric values (i.e., having the equivalent function or result). For example, this term can be construed as including a deviation of ±10 percent, alternatively ±5 percent, and alternatively ±1 percent of the given numeric value provided such a deviation does not alter the end function or result of the value. Accordingly, unless indicated to the contrary, the numerical parameters set forth in this specification and attached claims are approximations that can vary depending upon the desired properties sought to be obtained by the present invention.

(10) It is noted that, as used in this specification and the appended claims, the singular forms “a,” “an,” and “the,” include plural references unless expressly and unequivocally limited to one referent. As used herein, the term “include” and its grammatical variants are intended to be non-limiting, such that recitation of items in a list is not to the exclusion of other like items that can be substituted or added to the listed items. For example, as used in this specification and the following claims, the terms “comprise” (as well as forms, derivatives, or variations thereof, such as “comprising” and “comprises”), “include” (as well as forms, derivatives, or variations thereof, such as “including” and “includes”) and “has” (as well as forms, derivatives, or variations thereof, such as “having” and “have”) are inclusive (i.e., open-ended) and do not exclude additional elements or steps. Accordingly, these terms are intended to not only cover the recited element(s) or step(s), but may also include other elements or steps not expressly recited. Furthermore, as used herein, the use of the terms “a” or “an” when used in conjunction with an element may mean “one,” but it is also consistent with the meaning of “one or more,” “at least one,” and “one or more than one.” Therefore, an element preceded by “a” or “an” does not, without more constraints, preclude the existence of additional identical elements.

(11) Herein, top-down methods for the synthesis of 2D nanosheets are described. Methods in accordance with the present invention comprise heating a bulk material in a solvent. The process is scalable and can be used to produce 2D nanosheets with uniform properties in large volumes.

(12) As used herein, the term “2D nanosheet” is used to describe a particle having a thickness between 1 to 10 atomic or molecular monolayers, and wherein the lateral dimensions are greater than the thickness. The term “nanoparticle” is used to describe a particle with dimensions on the order of approximately 1 to 100 nm. The term “quantum dot” (QD) is used to describe a semiconductor nanoparticle displaying quantum confinement effects. The dimensions of QDs are typically, but not exclusively, between 1 to 10 nm. The terms “nanoparticle” and “quantum dot” are not intended to imply any restrictions on the shape of the particle. The term “2D nanoparticle” is used to describe a particle with lateral dimensions on the order of approximately 1 to 100 nm and a thickness between 1 to 10 atomic or molecular layers, and wherein the lateral dimensions are greater than the thickness. The term “2D nanoflake” is used to describe a particle with lateral dimensions on the order of approximately 1 to 100 nm and a thickness between 1 to 5 atomic or molecular monolayers. The term “2D quantum dot” or “2D QD” is used to describe a semiconductor nanoparticle with a thickness of about 1 to 5 atomic or molecular monolayers and lateral dimensions that result in the nanoparticle being in the quantum confinement regime, i.e. the electronic properties of the nanoparticle differ to those of the bulk material.

(13) As used herein, the term “bulk material” means a three-dimensional material wherein all three dimensions are 500 nm of greater.

(14) As used herein, the term “high boiling point solvent” means a solvent having a boiling point of 100° C. of greater. For example, a high boiling point solvent may have a boiling point in the range of 100-450° C., for example, 250-400° C., or more particularly 300-350° C.

(15) The composition of the bulk material is unrestricted. Suitable materials include, but are not restricted to:

(16) graphite;

(17) transition metal dichalcogenides (TMDCs) such as, for example, WO.sub.2; WS.sub.2; WSe.sub.2; WTe.sub.2; MnO.sub.2; MoO.sub.2; MoS.sub.2; MoSe.sub.2; MoTe.sub.2; NiO.sub.2; NiTe.sub.2; NiSe.sub.2; VO.sub.2; VS.sub.2; VSe.sub.2; TaS.sub.2; TaSe.sub.2; RuO.sub.2; RhTe.sub.2; PdTe.sub.2; HfS.sub.2; NbS.sub.2; NbSe.sub.2; NbTe.sub.2; FeS.sub.2; TiO.sub.2; TiS.sub.2; TiSe.sub.2; and ZrS.sub.2;

