Layer Breathing Research Articles

Determining by Raman spectroscopy the average thickness and N-layer-specific surface coverages of MoS2 thin films with domains much smaller than the laser spot size.

Raman spectroscopy is a widely used technique to characterize nanomaterials because of its convenience, non-destructiveness, and sensitivity to materials change. The primary purpose of this work is to determine via Raman spectroscopy the average thickness of MoS2 thin films synthesized by direct liquid injection pulsed-pressure chemical vapor deposition (DLI-PP-CVD). Such samples are constituted of nanoflakes (with a lateral size of typically 50 nm, i.e., well below the laser spot size), with possibly a distribution of thicknesses and twist angles between stacked layers. As an essential preliminary, we first reassess the applicability of different Raman criteria to determine the thicknesses (or layer number, N) of MoS2 flakes from measurements performed on reference samples, namely well-characterized mechanically exfoliated or standard chemical vapor deposition MoS2 large flakes deposited on 90 ± 6 nm SiO2 on Si substrates. Then, we discuss the applicability of the same criteria for significantly different DLI-PP-CVD MoS2 samples with average thicknesses ranging from sub-monolayer up to three layers. Finally, an original procedure based on the measurement of the intensity of the layer breathing modes is proposed to evaluate the surface coverage for each N (i.e., the ratio between the surface covered by exactly N layers and the total surface) in DLI-PP-CVD MoS2 samples.

Twist Angle-Dependent Intervalley Charge Carrier Transfer and Recombination in Bilayer WS2.

A twist angle at a van der Waals junction provides a handle to tune its optoelectronic properties for a variety of applications, and a comprehensive understanding of how the twist modulates electronic structure, interlayer coupling, and carrier dynamics is needed. We employ time-dependent density functional theory and nonadiabatic molecular dynamics to elucidate angle-dependent intervalley carrier transfer and recombination in bilayer WS2. Repulsion between S atoms in twisted configurations weakens interlayer coupling, increases the interlayer distance, and softens layer breathing modes. Twisting has a minor influence on K valleys while it lowers Γ valleys and raises Q valleys because their wave functions are delocalized between layers. Consequently, the reduced energy gaps between the K and Γ valleys accelerate the hole transfer in the twisted structures. Intervalley electron transfer proceeds nearly an order of magnitude faster than hole transfer. The more localized wave functions at K than Q values and larger bandgaps result in smaller nonadiabatic couplings for intervalley recombination, making it 3-4 times slower in twisted than high-symmetry structures. B2g breathing, E2g in-plane, and A1g out-of-plane modes are most active during intervalley carrier transfer and recombination. The faster intervalley transfer and extended carrier lifetimes in twisted junctions are favorable for optoelectronic device performance.

Enhanced Layer-Breathing Modes in van der Waals Heterostructures Based on Twisted Bilayer Graphene.

The characterization of interlayer coupling in two-dimensional van der Waals heterostructures (vdWHs) is essential to understand their quantum behaviors and structural functionalities. Interlayer shear and layer-breathing (LB) phonons carry rich information on interlayer interaction, but they are usually too weak to be detected via standard Raman spectroscopy due to the weak electron-phonon coupling (EPC). Here, we report a universal strategy to enhance LB modes of vdWHs based on twisted bilayer graphene (tBLG). In both tBLG/hBN and tBLG/MoS2 vdWHs, the resonantly excited electrons in tBLG can strongly couple to LB phonons extended over the entire layers in the vdWHs, whose resonance condition is tunable by the twist angle of tBLG. In vdWHs containing twisted graphene layers with multiple twisted interfaces, the EPC of LB phonons coming from the collective LB vibrations of entire heterostructure layers can be tuned by resonant excitation of programmable van Hove singularities according to each twisted interface. The universality and tunability of enhanced LB phonons by tBLG make it a promising method to investigate EPC and interlayer interaction in related vdWHs.

