Van Der Waals Crystals Research Articles

Interfacing differently oriented biaxial van der Waals crystals for negative refraction

Abstract Negative refraction has a wide range of applications in diverse fields such as imaging, sensing, and waveguides and typically entails the fabrication of intricate metamaterials endowed with hyperbolic features. In contrast to artificially engineered hyperbolic materials, natural van der Waals (vdW) materials are more accessible owing to their inherent strong in-plane covalent bonding and weak interlayer interactions. However, most vdW materials manifest uniaxial crystal properties, which restrict their behavior solely to out-of-plane hyperbolicity. This characteristic poses a considerable challenge to their seamless integration via planar fabrication techniques, unless a suitable pattern is employed. Recent advances have identified natural biaxial α-MoO3 as a promising vdW material capable of exhibiting in-plane hyperbolicity. In this study, we performed numerical simulations demonstrating that negative refraction could be achieved by interfacing differently oriented α-MoO3 slabs coated with tunable graphene on a gold substrate. Our comprehensive analysis yielded three notable outcomes: negative refraction, simultaneous positive and negative refractions, and diffractionless propagation. These outcomes could be operated in a broad range of frequencies and achieved at all angles to offer a superior platform for the flexible manipulation of mid-infrared polaritons. Our findings provide valuable insights into the potential application of other two-dimensional vdW materials for advances in nanoscale super-resolution imaging, molecular sensing, and on-chip photonic integrated circuits.

Photoemission Study of the Thermoelectric Group IV‐VI van der Waals Crystals (GeS, SnS, and SnSe)

AbstractGroup IV‐VI van der Waals crystals (MX, where M = Ge, Sn, and X = S, Se) are receiving increasing attention as semiconducting thermoelectric materials with nontoxic, earth‐abundant composition. Among them, SnSe is considered the most promising as it exhibits a remarkably high thermoelectric figure of merit (ZT), initially attributed to its low lattice thermal conductivity. However, it has been shown that the electronic band structure plays an equally important role in thermoelectric performance. A certain band shape, described as a “pudding mold” and characteristic for all MXs, has been predicted to significantly improve ZT by combining good electrical conductivity with high Seebeck coefficient. This subtle feature is explored experimentally for GeS, SnS, and SnSe by means of angle‐resolved photoemission spectroscopy. The technique also allows for the determination of the effective mass and Fermi level position of as‐grown undoped crystals. The findings are supported by ab initio calculations of the electronic band structure. The results greatly contribute to the general understanding of the valence band dispersion of MXs and reinforce their potential as high‐performance thermoelectric materials, additionally giving prospects for designing systems consisting of van der Waals heterostructures.

Ultra-broadband mid-infrared absorber based on hyperbolic α-MoO3

Owing to their broad operational bandwidth, broadband absorbers are extensively used in various applications, such as solar cells, microbolometers, and light modulators. To enhance energy harvesting, it is essential to achieve insensitivity to wide incident angles and polarization-independent absorption. α-MoO3 is a natural polar van der Waals crystal that hosts phonon polaritons in the mid-infrared spectral region. These polaritons can manipulate the infrared light at the nanoscale and break the diffraction limit, offering a great opportunity for the design of broadband absorbers. In this study, we propose a strategy based on an array of crossed the permittivity of α-MoO3 in [100] and [001] crystallographic axes to expand its broadband absorption. Triangular one-dimensional grating pattern is initially considered, which shows an ultra-broadband and wide-angle insensitive absorption within the range of 10.23–18.07 μm. Subsequently, square pyramidal two-dimensional arrays are investigated, which not only show ultra-broadband absorption and wide-angle insensitivity, but also exhibit polarization independence within the range of 10.46–18.32 μm. This remarkable broadband absorption is elucidated by the effective medium theory and the local power dissipation density. These results demonstrate an effective strategy for constructing ultra-broadband absorbers based on α-MoO3 for applications in solar thermal and photovoltaic systems.