(18) transition metal trichalcogenides such as, for example, TaO.sub.3; MnO.sub.3; WO.sub.3; ZrS.sub.3; ZrSe.sub.3; HfS.sub.3; and HfSe.sub.3;

(19) Group 13-16 (III-VI) compounds such as, for example, InS; InSe; GaS; GaSe; and GaTe;

(20) Group 15-16 (IV-VI) compounds such as, for example, Bi.sub.2Se.sub.3; and Bi.sub.2Te.sub.3;

(21) nitrides such as, for example, BN;

(22) oxides such as, for example, LaVO.sub.3; LaMnO.sub.3; V.sub.2O.sub.5; LaNbO.sub.7; Ca.sub.2Nb.sub.3O.sub.10; Ni(OH).sub.2; and Eu(OH).sub.2; layered copper oxides; micas; and bismuth strontium calcium copper oxide (BSCCO); and

(23) phosphides such as, for example, Li.sub.7MnP.sub.4; and MnP.sub.4.

(24) Within the aforementioned materials, adjacent layers are held together by van der Waals interactions, which can readily be broken to form 2D nanoparticles. In alternative embodiments, the bulk material comprises non-layered semiconductor materials, including, but not restricted to:

(25) Group 12-16 (II-VI) semiconductors such as, for example, ZnS; ZnSe; CdS; CdSe; CdTe;

(26) Group 13-15 (III-V) materials such as, for example, GaN; GaP; GaAs; InN; InP; InAs; and

(27) Group materials such as, for example, CuGaS.sub.2; CuGaSe.sub.2; CuGa(S,Se).sub.2; CuInS.sub.2, CuInSe.sub.2; CuIn(S,Se).sub.2; Cu(In,Ga)S.sub.2; Cu(In,Ga)Se.sub.2; Cu(In,Ga)(S,Se).sub.2; CuInTe.sub.2; AgInS.sub.2; and AgInSe.sub.2;

(28) Group 14 elements, for example, Si; Ge; and Sn;

(29) and including doped species and alloys thereof.

(30) In yet further embodiments, the bulk material may comprise a metal, such as, but not restricted to: Ag; Au; Cu; Pt; Pd; Ru; and Re, and including doped species and alloys thereof.

(31) In some instances, methods in accordance with the present disclosure comprise heating the bulk material in a solvent to form 2D nanosheets. One of ordinary skill in the art will recognize that the maximum temperature at which the bulk material is heated will depend on the boiling point of the solvent in which the solution is formed. In some instances, the solvent is heated to its boiling point and the bulk material is refluxed in the solvent. Without wishing to be bound by any particular theory, one possible mechanism is that the application of heat may thermally expand the layers within the bulk material; refluxing the material in a solvent may form a gas that locates between adjacent layers and then exfoliates or forces the layers apart. In some embodiments, the solution comprises a coordinating solvent. Examples of suitable coordinating solvents include, but are not restricted to: saturated alkyl amines such as, for example, C.sub.6-C.sub.50 alkyl amines; unsaturated alkyl amines such as, for example, oleylamine; fatty acids such as, for example, myristic acid, palmitic acid, and oleic acid; phosphines such as, for example, trioctylphosphine (TOP); phosphine oxides such as, for example, trioctylphosphine oxide (TOPO); alcohols such as, for example isopropanol, hexadecanol, benzylalcohol, ethylene glycol, propylene glycol; and may include primary, secondary, tertiary and branched solvents. In one embodiment, the solution comprises a coordinating solvent having more than two or more functional groups. The two or more functional groups may be the same or different. Suitable solvents include, but are not restricted to, diamines, for example, ethylenediamine. In some embodiments, the solution comprises a non-coordinating solvent, such as, but not restricted to, a C.sub.11-C.sub.50 alkane.

