Few-layer Form Research Articles

Ultrathin natural biotite crystals as a dielectric layer for van der Waals heterostructure applications

Biotite, an iron-rich mineral belonging to the trioctahedral mica group, is a naturally abundant layered material (LM) exhibiting attractive electronic properties for application in nanodevices. Biotite stands out as a non-degradable LM under ambient conditions, featuring high-quality basal cleavage-a significant advantage for van der Waals heterostructure (vdWH) applications. In this work, we present the micro-mechanical exfoliation of biotite down to monolayers (1Ls), yielding ultrathin flakes with large areas and atomically flat surfaces. To identify and characterize the mineral, we conducted a multi-elemental analysis of biotite using energy-dispersive spectroscopy mapping. Additionally, synchrotron x-ray fluorescence and infrared nano-spectroscopy were employed to probe its iron content and vibrational signature in few-layer form, respectively, with sensitivity to the layer number. We have also observed good morphological and structural stability in time (up to 12 months) and no important changes in their physical properties after thermal annealing processes in ultrathin biotite flakes. Conductive atomic force microscopy evaluated its electrical capacity, revealing an electrical breakdown strength of approximately 1 V nm-1. Finally, we explore the use of biotite as a substrate and encapsulating LM in vdWH applications. We have performed optical and magneto-optical measurements at low temperatures. We find that ultrathin biotite flakes work as a good substrate for 1L-MoSe2, comparable to hexagonal boron nitride flakes, but it induces a small change of the 1L-MoSe2g-factor values, most likely due to natural impurities on its crystal structure. Furthermore, our results show that biotite flakes are useful systems to protect sensitive LMs such as black phosphorus from degradation for up to 60 days in ambient air. Our study introduces biotite as a promising, cost-effective LM for the advancement of future ultrathin nanotechnologies.

Unveiling the electronic properties of BiP[formula omitted] triphosphide from bulk to graphene-based heterostructures by first-principles calculations

In our study, we investigated the structural and electronic properties of bismuth triphosphide (BiP3) in its bulk, few-layer, and monolayer forms. We found that BiP3 in bulk exhibits a metallic stable layered structure. The exfoliation energy of 1.07 J/m2 indicates ease exfoliation, comparable to other triphosphides. The band gap varies with thickness, transitioning from semiconductor–metal between four to five layers, influenced by interlayer coupling and quantum confinement. We also investigated the heterostructure created by depositing graphene (G) on few-layer BiP3. In monolayer (G/m-BiP3) and bilayer (G/2L-BiP3) forms, a metal–semiconductor junction is formed, characterized by weak vdW interactions at the interface and exhibiting p-type Schottky contacts. We observed that the Schottky Barrier Height (SBH) can be modulated by altering the interlayer distance between G and BiP3. This adjustment allows transitions between n-type and p-type Schottky contacts in G/m-BiP3 and the formation of an ohmic contact in G/2L-BiP3. Furthermore, applying an electric field affects the SBH, leading to similar transitions and the development of an ohmic contact. Additionally, our study shows that n-doping in graphene increases with the number of BiP3 layers and external electric field application. These properties position BiP3 few-layer as a promising material for nanoelectronic, optoelectronic, and graphene-based devices.

Electrical detection of the flat-band dispersion in van der Waals field-effect structures

Two-dimensional flat-band systems have recently attracted considerable interest due to the rich physics unveiled by emergent phenomena and correlated electronic states at van Hove singularities. However, the difficulties in electrically detecting the flat-band position in field-effect structures are slowing down the investigation of their properties. In this work, we use indium selenide (InSe) as a flat-band system due to a van Hove singularity at the valence-band edge in a few-layer form of the material without the requirement of a twist angle. We investigate tunnelling photocurrents in gated few-layer InSe structures and relate them to ambipolar transport and photoluminescence measurements. We observe an appearance of a sharp change in tunnelling mechanisms due to the presence of the van Hove singularity at the flat band. We further corroborate our findings by studying tunnelling currents as a reliable probe for the flat-band position up to room temperature. Our results create an alternative approach to studying flat-band systems in heterostructures of two-dimensional materials.

Электрохимическое восстановление многослойного оксида графена в щелочном электролите

The results of the study of the electrochemical reduction of multilayer graphene oxide in the potentiostatic mode are presented and the possibility of using alkaline electrolyte (KOH) with the concentration below 0.1 M is shown. The identification of the electrochemically reduced graphene oxide was carried out using the XRD, FTIR and Raman-spectroscopy methods. Applying the method of Raman spectroscopy the increase in the intensity of the G and 2D bands, indicating the formation of few-layer forms of reduced graphene oxide was found. The surface morphology of the electrochemically reduced graphene oxide was studied by means of the SEM method.