Phonon and Exciton Properties between WS2 and MoS2 Layers via Inversion Heterostructure Engineering.

Recently, two-dimensional (2D) van der Waals heterostructures (vdWHs) have exhibited emergent electronic and optical properties due to their peculiar phonons and excitons, which lay the foundation for the development of photoelectronic devices. The dielectric environment plays an important role in the interlayer coupling of vdWHs. Here, we studied the interlayer and extra-layer dielectric effects on phonon and exciton properties in WS2/MoS2 and MoS2/WS2 vdWHs by Raman and photoluminescence (PL) spectroscopy. The ultralow frequency (ULF) Raman modes are insensitive to atomic arrangement at the interface between 1LW and 1LM and dielectric environments of neighboring materials, and the layer breathing mode (LBM) frequency follows that of WS2. The shift of high-frequency (HF) Raman modes is attributable to interlayer dielectric screening and charge transfer effects. Furthermore, the energy of interlayer coupling exciton peak I is insensitive to atomic arrangement at the interface between 1LW and 1LM and its energy follows that of MoS2, but the slight intensity difference in inversion vdWHs means that the substrate's dielectric properties may induce doping on the bottom layer. This paper provides fundamental understanding of phonon and exciton properties of such artificially formed vdWHs structures, which is important for new insights into manipulating the performances of potential devices.

Molecular beam epitaxy of PtSe2 using a co-deposition approach

The structural properties of co-deposited ultrathin PtSe2 films grown at low temperatures by molecular beam epitaxy on c-plane Al2O3 are studied. By simultaneously supplying a Se flux from a Knudsen cell and Pt atoms from an electron-beam evaporator, crystalline (001)-oriented PtSe2 films were formed between 200 °C and 300 °C. The long separation between substrate and electron beam evaporator of about 60 cm ensured minimal thermal load. At optimum deposition temperatures, a ten times or even higher supply rate of Se compared to Pt ensured that the pronounced volatility of the Se was compensated and the PtSe2 phase was formed and stabilized at the growth front. Postgrowth anneals under a Se flux was found to dramatically improve the crystalline quality of the films. Even before the postgrowth anneal in Se, the crystallinity of PtSe2 films grown with the co-deposition method was superior to films realized by thermal assisted conversion. Postgrowth annealed films showed Raman modes with narrower peaks and more than twice the intensity. Transmission electron microscopy investigations revealed that the deposited material transitioned to a two-dimensional layered structure only after the postgrowth anneal. PtSe2 growth was found to start as single layer islands that preferentially nucleated at atomic steps of the substrate and progressed in a layer-by-layer like fashion. A close to ideal wetting behavior resulted in coalesced PtSe2 films after depositing about 1.5 PtSe2 layers. Detailed Raman investigation of the observed PtSe2 layer breathing modes of films grown under optimized co-deposition conditions revealed an interlayer coupling force constant of 5.0–5.6 × 1019 N m−3.

Different optical characteristics between monolayer and bilayer WS2 due to interlayer interaction

In this research Raman spectroscopy and photoluminescence (PL) spectroscopy measurements reveal different optical characteristics between monolayer (1 L) and bilayer (2 L) WS2 due to the interlayer interaction. First, ultralow frequency (ULF) Raman spectra indicate that 2 L WS2 shows additional shear mode (S) and layer-breathing (LB) mode in comparison with 1 L WS2. The 2 L WS2 has the in-plane vibration mode E2g1 red-shifted while the out-plane vibration mode A1g blue-shifted. Then, both direct transition (DT) and indirect transition (IT) emission are observed in the PL spectra for 2 L WS2 while only DT for 1 L WS2. The PL signal corresponding to localized excitons, that is measured as a low energy side tail with the DT emission, is more prominent for 1 L WS2 at low temperature of 7 K. The DT emission and IT emission show opposite variation trend as the temperature increases from 7 K to 300 K, while the average phonon energy in 2 L WS2 is estimated to be almost twice of that for 1 L WS2. These observations illustrate that the interlayer interaction not only change the phonon characteristics for WS2, but also impact the energy band structure and the exciton dynamics, including exciton radiative recombination and exciton-phonon interaction.