(32) In some embodiments, the boiling point of the solvent is between 60° C. to 600° C., for example, 160° C. to 400° C., or more particularly 180° C. to 360° C. In at least one embodiment, the solvent is a high boiling point solvent. In a particular embodiment, the solvent is myristic acid. The yield of 2D nanosheets formed may be influenced by the time in which the bulk material is heated in the solvent. Increasing the duration of time at which the bulk material is heated in the solvent may increase the yield of 2D nanosheets formed. The yield of the nanosheets formed may further be influenced by the temperature at which the bulk material is heated in the solvent. Increasing the temperature at which the bulk material is heated in the solvent may increase the yield of 2D nanosheets formed. In some instances, the bulk material can be heated in the solvent to a temperature of between about 200° C. and about 330° C. for about 15 minutes or longer, and more particularly for 1 hour or longer. In at least one embodiment, the bulk material is heated in the solvent and refluxed for 6 hours or longer. In some instances, heating of the material can be performed for a period of up to about 12 hours. Generally, as the heating time is increased, the yield of the 2D nanosheets increases. The inventors have also discovered, however, that as the heating time is increased the emission spectrum of the resulting 2D nanosheets broadens. Therefore, while increasing the heating time may result in a higher yield of product, such high yield product may have emission spectra which is undesirable broad and therefore unfavorable for use in applications requiring narrow emission profiles. In some instances, optimal reaction time depend upon the properties of the bulk material, such as composition, interlayer spacing (i.e., bulk material density), surface area, etc. In at least one embodiment, the bulk material is refluxed in a high boiling point fatty acid solvent.

(33) The choice of functional group(s) on the solvent may be used to control the dimensions and the size distribution of the nanosheets formed.

(34) The 2D nanosheets may be isolated using any method. Suitable methods include, but are not restricted to, centrifugation, filtration, dialysis, or column chromatography. In at least one embodiment, a size-selective isolation procedure may be used extract 2D nanosheets of similar dimensions and thus having similar emissive properties.

(35) When the 2D nanosheets are produced in a coordinating solvent, the coordinating solvent may act as a capping ligand that binds to a surface of the 2D nanosheets and alter their solubility. Thus, the 2D nanosheets may be dissolved or dispersed in a suitable solvent to provide solution processability. Solution-processable 2D nanosheets are particularly attractive for applications such as photoluminescent displays and lighting, electroluminescent displays and lighting, 2D heterostructure devices, sensors, and biological imaging.

(36) In some embodiments, the nanosheets are 2D nanoparticles. In some embodiments, the 2D nanosheets are 2D nanoflakes. 2D nanoflakes are of particular interest because of the unusual properties of many materials as their dimensions are reduced to a few monolayers or less.

(37) In some embodiments, the 2D nanoflakes are 2D QDs. Conventional QDs have widely been investigated for their unique optical, electronic and chemical properties, which originate from “quantum confinement effects”; as the dimensions of a semiconductor nanoparticle are reduced below twice the Bohr exciton radius, the energy levels become quantized, giving rise to discrete energy levels. The band gap increases with decreasing particle size, leading to size-tunable optical, electronic and chemical properties, such as size-dependent photoluminescence. Moreover, it has been found that reducing the lateral dimensions of a 2D nanoflake of a semiconductor material into the quantum confinement regime may give rise to yet further unique properties, depending on both the lateral dimensions and the number of layers of the 2D nanoflake. In some embodiments, the lateral dimensions of the 2D nanoflakes may be in the quantum confinement regime, wherein the optical, electronic and chemical properties of the nanoparticles may be manipulated by changing their lateral dimensions. For example, metal chalcogenide monolayer nanoflakes of materials such as MoSe.sub.2 and WSe.sub.2 with lateral dimensions of approximately 10 nm or less may display properties such as size-tunable emission when excited. This can enable the electroluminescence maximum (EL.sub.max) or photoluminescence (PL.sub.max) of the 2D nanoflakes to be tuned by manipulating the lateral dimensions of the nanoparticles.

(38) As used herein, a “2D quantum dot” or “2D QD” refers to a semiconductor nanoparticle with lateral dimensions in the quantum confinement regime and a thickness between 1-5 atomic or molecular monolayers and lateral dimensions that result in the nanoparticle being in the quantum confinement regime, i.e. the electronic properties of the nanoparticle differ to those of the bulk material. As used herein, a “single-layered quantum dot” or “single-layered QD” refers to a semiconductor nanoparticle with lateral dimensions in the quantum confinement regime and a thickness of a single monolayer. Compared with conventional QDs, 2D QDs have a much higher surface area-to-volume ratio, which increases as the number of monolayers is decreased. The highest surface area-to-volume ratio is seen for single-layered QDs. This may lead to 2D QDs having very different surface chemistry from conventional QDs, which may be exploited for applications such as catalysis.