Structure, Thermodynamics, and Raman Spectroscopy of Rhenium-Doped Bulk MoS2 from First Principles

Doping MoS$_2$ with Re is known to alter the electronic, structural, and tribological properties. Re-doped MoS$_2$ has been previously mainly studied in monolayer or few-layer form, but can also be relevant for applications in many-layer or bulk form. In this work, we use density functional theory to explore the structure, phase stability, and Raman spectrum of bulk Re-doped MoS$_2$. We consider the possibility of the Re dopant existing at different locations and provide experimentally distinguishable characteristics of the most likely sites: Mo-substitution and tetrahedral (t-) intercalation. We demonstrate and benchmark a general approach to calculate Raman spectra of doped materials with metallic densities of states by using atomic Raman tensors from the pristine material. Applying this method to the metallic Re-doped structures, we find characteristic shifts in the Raman-active peaks depending on Re dopant position: redshifts in both A$_{\rm 1g}$ and E$_{\rm 2g}^1$ peaks in the t-intercalated case versus a redshift for A$_{\rm 1g}$ and blueshift (sometimes accompanied by a smaller redshifted peak) for E$_{\rm 2g}^1$ peaks in the Mo-substituted case, which can be used to identify the dopant sites in experimental samples. We analyze the interactions giving rise to these shifts.

A pathway toward high-throughput quantum Monte Carlo simulations for alloys: A case study of two-dimensional (2D) GaSxSe1-x.

The study of alloys using computational methods has been a difficult task due to the usually unknown stoichiometry and local atomic ordering of the different structures experimentally. In order to combat this, first-principles methods have been coupled with statistical methods such as the cluster expansion formalism in order to construct the energy hull diagram, which helps to determine if an alloyed structure can exist in nature. Traditionally, density functional theory (DFT) has been used in such workflows. In this paper, we propose to use chemically accurate many-body variational Monte Carlo (VMC) and diffusion Monte Carlo (DMC) methods to construct the energy hull diagram of an alloy system due to the fact that such methods have a weakerdependence on the starting wavefunction and density functional, scale similarly to DFT with the number of electrons, and have had demonstrated success for a variety of materials. To carry out these simulations in a high-throughput manner, we propose a method called Jastrow sharing, which involves recycling the optimized Jastrow parameters between alloys with different stoichiometries. We show that this eliminates the need for extra VMC Jastrow optimization calculations and results in significant computational cost savings (on average 1/4 savings of total computational time). Since it is a novel post-transition metal chalcogenide alloy series that has been synthesized in its few-layer form, we used monolayer GaSxSe1-x as a case study for our workflow. By extensively testing our Jastrow sharing procedure for monolayer GaSxSe1-x and quantifying the cost savings, we demonstrate how a pathway toward chemically accurate high-throughput simulations of alloys can be achieved using many-body VMC and DMC methods.

Computational design of moiré assemblies aided by artificial intelligence

Two-dimensional (2D) layered materials offer a materials platform with potential applications from energy to information processing devices. Although some single- and few-layer forms of materials such as graphene and transition metal dichalcogenides have been realized and thoroughly studied, the space of arbitrary layered assemblies is still mostly unexplored. The main goal of this work is to demonstrate precise control of layered materials' electronic properties through careful choice of the constituent layers, their stacking, and relative orientation. Physics-based and AI-driven approaches for the automated planning, execution, and analysis of electronic structure calculations are applied to layered assemblies based on prototype one-dimensional (1D) materials and realistic 2D materials. We find it is possible to routinely generate moiré band structures in 1D with desired electronic characteristics such as a bandgap of any value within a large range, even with few layers and materials (here, four and six, respectively). We argue that this tunability extends to 2D materials by showing the essential physical ingredients are already evident in calculations of two-layer MoS2 and multi-layer graphene moiré assemblies.

Mechanical properties and applications of 2D black phosphorus

Single- or few-layer forms of black phosphorus, so called phosphorene, were isolated by exfoliation in 2014 as 2D layered materials holding great promise in electronic and optoelectronic fields. In this perspective, we highlight recent developments in black phosphorus research, in particular, we will focus on the mechanical properties of its 2D form. Its unique puckered structure is responsible for strong anisotropy in mechanical and transport properties, different from graphene and transition-metal dichalcogenide 2D materials. This peculiar mechanical anisotropy can be exploited for applications such as nanomechanical resonators, thermoelectric devices, and motion sensors with tunable functions inaccessible by isotropic materials. Current bottlenecks hindering further progress in devices applications involve first surface degradation in environmental conditions which, in turn, can be exploited in surface friction mechanics to achieve superlubricity. In this framework, the investigation of mechanical properties of phosphorene will be pivotal for facile fabrication, transfer, and resolution of technical hurdles as well the discovery of novel applications. As research directions in next foreseeable future, we will discuss the challenge of crosstalk between mechanical and transport properties, in particular, how the stress–strain stimulations can be used to tune optoelectronic and thermoelectric performance.

