Few-layer Samples Research Articles

Phonon sidebands of color centers in hexagonal boron nitride

Low temperature photoluminescence spectra of the phonon sidebands of a color center in hexagonal boron nitride are compared to an independent boson model. We infer that the LA-phonon sideband is described by deformation coupling proportional to in-plane strain, resulting in a phonon bath that is effectively two-dimensional. For optical phonons, sharp resonances close to turning points in the phonon dispersion are observed. We infer that the TO-electron coupling is described by deformation coupling proportional to in-plane lattice displacement, resulting in a TO bath that is also effectively two-dimensional. By contrast, for the LO branches we infer that the Fr\"ohlich coupling depends on the interactions between adjacent layers, and propose that the 200-meV peak is a signature of a few-layer sample. This work highlights features of electron-phonon coupling that arise from the layered structure of h-BN.

Possible Dual Bandgap in (C4H9NH3)2PbI4 2D Layered Perovskite: Single-Crystal and Exfoliated Few-Layer

Optoelectronic devices of 2D layered Pb-halide perovskites depend on light absorption/emission, exciton dissociation/transfer, and charge transfer processes, which in turn depend on bandgap and band edges. Here, we report that the surface/subsurface region of 2D (C4H9NH3)2PbI4 perovskite single crystals have a wider bandgap compared to the interior of the crystal. Consequently, single crystals exhibit dual excitonic emission peaks at 2.38 and 2.20 eV arising from the surface and interior, respectively. In contrast, exfoliated layers of (C4H9NH3)2PbI4 exhibit single photoluminescence peak at 2.38 eV, similar to the surface/subsurface of single crystals. Temperature-dependent (300–10 K) photoluminescence and single-crystal diffraction suggest that the overall structure–bandgap relationships are similar for both single-crystal and few-layer samples, but with some difference in phase transition hysteresis. Similar minor structural differences between the bulk (interior) and surface/subsurface of (C4H9NH3)2PbI...

Few-layer Bi2Te3: an effective 2D saturable absorber for passive Q-switching of compact solid-state lasers in the 1-μm region.

An experimental investigation was carried out to evaluate the potential of few-layer Bi2Te3 topological insulator in use as a saturable absorber for passive Q-switching of compact solid-state lasers in the 1-μm spectral region. By incorporating a sapphire-based few-layer Bi2Te3 sample into a Yb:LuPO4 laser that was formed with a 4-mm plane-parallel resonator, we realized efficient, high-power, high-repetition-rate pulsed laser operation. Depending on the output coupling utilized, single- or dual-wavelength laser action could be achieved. A maximum output power of 5.02 W at 1014.5 nm was produced at a pulse repetition rate of 1.67 MHz, with an optical-to-optical efficiency of 41% and a slope efficiency of 54%; while operating at 1004.9/1012.7 nm, the pulsed laser could produce an output power of 3.94 W at 1.38 MHz, with a pulse duration being as short as 34 ns. The largest pulse energy and highest peak power achieved were 3.0 μJ and 85.3 W. The results demonstrated in our experiment reveal the great potential of the few-layer Bi2Te3 topological insulator in the development of pulsed compact solid-state lasers in the 1-μm region.

Low-Frequency Raman Spectroscopy of Few-Layer 2H-SnS2

We investigated interlayer phonon modes of mechanically exfoliated few-layer 2H-SnS2 samples by using room temperature low-frequency micro-Raman spectroscopy. Raman measurements were performed using laser wavelengths of 441.6, 514.4, 532 and 632.8 nm with power below 100 μW and inside a vacuum chamber to avoid photo-oxidation. The intralayer Eg and A1g modes are observed at ~206 cm−1 and 314 cm−1, respectively, but the Eg mode is much weaker for all excitation energies. The A1g mode exhibits strong resonant enhancement for the 532 nm (2.33 eV) laser. In the low-frequency region, interlayer vibrational modes of shear and breathing modes are observed. These modes show characteristic dependence on the number of layers. The strengths of the interlayer interactions are estimated by fitting the interlayer mode frequencies using the linear chain model and are found to be 1.64 × 1019 N · m−3 and 5.03 × 1019 N · m−3 for the shear and breathing modes, respectively.