Operando Measurement of Layer Breathing Modes in Lithiated Graphite

Despite their ubiquitous usage and increasing societal dependence on Li-ion batteries, there remains a lack of detailed empirical evidence of Li intercalation/deintercalation into graphite even though this process dictates the performance, longevity, and safety of the system. Here, we report direct detection and dissociation of specific crystallographic phases in the lithiated graphite, which form through a stepwise staging process. Using operando measurements, LiC18, LiC12, and LiC6 phases are observed via distinct low-frequency Raman features, which are the result of displacement of the graphite lattice by induced local strain. Density functional theory calculations confirm the nature of the Raman-active vibrational modes, to the layer breathing modes (LBMs) of the lithiated graphite. The new findings indicate graphene-like characteristics in the lithiated graphite under the deep charged condition due to the imposed strain by the inserted Li. Moreover, our approach also provides a simple experimental tool to measure induced strain in the graphite structure under full intercalation conditions.

Temperature dependent Raman spectroscopy of shear and layer breathing modes in bilayer MoS2

We report low-frequency Raman scattering results of bilayer (2L) MoS2 structures with 3R and 2H stacking orders. The stacking orders were identified by Raman mapping images of the low-frequency shear (S) and layer breathing (B) modes. Linear temperature coefficients (χ) were obtained from temperature-dependent frequency changes of the shear and layer breathing modes for the 3R- and 2H-stacked 2L MoS2: χ3RS=−0.011±0.006cm−1/K, χ2HS=−0.009±0.002cm−1/K, χ3RB=−0.009±0.003cm−1/K, and χ2HB=−0.010±0.002cm−1/K. Interestingly, the temperature coefficients were significantly reduced after the MoS2 samples were thermally heated: χ3RS=−0.004±0.001cm−1/K, χ2HS=−0.004±0.001cm−1/K, χ3RB=−0.002±0.001cm−1/K, and χ2HB=−0.002±0.001cm−1/K. Similar behaviors were also observed for the temperature coefficients of the high-frequency E2g1 and A1g phonons. The heating-induced modifications in the temperature coefficients are attributed to changes in the MoS2–substrate coupling. Our result further paves the way for optimal design strategies for low-dimensional device applications where thermal management plays a crucial role in device performance.

Phonon-Mediated Interlayer Charge Separation and Recombination in a MoSe2/WSe2 Heterostructure

Monolayer transition metal dichalcogenides bear great potential for photodetection and light harvesting due to high absorption coefficients. However, these applications require dissociation of strongly bound photogenerated excitons. The dissociation can be achieved by vertically stacking different monolayers to realize band alignment that favors interlayer charge transfer. In such heterostructures, the reported recombination times vary strongly, and the charge separation and recombination mechanisms remain elusive. We use two color pump-probe microscopy to demonstrate that the charge separation in a MoSe2/WSe2 heterostructure is ultrafast (∼200 fs) and virtually temperature independent, whereas the recombination accelerates strongly with temperature. Ab initio quantum dynamics simulations rationalize the experiments, indicating that the charge separation is temperature-independent because it is barrierless, involves dense acceptor states, and is promoted by higher-frequency out-of-plane vibrations. The strong temperature dependence of the recombination, on the other hand, arises from a transient indirect-to-direct bandgap modulation by low-frequency shear and layer breathing motions.