(Invited) Laser-Assisted Exfoliation of Black Phosphorus with Thickness Control for Li-Ion Batteries

Few-layer black phosphorus (BP) is an emerging two-dimensional (2D) material with exciting properties such as tunable bandgap and high charge carrier mobility, which make it a suitable candidate for energy storage applications. However, its preparation remains challenging. Currently, the exfoliation of bulk crystal to its few-layer form assisted by liquid-phase exfoliation (LPE) process using ultrasonic agitation is commonly adopted, which is time-consuming and suffers low efficiency and lack of morphologic control. In this study, we demonstrate a highly-efficient route for the scalable production few-layer BP nanosheets using a pulsed laser in low-boiling point solvents. By adjusting the laser irradiation time and solvent type, the morphology (layer number and lateral size) of the few-layer BP nanosheets is tuned with a narrow distribution (layer number from 3 to 13, lateral size from <2 µm to >5 µm). The laser-assisted exfoliation is understood by a plasma quenching mechanism and interlayer interaction weakened by the in situ generated vapor bubbles. The fine control of thickness and lateral size of the BP nanosheets enables us to study their impact on Li-ion battery performance when applied as anode material. We present herein the correlation of the layer number and larger lateral size of BP with the electronic conductivity, Li+ ion transfer rate and diffusivity, as well as long-term cyclability, revealing the morphology-dependent battery performance. Figure 1

Group theory study of the vibrational modes and magnetic order in the topological antiferromagnet MnBi2Te4

We employ group theory to study the properties of the lattice vibrations and magnetic order in the antiferromagnetic topological insulator MnBi$_2$Te$_4$, both in bulk and few-layer form. In the paramagnetic phase, we obtain the degeneracies, the selection rules, and real-space displacements for the lattice vibrational modes for different stacking configurations. We discuss how magnetism influences these results. As a representative example, we consider a double septuple layer system and obtain the form of the magnetic order allowed by the symmetries of the crystal. We derive the allowed coupling terms that describe the paramagnetic to antiferromagnetic transition. Finally, we discuss the implications of our results for Raman scattering and other optical measurements. Our work sets the stage for a deeper understanding of the interplay of lattice modes, band topology, and magnetic order in MnBi$_2$Te$_4$ and other symmetry-related materials.

Impetuous exfoliation of tungsten disulfide into a few-layer nanoscale form due to super active collagenase biomolecules

We report on the collagenase activated progressive, yet spontaneous exfoliation of the stacked tungsten disulfide (WS2) system into a few-layer form via interface engineering and taking advantage of diffusion of hydronium ions (H3O+) through the interfaces. As evidenced from the Raman spectra, the apparent improvement of intensity ratio (E12g -to- A1g) from a value of 0.55 to 1.5, along with the evolution of (E12g+ LA), (A1g+ LA) modes have confirmed irreversible exfoliation of the stack of WS2 layers into its nano-dimensional form. Atomic force microscopy imaging confirms the exfoliation of WS2 system down to ten layers after eight days of continuous treatment with the super active biomolecules. The passage of H3O+ ions was believed to weaken the van der Waal forces between the WS2 layers and eventually cause impetuous exfoliation. The entropy change (ΔSt) during exfoliation and up to ten layers was predicted as, 1.83 ± 0.03 mJ m−2 K−1. The saturative trends of work accomplished and entropy change beyond six days of treatment indicate occurrence of complete exfoliation and with a high yield of nanoscale WS2. The scope of understanding the development of exfoliated layers linking diffraction, spectroscopic and imaging data is immensely beneficial for exploiting hybrid 2D nanostructures with suitable surface anchoring and designing miniaturized elements.