Producing air-stable InSe nanosheet through mild oxygen plasma treatment

Ultrathin indium selenide (InSe), as a newly emerging two-dimensional material with high carrier mobility and broadband optical absorption, is considered as a promising candidate for electronic and optoelectronic devices. It has been a challenge to produce air-stable mono- or few-layer InSe nanosheets because they degrade rapidly in an ambient environment. Here, we demonstrate a facile mild oxygen plasma treatment route to fabricate air-stable few-layer InSe samples. Photoluminescence (PL) and x-ray photoelectron spectroscopy (XPS) analysis indicate that the plasma treatment can introduce an oxidation process that forms a dense InSe1−xOx capping layer on the surface, and thus prevent the sample from degradation. Furthermore, the oxide layer would introduce a PL quenching of the pristine InSe, while a new and strong PL peak belonging to the emission from InSe1−xOx appears. This work offers a practical and efficient route to improve the performance of InSe based electrical and optoelectronic devices.

Tuning Ising superconductivity with layer and spin\u2013orbit coupling in two-dimensional transition-metal dichalcogenides

Systems simultaneously exhibiting superconductivity and spin–orbit coupling are predicted to provide a route toward topological superconductivity and unconventional electron pairing, driving significant contemporary interest in these materials. Monolayer transition-metal dichalcogenide (TMD) superconductors in particular lack inversion symmetry, yielding an antisymmetric form of spin–orbit coupling that admits both spin-singlet and spin-triplet components of the superconducting wavefunction. Here, we present an experimental and theoretical study of two intrinsic TMD superconductors with large spin–orbit coupling in the atomic layer limit, metallic 2H-TaS2 and 2H-NbSe2. We investigate the superconducting properties as the material is reduced to monolayer thickness and show that high-field measurements point to the largest upper critical field thus reported for an intrinsic TMD superconductor. In few-layer samples, we find the enhancement of the upper critical field is sustained by the dominance of spin–orbit coupling over weak interlayer coupling, providing additional candidate systems for supporting unconventional superconducting states in two dimensions.

Defect Engineering in Few-Layer Phosphorene.

Defect engineering in 2D phosphorene samples is becoming an important and powerful technique to alter their properties, enabling new optoelectronic applications, particularly at the infrared wavelength region. Defect engineering in a few-layer phosphorene sample via introduction of substrate trapping centers is realized. In a three-layer (3L) phosphorene sample, a strong photoluminescence (PL) emission peak from localized excitons at ≈1430 nm is observed, a much lower energy level than free excitonic emissions. An activation energy of ≈77 meV for the localized excitons is determined in temperature-dependent PL measurements. The relatively high activation energy supports the strong stability of the localized excitons even at elevated temperature. The quantum efficiency of localized exciton emission in 3L phosphorene is measured to be approximately three times higher than that of free excitons. These results could enable exciting applications in infrared optoelectronics.

Strongly Coupled Electron–Phonon Dynamics in Few-Layer TiSe2 Exfoliates

Ultrafast electron diffraction is used to probe the time-resolved dynamics in a few-layer TiSe2 sample. At normal incidence, the suppression of the Bragg diffraction peak intensities following photoexcitation displays strongly biexponential behavior. For tilted samples, changes in the diffraction peak positions reveal coherent acoustic vibrations that are dependent on the sample thickness and that further permit a calculation of the Young’s modulus. The complex room temperature lattice dynamics observed are attributed to strong electron–phonon coupling and electron–lattice equilibration processes, which support a Jahn–Teller origin of the charge density wave behavior in TiSe2. Additionally, the significant role that the related Kohn anomalies may play in the electron transport dynamics and transition mechanism of this material is emphasized. These results demonstrate the importance of strongly coupled electron–phonon dynamics in the relaxation of electronically excited room temperature TiSe2, which is exp...

Current rectification and asymmetric photoresponse in MoS2 stacking-induced homojunctions**J.X. and Q.S.Z. performed the experiments. J.X.Y. provided band structure simulation. J.D.Z. and Z.L. helped to prepare the samples. W.Z. provided the STEM images. All authors discussed the results. J.X, J.X.Y. and Z.X.S. conceived the study. J.X. and Q.S.Z. wrote the manuscript with contributions from co-authors.