Strong and controlled photonic spin Hall effect in a van der Waals semiconducting transition metal oxide slab

A natural biaxial van der Waals material α-MoO3 hosts the in-plane anisotropy as well as the ultra-low-loss polaritons, which hold great potential in the applications of subwavelength focusing, planar nanooptics as well as polarization converters. Here, we show that the simple α-MoO3 slab supports giant spin shifts of the reflected wave for either the horizontal (H) or vertical (V) polarized incident waves at specific frequencies and the low as well as large incident angle regions, whose maximum values can reach their theoretical upper limit. Such obtained giant spin shifts at the low and large incident angles are governed by the intrinsically in-plane anisotropy of α-MoO3 and the zero values of the reflectance at the transverse magnetic or electric wave. In addition, we also examine how the orientation of the optical axis of α-MoO3 slab controls the sign and magnitude of the reflected spin shifts and find that the positions where the maximum spin shifts of the reflected wave happen can be switched by rotating it. Our results on the reflected spin shifts in the α-MoO3 slab lay a foundation for unraveling the photonic spin Hall effects of anisotropic van der Waals crystals.

Anisotropy-Driven Crystallization of Dimensionally Resolved Quasi-1D Van der Waals Nanostructures.

Unusual behavior in solids emerges from the complex interplay between crystalline order, composition, and dimensionality. In crystals comprising weakly bound one-dimensional (1D) or quasi-1D (q-1D) chains, properties such as charge density waves, topologically protected states, and indirect-to-direct band gap crossovers have been predicted to arise. However, the experimental demonstration of many of these nascent physics in 1D or q-1D van der Waals (vdW) crystals is obscured by the highly anisotropic bonding between the chains, stochasticity of top-down exfoliation, and the lack of synthetic strategies to control bottom-up growth. Herein, we report the directed crystallization of a model q-1D vdW phase, Sb2S3, into dimensionally resolved nanostructures. We demonstrate the uncatalyzed growth of highly crystalline Sb2S3 nanowires, nanoribbons, and quasi-2D nanosheets with thicknesses in the range of 10 to 100 nm from the bottom-up crystallization of [Sb4S6]n chains. We found that dimensionally resolved nanostructures emerge from two distinct chemical vapor growth pathways defined by diverse covalent intrachain and anisotropic vdW interchain interactions and controlled precursor ratios in the vapor phase. At sub-100 nm nanostructure thicknesses, we observe the hardening of phonon modes, blue-shifting of optical band gaps, and the emergence of a new high-energy photoluminescence peak. The directional growth of weakly bound 1D ribbons or chains into well-resolved nanocrystalline morphologies provides opportunities to develop ordered nanostructures and hierarchical assemblies that are suitable for a wide range of optoelectronic and quantum devices.

Magnetocaloric effect near room temperature in a freestanding two-dimensional non–van der Waals crystal of MnCoAs

Magnetocaloric effect near room temperature in a freestanding two-dimensional non–van der Waals crystal of MnCoAs

Polarization conversion in bottom-up grown quasi-1D fibrous red phosphorus flakes

Fibrous red phosphorus (RP) has triggered growing attention as an emerging quasi-one-dimensional (quasi-1D) van der Waals crystal recently. Unfortunately, it is difficult to achieve substrate growth of high-quality fibrous RP flakes due to their inherent quasi-1D structure, which impedes their fundamental property exploration and device integration. Herein, we demonstrate a bottom-up approach for the growth of fibrous RP flakes with (001)-preferred orientation via a chemical vapor transport (CVT) reaction in the P/Sn/I2 system. The formation of fibrous RP flakes can be attributed to the synergistic effect of Sn-mediated P4 partial pressure and the SnI2 capping layer-directed growth. Moreover, we investigate the optical anisotropy of the as-grown flakes, demonstrating their potential application as micro phase retarders in polarization conversion. Our developed bottom-up approach lays the foundation for studying the anisotropy and device integration of fibrous red phosphorus, opening up possibilities for the two-dimensional growth of quasi-1D van der Waals materials.