Structural configurations and Raman spectra of carbon nanoscrolls

Three types of carbon nanoscroll (CNS) structures that are formed when scrolling up graphene sheets are investigated using Raman spectroscopy and atomic force microscopy (AFM). The CNSs were produced from exfoliated monolayer graphene deposited on a Si chip by applying a droplet of isopropyl alcohol (IPA) solution. The three types of CNS are classified as single-elliptical-core, double-elliptical-core (both with large internal volumes) and collapsed ribbon-like, based on AFM surface profile measurements. We discuss the structure and formation of CNS with much larger hollow cores than is commonly assumed and relate this to the large effective 2D bending stiffness of graphene in the IPA solution. The large elliptical core structures show Raman spectra similar to those previously reported for CNS and indicate little interaction between the scrolled layers. The Raman spectra from ribbon-like structures show additional features that are similar to that of folded graphene. These new features can be related to layer breathing modes combined with some resonance enhancement at specific regions of the ribbon-like CNSs that are due to specific twist angles produced when the structure folds/collapses.

Phonons in twisted transition-metal dichalcogenide bilayers: Ultrasoft phasons and a transition from a superlubric to a pinned phase

The tunability of the interlayer coupling by twisting one layer with respect to another layer of two-dimensional materials provides a unique way to manipulate the phonons and related properties. We refer to this engineering of phononic properties as "Twistnonics". We study the effects of twisting on low-frequency shear (SM) and layer breathing (LBM) modes in transition metal dichalcogenide (TMD) bilayer using atomistic classical simulations. We show that these low-frequency modes are extremely sensitive to twist and can be used to infer the twist angle. We find unique "ultra-soft" phason modes (frequency $\lesssim 1\ \mathrm{cm^{-1}}$, comparable to acoustic modes) for any non-zero twist, corresponding to an \textit{effective} translation of the moir{\'e} lattice by relative displacement of the constituent layers in a non-trivial way. Unlike the acoustic modes, the velocity of the phason modes is quite sensitive to twist angle. As twist angle decreases, ($\theta \lesssim 3^{\circ},\ \gtrsim 57^{\circ}$) the ultra-soft modes represent the acoustic modes of the "emergent" soft moir{\'e} scale lattice. Also, new high-frequency SMs appear, identical to those in stable bilayer TMD ($\theta = 0\degree/60\degree$), due to the overwhelming growth of stable stacking regions in relaxed twisted structures. Furthermore, we find remarkably different structural relaxation as $\theta \to 0^{\circ}$, $\to 60^{\circ}$ due to sub-lattice symmetry breaking. Our study reveals the possibility of an intriguing $\theta$ dependent superlubric to pinning behavior and of the existence of ultra-soft modes in \textit{all} two-dimensional (2D) materials.

Vertical van der Waals Heterostructure of Single Layer InSe and SiGe

We present a first-principles investigation on the stability, electronic structure and mechanical response of ultra-thin heterostructure composed of single layers of InSe and SiGe. First, by per- forming total energy optimization and phonon calculations, we show that single layers of InSe and SiGe can form dynamically stable heterostructures in 12 different stacking types. Valence and conduction band edges of the heterobilayers form a type-I heterojunction having a tiny bandgap ranging between 0.09-0.48 eV. Calculations on elastic-stiffness tensor reveal that two mechanically soft single layers form a heterostructure which is stiffer than constituent layers due to relatively strong interlayer interaction. Moreover, phonon analysis show that the bilayer heterostructure has highly Raman active modes at 205.3 and 43.7 cm −1 , stemming from out-of-plane interlayer mode and layer breathing mode, respectively. Our results show that, as a stable type-I heterojunction, ultra-thin heterobilayer of InSe/SiGe holds ...