EXAMPLES

(39) In many of the examples below, certain steps are performed under reflux conditions. As used herein, reflux is understood to be a distillation technique involving the condensation of vapors and the return of this condensate to the system from which it originated. Specifically, a mixture of reactants and solvent is placed in a suitable reaction vessel. This vessel is connected to a water-cooled Liebig or Vigreux condenser, which is may be sealed or open to the atmosphere at the top. The reaction vessel is heated in order to boil the reaction mixture; vapours produced from the mixture are condensed by the condenser, and return to the vessel through gravity. The purpose is to thermally accelerate the reaction by conducting it at an elevated, controlled temperature (i.e. the solvent's boiling point) and ambient pressure.

Example 1: Preparation of MoS.SUB.2 .2D Nanosheets

(40) Bulk MoS.sub.2 powder (0.120 g) and myristic acid (10 g) were combined in a round-bottom flask. The mixture was heated under vacuum at 110° C. for 1 hour, then placed under N.sub.2. The reaction mixture was heated to reflux temperature (˜330° C.) and held for a given time period (see Table 1), before cooling to 60° C. Toluene (30 mL) was added, followed by centrifugation at 8,000 rpm for 5 minutes. A dark yellow supernatant was separated from black unexfoliated bulk MoS.sub.2. The black unexfoliated bulk MoS.sub.2 was re-washed with toluene (20 mL) and centrifuged at 8,000 rpm for 5 minutes. The supernatant was combined with that from the first centrifugation, then dried under vacuum.

(41) Acetonitrile (150 mL) was added to the dried residue from the supernatant, then the sample was warmed to 60° C. Free excess myristic acid dissolved, leaving an oily solid. The supernatant was decanted and discarded. The process was repeated three times.

(42) To the oil, once dried, a 0.25 M solution of potassium carbonate (50 mL) was added, and the mixture was warmed to 50° C. with shaking. The supernatant was decanted and discarded, while a dark coloured material containing the MoS.sub.2 2D nanosheets was retained, then washed twice with deionised water.

(43) Acetonitrile (100 mL) was added to the dark coloured material, followed by warming, then the supernatant was decanted and discarded. The process was repeated twice further and the product retained as a solid.

(44) When the time period for reflux was varied between 50 minutes and 6 hours, the photoluminescence (PL) contour map of the material very similar, but the longer reflux time led to a greatly enhanced reaction yield. A typical PL contour map is shown in FIG. 1. The PL contour map shows the emission wavelength (x-axis) plotted against excitation wavelength (y-axis) for a solution of the MoS.sub.2 2D nanosheets dissolved in toluene. Broad, bright PL was observed, spanning the ultraviolet to red regions of the electromagnetic spectrum, with a PL.sub.max at approximately 450 nm.

Example 2: Preparation of Other 2D Nanosheets

(45) The process in Example 1 was repeated but with the bulk powder and/or solvent and/or reaction temperature and/or reaction time changed, as summarized in Table 1.

(46) TABLE-US-00001 TABLE 1 BULK MATE- OBSER- RIAL SOLVENT RXN TEMP. RXN TIME VATIONS MoS.sub.2 Hexadecyl- Reflux 20 min Poor yield amine (~330° C.) PL spanning UV to green (PL.sub.max ~420 nm) MoS.sub.2 Hexadecyl- Reflux 6 h Good yield amine (~330° C.) PL spanning UV to green (PL.sub.max ~420 nm) MoS.sub.2 Trioctyl- 330° C. 6 h Poor yield phosphine Short PL material oxide spanning UV to blue (PL.sub.max ~360 nm) MoS.sub.2 Trioctyl- Reflux 6 h Poor yield phosphine (~400° C.) Short PL material oxide spanning UV to blue (PL.sub.max ~360 nm) MoS.sub.2 Hexadecanol Reflux 6 h High yield (~325° C.) PL spanning UV to green (PL.sub.max ~375 nm) MoS.sub.2 Octadecane Reflux 6 h Short PL (~317° C.) spanning UV to blue (PL.sub.max ~370 nm) MoS.sub.2 Acetic acid Reflux 6 h Poor yield (~117- Short PL material 118° C.) spanning blue to green (PL.sub.max ~440 nm) MoS.sub.2 Octane + Reflux 6 h Poor yield myristic (~125° C.) Short PL acid MoS.sub.2 Ethylene Reflux 6 h PL spanning UV diamine (~116° C.) to yellow (PL.sub.max ~420 & 480 nm) MoSe.sub.2 Myristic acid Reflux 6 h Broad PL (~330° C.) spanning UV to red (PL.sub.max ~380 nm) WS.sub.2 Myristic acid Reflux 6 h PL spanning blue (~330° C.) to red (PL.sub.max ~500 nm)