A comparative study for producing few-layer graphene sheets via electrochemical and microwave-assisted exfoliation from graphite powder

Graphene’s astonishing properties drew attention of many scientists to dedicate a lot of their time to find out more about this extraordinary material. However, challenges continue to produce high-quality graphene in large quantities by using inexpensive and readily available methods. In this study, three different graphite powders have been used as starting materials to produce few-layer graphene sheets, which are pure natural graphite (NGr) and two different electrochemically treated expanded graphite EE1 and EE2. Two simple and time-effective techniques have been applied on the samples interchangeably to investigate the order effect on producing graphene sheets in few-layer form. These techniques are sonication in dimethylformamide (DMF) for one hour and rapid microwave irradiation for 30 s. The study suggests that if the graphite powder is treated first with a strong exfoliation reagent followed by microwave irradiation, the obtained graphene will be high-quality few-layer (~ 5 layers). Sonication in DMF has worked to increase the inter-planar spacing between graphite layers, while microwave irradiation has worked to decrease the defect density ratio that resulted after sonication process. Our work suggests a novel route to prepare high-quality few-layer graphene sheets, not only with time efficiency, low-cost, and without using harmful chemicals, but also an adequate method for large-scale high-efficiency production of graphene materials.

Ultrafast 27\u2009GHz cutoff frequency in vertical WSe2 Schottky diodes with extremely low contact resistance

Ultra-thin two-dimensional semiconducting crystals in their monolayer and few-layer forms show promising aspects in nanoelectronic applications. However, the ultra-thin nature of two-dimensional crystals inevitably results in high contact resistance from limited channel/contact volume as well as device-to-device variability, which seriously limit reliable applications using two-dimensional semiconductors. Here, we incorporate rather thick two-dimensional layered semiconducting crystals for reliable vertical diodes showing excellent Ohmic and Schottky contacts. Using the vertical transport of WSe2, we demonstrate devices which are functional at various frequency ranges from megahertz AM demodulation of audio signals, to gigahertz rectification for fifth-generation wireless electronics, to ultraviolet–visible photodetection. The WSe2 exhibits an excellent Ohmic contact to bottom platinum electrode with record-low contact resistance (~50 Ω) and an exemplary Schottky junction to top transparent conducting oxide electrode. Our semitransparent vertical WSe2 Schottky diodes could be a key component of future high frequency electronics in the era of fifth-generation wireless communication.

Phosphorene and Black Phosphorus: The 31P NMR View.

This work aims at characterizing for the first time the 31P spin interactions determining the nuclear magnetic resonance (NMR) properties of solid black phosphorus (bP) and of its few-layer exfoliated form (fl-bP). Indeed, the knowledge of these properties is still very poor, despite the great interest received by this layered phosphorus allotrope and its exfoliated 2D form, phosphorene. By combining density functional theory (DFT) calculations and solid-state NMR experiments on suspensions of fl-bP nanoflakes and on solid bP, it has been possible to characterize the 31P homonuclear dipolar and chemical shift interactions, identifying the network of 31P nuclei more strongly dipolarly coupled and highlighting two kinds of magnetically nonequivalent 31P nuclei. These results add an important missing piece of information to the fundamental chemico-physical knowledge of bP and support future extensive applications of NMR spectroscopy to the characterization of phosphorene-based materials.

Carrier dynamics and spin–valley–layer effects in bilayer transition metal dichalcogenides

Transition metal dichalcogenides are an interesting class of low dimensional materials in mono- and few-layer form with diverse applications in valleytronic, optoelectronic and quantum devices. Therefore, the general nature of the band-edges and the interplay with valley dynamics is important from a fundamental and technological standpoint. Bilayers introduce interlayer coupling effects which can have a significant impact on the valley polarization. The combined effect of spin-orbit and interlayer coupling can strongly modify the band structure, phonon interactions and overall carrier dynamics in the material. Here we use first-principles calculations of electron-electron and electron-phonon interactions to investigate bilayer MoS2 and WSe2 in both the AA' and AB stacking configurations. We find that in addition to spin-orbit coupling, interlayer interactions present in the two configurations significantly alter the near-band-edge dynamics. Scattering lifetimes and dynamic behavior are highly material-dependent, despite the similarities and typical trends in TMDCs. Additionally, we capture significant differences in dynamics for the AA' and AB stacking configurations, with lifetime values differing by up to an order of magnitude between them for MoS2. Further, we evaluate the valley polarization times and find that maximum lifetimes at room temperature are of the scale of 1 picosecond for WSe2 in the AB orientation. These results present a pathway to understanding complex heterostructure configurations and 'magic angle' physics in TMDCs.