Layer breathing and shear modes in multilayer graphene: a DFT-vdW study

In this work, we study structural and vibrational properties of multilayer graphene using density-functional theory with van der Waals (vdW) functionals. Initially, we analyze how different vdW functionals compare by evaluating the lattice parameters, elastic constants and vibrational frequencies of low energy optical modes of graphite. Our results indicate that the vdW-DF1-optB88 functional has the best overall performance on the description of vibrational properties. Next, we use this functional to study the influence of the vdW interactions on the structural and vibrational properties of multilayer graphene. Specifically, we evaluate binding energies, interlayer distances and phonon frequencies of layer breathing and shear modes. We observe excellent agreement between our calculated results and available experimental data, which suggests that this functional has truly predictive power for layer-breathing and shear frequencies that have not been measured yet. This indicates that careful selected vdW functionals can describe interlayer bonding in graphene-related systems with good accuracy.

Effect of humidity on the interlayer interaction of bilayer graphene

The lubricating ability of graphite largely depends on the environmental humidity, essentially the amount of water in between its layers. In general, intercalated molecules in layered materials modify their extraordinary properties by interacting with the layers. To understand the interaction of intercalated water molecules with graphene layers, we performed Raman measurements on bi-layer graphene at various humidity levels and observed an additional peak close to that of the low-frequency layer breathing mode between two graphene layers. The additional peak is attributed to the vibration between an intercalated water layer and the graphene layers. We further propose that the monolayer coverage of water increases between bilayer graphene with increasing environmental humidity while the interaction between the water layer and graphene layers remains approximately unchanged, until too much water is intercalated to keep the monolayer structure, at just over 50\% relative humidity. Notably, the results suggest that unexpectedly humidity could be an important factor affecting the properties of layered materials, as it significantly modifies the interlayer interaction.

Dependence of characteristic interlayer vibration modes on interlayer spin arrangement in stacked graphene nanofragments

The freedom of interlayer spin arrangement could emerge when assembling small-sized graphene-based nanostructures through stacking. Its possible influence on interlayer vibrations could be significant for developing Raman probes towards small complexes and device design involving intermolecular vibronic process. In this paper, using density-functional-theory calculations on bilayer and trilayer rhombic graphene fragments, we compare finite-size analogues to interlayer shear and breathing modes regarding to ferromagnetic and antiferromagnetic interlayer spin arrangements. For bilayer units, the antiferromagnetic configuration further separate two shear mode components by around 10 cm−1, inducing a further Raman peak splitting. This response is robust regarding to slightly enlarging the fragment and increasing layer number to three. Layer breathing mode is spin-arrangement robust in bilayers but show different arrangement-sensitivity in ABA-like and ABC-like trilayers. Visualization of interface electron density reveals the dependence of anisotropic interface environment to interlayer spin arrangement and unambiguously correlates the arrangement style with shearing responses. Further application of this analysis clarifies the arrangement-based phase-cooperation in trilayer shearing. Results and analysis in this work may contribute to the characterization and design of graphene-based nanostructures as well as understanding the interfacial nature beneath their intermolecular varieties in dynamic processes.

Anharmonicities in phonon combinations and overtones in bilayered graphene: A temperature-dependent approach

This paper studies phonon anharmonicities related to the phonon combination ${\mathrm{LOZO}}^{\ensuremath{'}}$ and phonon overtone 2ZO in a $AB$-stacked bilayer graphene (2LG). The results explain in detail the rule of the ${\mathrm{ZO}}^{\ensuremath{'}}$ layer breathing mode in the 2LG electron and phonon relaxations, especially at temperatures above 543 K, where anomalous behaviors are observed for the ${\mathrm{LOZO}}^{\ensuremath{'}}$ frequencies, linewidths (and therefore, lifetimes), and integrated areas. Surprisingly, the 2ZO frequencies and linewidths do not show any dependence with temperature (ZO is the out-of-phase vibration of the layers). This result is explained via nonsymmetric lattice distortions and via the almost null $\mathrm{Gr}\stackrel{\ifmmode \ddot{}\else \"{}\fi{}}{\text{u}}\mathrm{neisen}$ parameter associated to the ZO mode. Recently, the correct assignments for the phonon combination and overtone modes studied here have been put in debate once again in a theoretical work by Popov [Carbon 91, 436 (2015)]. This work shows how temperature-dependent Raman spectroscopy is used to propose a solution for these recent assignment problems. Finally, although 2LG is the system used here, the measurements and discussions to approach electron and phonon relaxations have the potential to be extended to any other multilayered structure that presents ${\mathrm{ZO}}^{\ensuremath{'}}$- and ZO-like phonon modes.