The layer-dependent electronic and optoelectronic properties in transition metal dichalcogenides (TMDs) have been investigated extensively. Current rectification behavior has been demonstrated using heterojunctions constructed from different TMDs materials, as well as single layer-few layer homojunctions utilizing the layer-dependent behavior of TMDs. MoS2 is the best known TMDs and high quality few-layer samples with different stacking sequences can be facilely obtained by the chemical vapor deposition (CVD) method. In this paper, we firstly report the stacking-dependent junctions formed by the interface of AA-AB stacked bilayer MoS2 samples, together with AA bilayer-single layer (AA-1L) and AB bilayer-single layer (AB-1L) junctions. Current rectification and asymmetric photoresponse are observed for the unique AA-AB junctions, similar to that of bilayer-monolayer (2L-1L) junctions. Current mappings clearly show that the photocurrents are mainly localized along the interfaces, confirming that intrinsic junctions are responsible to their electronic/optoelectronic performances, rather than Schottky barrier between electrode and sample. Our finding demonstrates the promise of using stacking-modulated 2D materials for future electronics and optoelectronics.

Effects of rhenium dopants on photocarrier dynamics and optical properties of monolayer, few-layer, and bulk MoS2.

We report a comprehensive study on the effects of rhenium doping on optical properties and photocarrier dynamics of MoS2 monolayer, few-layer, and bulk samples. Monolayer and few-layer samples of Re-doped (0.6%) and undoped MoS2 were fabricated by mechanical exfoliation, and were studied by Raman spectroscopy, optical absorption, photoluminescence, and time-resolved differential reflection measurements. Similar Raman, absorption, and photoluminescence spectra were obtained from doped and undoped samples, indicating that the Re doping at this level does not significantly alter the lattice and electronic structures. Red-shift and broadening of the two phonon Raman modes were observed, showing the lattice strain and carrier doping induced by Re. The photoluminescence yield of the doped monolayer is about 15 times lower than that of the undoped sample, while the photocarrier lifetime is about 20 times shorter in the doped monolayer. Both observations can be attributed to diffusion-limited Auger nonradiative recombination of photocarriers at Re dopants. These results provide useful information for developing a doping strategy of MoS2 for optoelectronic applications.

Observation of Optical and Electrical In-Plane Anisotropy in High-Mobility Few-Layer ZrTe5.

Transition metal pentatelluride ZrTe5 is a versatile material in condensed-matter physics and has been intensively studied since the 1980s. The most fascinating feature of ZrTe5 is that it is a 3D Dirac semimetal which has linear energy dispersion in all three dimensions in momentum space. Structure-wise, ZrTe5 is a layered material held together by weak interlayer van der Waals force. The combination of its unique band structure and 2D atomic structure provides a fertile ground for more potential exotic physical phenomena in ZrTe5 related to 3D Dirac semimentals. However, the physical properties of its few-layer form have yet to be thoroughly explored. Here we report strong optical and electrical in-plane anisotropy of mechanically exfoliated few-layer ZrTe5. Raman spectroscopy shows a significant intensity change with sample orientations, and the behavior of angle-resolved phonon modes at the Γ point is explained by theoretical calculations. DC conductance measurement indicates a 50% of difference along different in-plane directions. The diminishing of resistivity anomaly in few-layer samples indicates the evolution of band structure with a reduced thickness. A low-temperature Hall experiment sheds light on more intrinsic anisotropic electrical transport, with a hole mobility of 3000 and 1500 cm2/V·s along the a-axis and c-axis, respectively. Pronounced quantum oscillations in magnetoresistance are observed at low temperatures with the highest electron mobility up to 44 000 cm2/V·s.

Zone-center phonons of bulk, few-layer, and monolayer1T−TaS2: Detection of commensurate charge density wave phase through Raman scattering

We present first-principles calculations of the vibrational properties of the transition metal dichalcogenide 1T-TaS$_2$ for various thicknesses in the high-temperature (undistorted) phase and the low-temperature commensurate charge density wave (CDW) phase. We also present measurements of the Raman spectra for bulk, few-layer, and monolayer samples at temperatures well below that of the bulk transition to the commensurate phase. Through our calculations, we identify the low-frequency folded-back acoustic modes as a convenient signature of the commensurate CDW wave structure in vibrational spectra. In our measured Raman spectra, this signature is clearly evident in all of the samples, indicating that the commensurate phase remains the ground state as the material is thinned, even down to a single layer. This is in contrast to some previous studies which suggest a suppression of the commensurate CDW transition in thin flakes. We also use polarized Raman spectroscopy to probe c-axis orbital texture in the low-T phase, which has recently been suggested as playing a role in the metal-insulator transition that accompanies the structural transition to the commensurate CDW phase.