Structural Damage of Few-Layer Silicene in Vertical and Parallel Lithiations

Few-layer silicene is a promising anode material for lithium (Li) ion batteries. In this work, the structural damage of few-layer silicene in vertical and parallel lithiation processes are investigated using reactive force field molecular dynamics simulations. Simulation results showed that within a certain degree of lithiation, the layered structure of few-layer silicene is severely damaged during parallel lithiation but can be preserved during vertical lithiation. During lithiation, Li atom has two typical reacting paths, namely, damaging and migrating paths. In the damaging path, Li atoms form Li-Si (Silicon) bonds with Si atoms at the surface and participate in structural damage. In the migrating path, Li atoms migrate into the few-layer silicene and form Li-Si bonds with the inner Si atoms. The migrating path has significantly lower energy barrier height than the damaging path in vertical direction, whereas their energy barriers have similar height in the parallel direction. Li atoms prefer the damaging path during parallel lithiation and the migrating path during vertical lithiation. As the edge area of few-layer silicene is limited, the probability of parallel lithiation is relatively low. Reducing the height and enlarging the width and length of few-layer silicene pieces might improve the cyclability of silicene anodes.

Electronic band structure of 4d and 5d transition metal trichalcogenides

Transition metal trichalcogenides (TMTs), a family of van der Waals materials, have gained increasing interests from the discovery of magnetism in few-layer forms. Although TMTs with 3d transition metal elements have been studied extensively, much less is explored for the 4d and 5d cases, where the interesting interplay between electron correlations and the relativistic spin-orbit coupling is expected. Using ab initio calculations, we here investigate the electronic property of TMTs with 4d and 5d transition metal elements. We show that the band structures exhibit multiple node-like features near the Fermi level. These are the remnant of multiple Dirac cones that were recently discovered in the monolayer cases. Our results indicate that the peculiar two-dimensional multiple Dirac cones are concealed even in the layered bulk systems.

Recent Progress on Antimonene: A New Bidimensional Material.

Antimonene, defined in sensu stricto as a single layer of antimony atoms, is recently the focus of numerous theoretical works predicting a variety of interesting properties and is quickly attracting the attention of the scientific community. However, what places antimonene in a different category from other 2D crystals is its strong spin-orbit coupling and a drastic evolution of its properties from the monolayer to the few-layer system. The recent isolation of this novel 2D material pushes the interest for antimonene even further. Here, a review of both theoretical predictions and experimental results is compiled. First, an account of the calculations anticipating an electronic band structure suitable for optoelectronics and thermoelectric applications in monolayer form and a topological semimetal in few-layer form is given. Second, the different approaches to produce antimonene-mechanical and liquid phase exfoliation, and epitaxial growth methods-are reviewed. In addition, this work also reports the main characterization techniques used to study this exotic material. This review provides insights for further exploring the appealing properties of antimonene and puts forward the opportunities and challenges for future applications from (opto)electronic device fabrication to biomedicine.

Tunable indirect-direct transition of few-layer SnSe via interface engineering

Tin selenide (SnSe) is one of the best thermoelectric materials reported to date. The possibility of growing few-layer SnSe helped boost the interest in this long-known, earth abundant material. Pristine SnSe in bulk, mono- and few-layer forms are reported to have indirect electronic bandgaps. Possible indirect-direct transition in SnSe is attractive for its optoelectronic-related applications. Based on the results from first principles density functional theory calculations, we carefully analyzed electronic band structures of bulk, and bilayer SnSe with various interlayer stackings. We report the possible stacking-dependent indirect-direct transition of bilayer SnSe. By further analysis, our results reveal that it is the directionality of interlayer interactions that determine the critical features of their electronic band structures. In fact, by engineering the interface stacking between layers, it is possible to achieve few-layer SnSe with direct electronic band gap. This study provides fundamental insights to design few-layer SnSe and SnSe heterostructures for electronic/optoelectronic applications, where the interface geometry plays a fundamental role in device performance.

Efficient electrical control of thin-film black phosphorus bandgap

Recently rediscovered black phosphorus is a layered semiconductor with promising electronic and photonic properties. Dynamic control of its bandgap can allow for the exploration of new physical phenomena. However, theoretical investigations and photoemission spectroscopy experiments indicate that in its few-layer form, an exceedingly large electric field in the order of several volts per nanometre is required to effectively tune its bandgap, making the direct electrical control unfeasible. Here we reveal the unique thickness-dependent bandgap tuning properties in intrinsic black phosphorus, arising from the strong interlayer electronic-state coupling. Furthermore, leveraging a 10 nm-thick black phosphorus, we continuously tune its bandgap from ∼300 to below 50 meV, using a moderate displacement field up to 1.1 V nm−1. Such dynamic tuning of bandgap may not only extend the operational wavelength range of tunable black phosphorus photonic devices, but also pave the way for the investigation of electrically tunable topological insulators and semimetals.