Mixed-dimensional moiré systems of twisted graphitic thin films.

Moiré patterns formed by stacking atomically thin van der Waals crystals with a relative twist angle can give rise to notable new physical properties1,2. The study of moiré materials has so far been limited to structures comprising no more than a few van der Waals sheets, because a moiré pattern localized to a single two-dimensional interface is generally assumed to be incapable of appreciably modifying the properties of a bulk three-dimensional crystal. Here, we perform transport measurements of dual-gated devices constructed by slightly rotating a monolayer graphene sheet atop a thin bulk graphite crystal. We find that the moiré potential transforms the electronic properties of the entire bulk graphitic thin film. At zero and in small magnetic fields, transport is mediated by a combination of gate-tuneable moiré and graphite surface states, as well as coexisting semimetallic bulk states that do not respond to gating. At high field, the moiré potential hybridizes with the graphitic bulk states due to the unique properties of the two lowest Landau bands of graphite. These Landau bands facilitate the formation of a single quasi-two-dimensional hybrid structure in which the moiré and bulk graphite states are inextricably mixed. Our results establish twisted graphene-graphite as the first in a new class of mixed-dimensional moiré materials.

Sonication-assisted liquid phase exfoliation of two-dimensional CrTe3 under inert conditions

Liquid phase exfoliation (LPE) has been used for the successful fabrication of nanosheets from a large number of van der Waals materials. While this allows to study fundamental changes of material properties’ associated with reduced dimensions, it also changes the chemistry of many materials due to a significant increase of the effective surface area, often accompanied with enhanced reactivity and accelerated oxidation. To prevent material decomposition, LPE and processing in inert atmosphere have been developed, which enables the preparation of pristine nanomaterials, and to systematically study compositional changes over time for different storage conditions. Here, we demonstrate the inert exfoliation of the oxidation-sensitive van der Waals crystal, CrTe3. The pristine nanomaterial was purified and size-selected by centrifugation, nanosheet dimensions in the fractions quantified by atomic force microscopy and studied by Raman, X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectroscopy (EDX) and photo spectroscopic measurements. We find a dependence of the relative intensities of the CrTe3 Raman modes on the propagation direction of the incident light, which prevents a correlation of the Raman spectral profile to the nanosheet dimensions. XPS and EDX reveal that the contribution of surface oxides to the spectra is reduced after exfoliation compared to the bulk material. Further, the decomposition mechanism of the nanosheets was studied by time-dependent extinction measurements after water titration experiments to initially dry solvents, which suggest that water plays a significant role in the material decomposition.

Anisotropic hybridization probed by polarization dependent x-ray absorption spectroscopy in VI3 van der Waals Mott ferromagnet

Polarization dependent x-ray absorption spectroscopy was used to study the magnetic ground state and the orbital occupation in bulk-phase VI3 van der Waals crystals below and above the ferromagnetic and structural transitions. X-ray natural linear dichroism and x-ray magnetic circular dichroism spectra acquired at the V edges are compared against multiplet cluster calculations within the frame of the ligand field theory to quantify the intra-atomic electronic interactions at play and evaluate the effects of symmetry reduction occurring in a trigonally distorted VI6 unit. We observed a non zero linear dichroism proving the presence of an anisotropic charge density distribution around the V3+ ion due to the unbalanced hybridization between the vanadium and the ligand states. Such hybridization acts as an effective trigonal crystal field, slightly lifting the degeneracy of the ground state. However, the energy splitting associated to the distortion underestimates the experimental band gap, suggesting that the insulating ground state is stabilized by Mott correlation effects rather than via a Jahn–Teller mechanism. Our results clarify the role of the distortion in VI3 and establish a benchmark for the study of the spectroscopic properties of other van der Waals halides, including emerging 2D materials with mono and few-layers thickness, whose fundamental properties might be altered by reduced dimensions and interface proximity.