Patterning Superatom Dopants on Transition Metal Dichalcogenides.

This study describes a new and simple approach to dope two-dimensional transition metal dichalcogenides (TMDCs) using the superatom Co6Se8(PEt3)6 as the electron dopant. Semiconducting TMDCs are wired into field-effect transistor devices and then immersed into a solution of these superatoms. The degree of doping is determined by the concentration of the superatoms in solution and by the length of time the films are immersed in the dopant solution. Using this chemical approach, we are able to turn mono- and few-layer MoS2 samples from moderately to heavily electron-doped states. The same approach applied on WSe2 films changes their characteristics from hole transporting to electron transporting. Moreover, we show that the superatom doping can be patterned on specific areas of TMDC films. To illustrate the power of this technique, we demonstrate the fabrication of a lateral p-n junction by selectively doping only a portion of the channel in a WSe2 device. Finally, encapsulation of the doped films with crystalline hydrocarbon layers stabilizes their properties in an ambient environment.

Third order nonlinear optical response exhibited by mono- and few-layers of WS2

In this work, strong third order nonlinear optical properties exhibited by WS2 layers are presented. Optical Kerr effect was identified as the dominant physical mechanism responsible for these third order optical nonlinearities. An extraordinary nonlinear refractive index together with an important contribution of a saturated absorptive response was observed to depend on the atomic layer stacking. Comparative experiments performed in mono- and few-layer samples of WS2 revealed that this material is potentially capable of modulating nonlinear optical processes by selective near resonant induced birefringence. We envision applications for developing all-optical bidimensional nonlinear optical devices.

Exfoliation and Raman Spectroscopic Fingerprint of Few-Layer NiPS3 Van der Waals Crystals.

The range of mechanically cleavable Van der Waals crystals covers materials with diverse physical and chemical properties. However, very few of these materials exhibit magnetism or magnetic order, and thus the provision of cleavable magnetic compounds would supply invaluable building blocks for the design of heterostructures assembled from Van der Waals crystals. Here we report the first successful isolation of monolayer and few-layer samples of the compound nickel phosphorus trisulfide (NiPS3) by mechanical exfoliation. This material belongs to the class of transition metal phosphorus trisulfides (MPS3), several of which exhibit antiferromagnetic order at low temperature, and which have not been reported in the form of ultrathin sheets so far. We establish layer numbers by optical bright field microscopy and atomic force microscopy, and perform a detailed Raman spectroscopic characterization of bilayer and thicker NiPS3 flakes. Raman spectral features are strong functions of excitation wavelength and sample thickness, highlighting the important role of interlayer coupling. Furthermore, our observations provide a spectral fingerprint for distinct layer numbers, allowing us to establish a sensitive and convenient means for layer number determination.

Rhenium Dichalcogenides: Layered Semiconductors with Two Vertical Orientations.

The rhenium and technetium diselenides and disulfides are van der Waals layered semiconductors in some respects similar to more well-known transition metal dichalcogenides (TMD) such as molybdenum sulfide. However, their symmetry is lower, consisting only of an inversion center, so that turning a layer upside-down (that is, applying a C2 rotation about an in-plane axis) is not a symmetry operation, but reverses the sign of the angle between the two nonequivalent in-plane crystallographic axes. A given layer thus can be placed on a substrate in two symmetrically nonequivalent (but energetically similar) ways. This has consequences for the exploitation of the anisotropic properties of these materials in TMD heterostructures and is expected to lead to a new source of domain structure in large-area layer growth. We produced few-layer ReS2 and ReSe2 samples with controlled "up" or "down" orientations by micromechanical cleavage and we show how polarized Raman microscopy can be used to distinguish these two orientations, thus establishing Raman as an essential tool for the characterization of large-area layers.