(47) The PL contour maps of the MoS.sub.2 nanosheets produced in hexadecanol and in acetic acid are shown in FIGS. 2 and 3, respectively. FIG. 2 shows that, when MoS.sub.2 was heated to reflux (˜325° C.) in hexadecanol, the emission spanned from ˜325 nm (UV) to ˜525 nm (green), with a PL.sub.max at ˜375 nm. FIG. 3 shows that, when MoS.sub.2 was heated to reflux (˜117-118° C.) in acetic acid, the emission spanned from ˜375 nm (UV) to ˜525 nm (green), with a PL.sub.max at ˜440 nm.

Example 3: Preparation of MoS.SUB.2 .2D Nanosheets

(48) Bulk MoS.sub.2 powder (0.2 g) was mixed with myristic acid (10 g) and tetramethylammonium hydroxide pentahydrate (4 g). The mixture was placed under a high vacuum and warmed to 100° C. for 1 hour. The reaction was then heated to reflux for 15 hours. A large amount of material had boiled off, so hexadecane (10 mL) was added and held at 250° C. for 2 hours, before cooling to room temperature. A PL contour map of the resulting material is shown in FIG. 4, which shows PL spanning the UV (˜400 nm) to red (˜610 nm) with a PL.sub.max 480 nm.

(49) To clean and extract the material emitting with a PL.sub.max greater than 480 nm, corresponding to larger MoS.sub.2 2D nanosheets, isopropanol (500 mL) was added, then stirred for 5 minutes, followed by centrifugation. The supernatant contained blue-emitting material and was set aside. This material was found in the precipitate and was dissolved in toluene, before filtering through a 0.2 μm PTFE syringe filter. The sample was dried and the material was rinsed with further portions of isopropanol, with 5 minute stirring intervals before decanting the isopropanol, adding more isopropanol and repeating until little to no PL was detected in the isopropanol rinses. To the residual solid, acetone was added and a bright (25-30% QY at 360 nm excitation) material was extracted with emission spanning the blue (˜425 nm) to red (˜625 nm) and a PL.sub.max of 518 nm (see FIG. 5). The remaining material (once the material emitting at 518 nm had been removed) displayed longer emission but was less bright (see FIG. 6). The material in FIG. 6 showed emission spanning the blue (˜475 nm) to the NIR (700 nm), with a PL.sub.max˜575 nm.

(50) Comparing FIGS. 2-4, in the case of hexadecanol and acetic acid, the higher reaction temperature produced material with a shorter PL.sub.max, corresponding to smaller nanosheets. However, in the case of myristic acid (FIG. 4), though this was heated to reflux (˜330° C.) for 15 hours, then 250° C. for a further 2 hours after the addition of hexadecane, these temperatures being higher than when using acetic acid as the solvent, surprisingly, longer wavelength-emitting nanosheets (corresponding with larger nanosheet dimensions) were produced at the higher temperature. These surprising observations are supported by the data in Table 1, where, for example, in the case of TOPO, increasing the reaction temperature from 330° C. to reflux (˜400° C.) did not result in a blue-shift in the PL.sub.max. Similarly, hexadecylamine (heated to ˜330° C.) and acetic acid (heated to ˜117-118° C.) resulted in similar PL.sub.max values. Thus, it was found that there is no direct correlation between reaction temperature and the resulting nanosheet size.

(51) Comparing FIGS. 4 and 5, the data show that material emitting at different wavelengths, corresponding with different nanosheet sizes, can be extracted from the reaction solution using different solvents.

(52) These and other advantages of the present invention will be apparent to those skilled in the art from the foregoing disclosure. Accordingly, it is to be recognized that changes or modifications may be made to the above-described embodiments without departing from the broad inventive concepts of the invention. It is to be understood that this invention is not limited to the particular embodiments described herein and that various changes and modifications may be made without departing from the scope of the present invention as literally and equivalently covered by the following claims.