Probing anharmonic phonons in WS2 van der Waals crystal by Raman spectroscopy and machine learning

Understanding the optothermal physics of quantum materials will enable the efficient design of next-generation photonic and superconducting circuits. Anharmonic phonon dynamics is central to strongly interacting optothermal physics. This is because the pressure of a gas of anharmonic phonons is temperature dependent. Phonon-phonon and electron-phonon quantum interactions contribute to the anharmonic phonon effect. Here we have studied the optothermal properties of physically exfoliated WS2 van der Waals crystal via temperature-dependent Raman spectroscopy and machine learning strategies. This fundamental investigation will lead to unveiling the dependence of temperature on in-plane and out-of-plane Raman shifts (Raman thermometry) of WS2 to study the thermal conductivity, hot carrier diffusion coefficient, and thermal expansion coefficient.

Cavity Quantum Electrodynamics with Hyperbolic van der Waals Materials.

The ground-state properties and excitation energies of a quantum emitter can be modified in the ultrastrong coupling regime of cavity quantum electrodynamics (QED) where the light-matter interaction strength becomes comparable to the cavity resonance frequency. Recent studies have started to explore the possibility of controlling an electronic material by embedding it in a cavity that confines electromagnetic fields in deep subwavelength scales. Currently, there is a strong interest in realizing ultrastrong-coupling cavity QED in the terahertz (THz) part of the spectrum, since most of the elementary excitations of quantum materials are in this frequency range. We propose and discuss a promising platform to achieve this goal based on a two-dimensional electronic material encapsulated by a planar cavity consisting of ultrathin polar van der Waals crystals. As a concrete setup, we show that nanometer-thick hexagonal boron nitride layers should allow one to reach the ultrastrong coupling regime for single-electron cyclotron resonance in a bilayer graphene. The proposed cavity platform can be realized by a wide variety of thin dielectric materials with hyperbolic dispersions. Consequently, van der Waals heterostructures hold the promise of becoming a versatile playground for exploring the ultrastrong-coupling physics of cavity QED materials.

Focusing of Hyperbolic Phonon Polaritons by Bent Metal Nanowires and Their Polarization Dependence

Manipulating in-plane hyperbolic phonon polaritons on biaxial van der Waals crystals provides an opportunity for the development of planar photonic devices. Recent studies show that nanometal disks constructed on the surface of hyperbolic media can focus phonon polaritons, which is a remarkable breakthrough in planar photonics. Here, we demonstrate that using bent metal nanowires made by strain engineering not only produces the focusing of hyperbolic phonon polaritons but also introduces a new modulation factor, the polarization of incident light, which shows a clear affection on focusing. In this study, we investigate the operating mechanism and applicability of this nanolens from the perspective of device size, incident light frequency, and polarization, where the effect of polarization is unprecedented for this type of surface engineering. With the support of super-resolution technology, the foci with high confinement are clearly observed and the focal length from 0.7 to 2.01 μm is achieved. Moreover, the angle between the in-plane polarization direction and the axial direction of the nanowires directly affects the intensity of the local field. This approach provides a new idea to control electromagnetic fields in a two-dimensional plane, which is beneficial to further promote the design of planar optical functional devices.

Advances in Physics of Semiconductors

It is my pleasure to write this preface to the Special Section in the May 2023 issue of pss(b), dedicated to the collection of selected works presented during the 35th International Conference on Physics of Semiconductors (ICPS) held in Sydney, Australia in 2022. It was one of the first meetings post the pandemic and it was wonderful to see the community gathering physically together. The ICPS series traditionally encompasses a variety of topics spanning device physics, quantum technologies, spin physics, wide bandgap materials, light–matter interactions, and other branches of materials science, physics and engineering. The collection to follow offers a glimpse into what has been presented, and showcases the excellent science undertaken around the globe. A growing interest in the scientific community is currently evolving around van der Waals crystals, and other two-dimensional systems. It is therefore no surprise, several works focus on these topics – discussing various excitonic, photonic, magnetic, and terahertz properties. Various spin phenomena effects are also discussed in traditional semiconductors such as GaAs/GaN and SiGe. Works on plasmonic gap cavities and electroluminescence as well as theoretical calculations of electronic structures are also included. The ICPS series has been continuously going now for over 70 years, one of the longest running conference series in the world. As we are preparing for the next meeting in Ottawa, Canada, the collection of papers should inspire our junior colleagues, that not only semiconductor physics is here to stay, but in fact, it is a multi-disciplinary and burgeoning field of research.