Raman fingerprint for semi-metal WTe2 evolving from bulk to monolayer

Tungsten ditelluride (WTe2), a layered transition-metal dichalcogenide (TMD), has recently demonstrated an extremely large magnetoresistance effect, which is unique among TMDs. This fascinating feature seems to be correlated with its special electronic structure. Here, we report the observation of 6 Raman peaks corresponding to the , , , , and phonons, from the 33 Raman-active modes predicted for WTe2. This provides direct evidence to distinguish the space group of WTe2 from those of other TMDs. Moreover, the Raman evolution of WTe2 from bulk to monolayer is clearly revealed. It is interesting to find that the mode, centered at ~109.8 cm−1, is forbidden in a monolayer, which may be attributable to the transition of the point group from C2v (bulk) to C2h (monolayer). Our work characterizes all observed Raman peaks in the bulk and few-layer samples and provides a route to study the physical properties of two-dimensional WTe2.

Stacking-Dependent Interlayer Coupling in Trilayer MoS₂ with Broken Inversion Symmetry.

The stacking configuration in few-layer two-dimensional (2D) materials results in different structural symmetries and layer-to-layer interactions, and hence it provides a very useful parameter for tuning their electronic properties. For example, ABA-stacking trilayer graphene remains semimetallic similar to that of monolayer, while ABC-stacking is predicted to be a tunable band gap semiconductor under an external electric field. Such stacking dependence resulting from many-body interactions has recently been the focus of intense research activities. Here we demonstrate that few-layer MoS2 samples grown by chemical vapor deposition with different stacking configurations (AA, AB for bilayer; AAB, ABB, ABA, AAA for trilayer) exhibit distinct coupling phenomena in both photoluminescence and Raman spectra. By means of ultralow-frequency (ULF) Raman spectroscopy, we demonstrate that the evolution of interlayer interaction with various stacking configurations correlates strongly with layer-breathing mode (LBM) vibrations. Our ab initio calculations reveal that the layer-dependent properties arise from both the spin-orbit coupling (SOC) and interlayer coupling in different structural symmetries. Such detailed understanding provides useful guidance for future spintronics fabrication using various stacked few-layer MoS2 blocks.

Surface Recombination Limited Lifetimes of Photoexcited Carriers in Few-Layer Transition Metal Dichalcogenide MoS2

We present results on photoexcited carrier lifetimes in few-layer transition metal dichalcogenide MoS2 using nondegenerate ultrafast optical pump-probe technique. Our results show a sharp increase of the carrier lifetimes with the number of layers in the sample. Carrier lifetimes increase from few tens of picoseconds in monolayer samples to more than a nanosecond in 10-layer samples. The inverse carrier lifetime was found to scale according to the probability of the carriers being present at the surface layers, as given by the carrier wave function in few layer samples, which can be treated as quantum wells. The carrier lifetimes were found to be largely independent of the temperature, and the inverse carrier lifetimes scaled linearly with the photoexcited carrier density. These observations are consistent with defect-assisted carrier recombination, in which the capture of electrons and holes by defects occurs via Auger scatterings. Our results suggest that carrier lifetimes in few-layer samples are surface recombination limited due to the much larger defect densities at surface layers compared with the inner layers.

Direct Growth of Single- and Few-Layer MoS2 on h-BN with Preferred Relative Rotation Angles.

Monolayer molybdenum disulfide (MoS2) is a promising two-dimensional direct-bandgap semiconductor with potential applications in atomically thin and flexible electronics. An attractive insulating substrate or mate for MoS2 (and related materials such as graphene) is hexagonal boron nitride (h-BN). Stacked heterostructures of MoS2 and h-BN have been produced by manual transfer methods, but a more efficient and scalable assembly method is needed. Here we demonstrate the direct growth of single- and few-layer MoS2 on h-BN by chemical vapor deposition (CVD) method, which is scalable with suitably structured substrates. The growth mechanisms for single-layer and few-layer samples are found to be distinct, and for single-layer samples low relative rotation angles (<5°) between the MoS2 and h-BN lattices prevail. Moreover, MoS2 directly grown on h-BN maintains its intrinsic 1.89 eV bandgap. Our CVD synthesis method presents an important advancement toward controllable and scalable MoS2-based electronic devices.