Temperature-dependent layer breathing modes in two-dimensional materials

Relative out-of-plane displacements of the constituent layers of two-dimensional materials give rise to unique low-frequency breathing modes. By computing the height-height correlation functions from molecular dynamics simulations, we show that the layer breathing modes (LBMs) can be mapped consistently to vibrations of a simple linear chain model. Our calculated thickness dependence of LBM frequencies for few-layer (FL) graphene and molybdenum disulfide $({\mathrm{MoS}}_{2})$ are in excellent agreement with available experiments. Our results show a redshift of LBM frequency with an increase in temperature, which is a direct consequence of anharmonicities present in the interlayer interaction. We also predict the thickness and temperature dependence of LBM frequencies for FL hexagonal boron nitride. Our Rapid Communication provides a simple and efficient way to probe the interlayer interaction for layered materials and their heterostructures with the inclusion of anharmonic effects.

Graphite under compression: shift of layer breathing and shear modes frequencies with interlayer spacing

Layered materials have huge potential in various applications due to their extraordinary properties. To determine the interlayer interaction (or equivalently the layer spacing under different perturbations) is of critical importance. In this paper, we focus on one of the most prominent layered materials, graphite, and theoretically quantify the relationship between its interlayer spacing and the vibrational frequencies of its layer breathing and shear modes, which are measures of the interlayer interaction. The method used here to determine the interlayer interaction can be further applied to other layered materials.

Probing the shear and layer breathing modes in multilayer graphene by Raman spectroscopy

The measurements of interlayer vibrations in multilayer graphene (MLG) have triggered a huge effort to understand phonons, electron–electron, electron–phonon, magneto–phonon interactions and the effect of layer number, stacking sequences, and layer orientations on the Raman spectroscopy of MLG. Here, we provide a review on the optical probe of interlayer vibrations, comprising the shear (C) and layer breathing (LB) modes. At first, we discuss different symmetries of MLGs in AB, ABC, and twisted stacking with an example of trilayer graphene, which dramatically influence the observations of interlayer vibrations. Then a brief description about the physical origins of the C and LB modes is introduced. Finally, two ways are elucidated to probe the interlayer modes in detail. The C and LB modes can be directly probed in the ultralow‐wavenumber Raman spectroscopy with special configurations, as depicted by the Raman spectra in MLG with diverse stacking orders. On the other hand, the LB modes can also be derived from the two‐phonon overtones in doubly resonant Raman spectra. These approaches can be extended to the other two‐dimensional layered materials, which pave the way to measure the interlayer coupling from experiments and thus greatly benefit the future research studies on their fundamental physics and potential applications. Copyright © 2017 JohnWiley & Sons, Ltd.

Seebeck Coefficient of a Single van der Waals Junction in Twisted Bilayer Graphene.

When two planar atomic membranes are placed within the van der Waals distance, the charge and heat transport across the interface are coupled by the rules of momentum conservation and structural commensurability, leading to outstanding thermoelectric properties. Here we show that an effective "interlayer phonon drag" determines the Seebeck coecient (S) across the van der Waals gap formed in twisted bilayer graphene (tBLG). The cross-plane thermovoltage, which is nonmonotonic in both temperature and density, is generated through scattering of electrons by the out-of-plane layer breathing (ZO'/ZA2) phonon modes and differs dramatically from the expected Landauer-Buttiker formalism in conventional tunnel junctions. The tunability of the cross-plane Seebeck effect in van der Waals junctions may be valuable in creating a new genre of versatile thermoelectric systems with layered solids.