Nanoscale Disorder and Deintercalation Evolution in K‐Doped MoS2 Analysed Via In Situ TEM

AbstractIntercalation and deintercalation processes in van der Waals crystals underpin their use in nanoelectronics, energy storage, and catalysis but there remains significant uncertainty regarding these materials’ structural and chemical heterogeneity at the nanoscale. Deintercalation in particular often controls the robustness and cyclability of the involved processes. Here, a detailed analysis of potassium ordering and compositional variations in as‐synthesised K intercalated MoS2 as well an analysis of deintercalation induced changes in the structure and K/Mo elemental composition is presented. By combining 4D scanning transmission electron microscopy (4DSTEM), in situ atomic resolution STEM imaging, selected area electron diffraction (SAED) and energy dispersive X‐ray spectroscopy (EDS) the formation of previously unknown intermediate superstructures during deintercalation is revealed. The results provide evidence supporting a new deintercalation mechanism that favors formation of local regions with thermodynamically stable ordering rather than isotropic release of K. Systematic time‐temperature measurements demonstrate the deintercalation behavior to follow first‐order kinetics, allowing compositional and superstructural changes to be predicted. It is expected that the in situ correlative STEM‐EDS/SAED methodology developed in this work has the potential to determine optimal synthesis, processing and working conditions for a variety of intercalated or pillared materials.

Intrinsic ferroelectrics and carrier doping-induced metallic multiferroics in an atomic wire

Low-dimensional multiferroic metals characterized by the simultaneous coexistence of ferroelectricity, conductivity, and magnetism hold tremendous potential for scientific and technological endeavors. However, the mutually exclusive mechanisms among these properties impede the discovery of multifunctional conducting multiferroics, especially at the atomic-scale. Here, based on first-principles calculations, we design and demonstrate intrinsic one-dimensional (1D) ferroelectrics and carrier doping-induced metallic multiferroics in an atomic WOF4 wire. The WOF4 atomic wire that can be derived from a 1D van der Waals crystal exhibits pronounced ferroelectricity manifested in the form of large cooperative atomic displacements. By performing Monte Carlo simulations with an effective Hamiltonian method, we obtain the nanowire that can sustain a high Curie temperature, indicating its potential for room-temperature applications. Moreover, doping with electrons is found to induce magnetism and metallic conductivity that coexists with the ferroelectric distortion in the nanowire. These appealing properties in conjunction with the experimental feasibility enable the doped WOF4 nanowire to act as a promising atomic-scale multifunctional material.

Magnetical Manipulation of Hyperbolic Phonon Polaritons in Twisted Double-Layers of Molybdenum Trioxide.

Controlling the twist angle between double stacked van der Waals (vdW) crystals holds great promise for nanoscale light compression and manipulation in the mid-infrared (MIR) range. A lithography-free geometry has been proposed to mediate the coupling of phonon polaritons (PhPs) in double-layers of vdW α-MoO3. The anisotropic hyperbolic phonon polaritons (AHPhPs) are further hybridized by the anisotropic substrate environment of magneto-optic indium arsenide (InAs). The AHPhPs can be tuned by twisting the angle between the optical axes of the two separated layers and realize a topological transition from open to closed dispersion contours. Moreover, in the presence of external magnetic field, an alteration of the hybridization of PhPs will be met, which enable an efficient way for the control of light-matter interaction at nanoscale in the MIR region.

Effect of hydrophobic and hydrophilic surfaces on the morphological and physical properties of supported lipid membranes.

The characteristics of supported lipid bilayers (SLBs) have long been studied as SLBs are commonly accepted as basic model systems of cell membranes. Atomic force microscopy (AFM) has proved to be effective in characterising physical and thermodynamic properties of SLBs, owing to its high resolution and the ability of environmental control. Through study of these properties, information such as lipid phase transitions can be investigated. Lipid phase transitions, from solid-ordered to liquid-disordered states, are well known to vary depending upon temperature, pH and ionic strength etc., and play a substantial role into events such as membrane protein mobility. Although previously studied on hydrophilic substrates, knowledge on the impact of hydrophobic substrates, such as van der Waals (vdW) crystals, on lipid phase transition is still lacking. This is particularly important for developing new bio- and electrochemical sensing technologies, where conductive vdW materials are used as sensing electrodes. It is expected that the thermodynamic properties of SLBs affect their conductive and dielectric polarisation and in turn molecular charge distribution and dielectric properties are known to strongly influence hydration layers occurring at the interface of lipids. Here, we present the study of adsorption of lipid membranes on various substrates, where morphological and physical (i.e. thermodynamic, electrical, and interfacial) properties of the membrane were investigated using advanced AFM modes as a function of temperature. We find that the transition temperature of the lipid monolayers greatly differs depending upon the chosen substrate. We then probe interfacial properties of these electrically charged interfaces. Finally, we demonstrate that substrates with different chemical-physical properties used as a lipids support have a substantial effect on the physical properties of lipid monolayers.

Revealing the Origin of Time-Reversal Symmetry Breaking in Fe-Chalcogenide Superconductor FeTe_{1-x}Se_{x}.

Recently, evidence has emerged in the topological superconductor Fe-chalcogenide FeTe_{1-x}Se_{x} for time-reversal symmetry breaking (TRSB), the nature of which has strong implications on the Majorana zero modes (MZM) discovered in this system. It remains unclear, however, whether the TRSB resides in the topological surface state (TSS) or in the bulk, and whether it is due to an unconventional TRSB superconducting order parameter or an intertwined order. Here, by performing in superconducting FeTe_{1-x}Se_{x} crystals both surface-magneto-optic-Kerr effect measurements using a Sagnac interferometer and bulk magnetic susceptibility measurements, we pinpoint the TRSB to the TSS, where we also detect a Dirac gap. Further, we observe surface TRSB in nonsuperconducting FeTe_{1-x}Se_{x} of nominally identical composition, indicating that TRSB arises from an intertwined surface ferromagnetic (FM) order. The observed surface FM bears striking similarities to the two-dimensional (2D) FM found in 2D van der Waals crystals, and is highly sensitive to the exact chemical composition, thereby providing a means for optimizing the conditions for Majorana particles that are useful for robust quantum computing.

Ultrathin quantum light source with van der Waals NbOCl2 crystal.

Interlayer electronic coupling in two-dimensional materials enables tunable and emergent properties by stacking engineering. However, it also results in significant evolution of electronic structures and attenuation of excitonic effects in two-dimensional semiconductors as exemplified by quickly degrading excitonic photoluminescence and optical nonlinearities in transition metal dichalcogenides when monolayers are stacked into van der Waals structures. Here we report a van der Waals crystal, niobium oxide dichloride (NbOCl2), featuring vanishing interlayer electronic coupling and monolayer-like excitonic behaviour in the bulk form, along with a scalable second-harmonic generation intensity of up to three orders higher than that in monolayer WS2. Notably, the strong second-order nonlinearity enables correlated parametric photon pair generation, through a spontaneous parametric down-conversion (SPDC) process, in flakes as thin as about 46 nm. To our knowledge, this is the first SPDC source unambiguously demonstrated in two-dimensional layered materials, and the thinnest SPDC source ever reported. Our work opens an avenue towards developing van der Waals material-based ultracompact on-chip SPDC sources as well as high-performance photon modulators in both classical and quantum optical technologies1-4.