Anisotropic Optical Response Research Articles

Isolation and characterisation of monolayer phosphorene analogues

Atomically thin group IV monochalcogenides or phosphorene analogues are a promising family of materials. Theoretical calculations predict that monolayers (MLs) should be semiconducting, ferroelectric and ferroelastic at room temperature, exhibit large charge mobilities and large non-linear optical response. Yet, experimental studies of these systems are scarce because of the difficulty to produce such MLs. Here we focus on two members of this family: GeSe and SnS. We demonstrate a simple mechanical exfoliation method to produce ML samples on gold substrates. We observe the evolution of the Raman scattering as a function of layers and the anisotropic optical response from reflectance contrast measurements. To the best of our knowledge this is the first report of mechanical exfoliation down to the ML of these materials and the first realisation of ML GeSe.

Low-Symmetry Van der Waals Dielectric GaInS3 Triggered 2D MoS2 Giant Anisotropy via Symmetry Engineering.

Low-symmetry structures in van der Waals materials have facilitated the advancement of anisotropic electronic and optoelectronic devices. However, the intrinsic low symmetry structure exhibits a small adjustable anisotropy ratio (1-10), which hinders its further assembly and processing into high-performance devices. Here, a novel 2D anisotropic dielectric, GaInS3 (GIS), which induces isotropic MoS2 to exhibit significant anisotropic optical and electrical responses is demonstrated. With the excellent gate modulation ability of 2D GIS (dielectric constant k ∼12), MoS2 field effect transistor (FET) shows an adjustable conductance ratio from isotropic to anisotropic under dual-gate modulation, up to 106. Theoretical calculations indicate that anisotropy originates from lattice mismatch-induced charge density deformation at the interface. Moreover, the MoS2/GIS photodetector demonstrates high responsivity (≈4750 A W-1) and a large dichroic ratio (≈167). The anisotropic van der Waals dielectric GIS paves the way for the development of 2D transition metal dichalcogenides (TMDCs) in the fields of anisotropic photonics, electronics, and optoelectronics.

Anisotropic optical response of Nb2SiTe4 under pressure

The optical response of a layered anisotropic crystal Nb2SiTe4 was investigated under varying pressure using synchrotron infrared spectroscopy, Raman spectroscopy, and first-principles calculation. This study revealed diverse trends in optical response and bandgap at different pressure levels. Below 5 GPa, the bandgap decreases rapidly due to the reduction of interlayer distance. The Raman and infrared optical response show significant changes at 11 and 21 GPa, suggesting structural and electronic structure transformation at these pressure points. Meanwhile, the optical responses exhibited distinct pressure effects along different crystal axes. Overall, these results provide valuable insights into the pressure-induced lattice deformation and optical transitions in Nb2SiTe4 and similar layered anisotropic materials, contributing to an insightful understanding of layered materials under pressure.

Extraordinary Polarization and Thickness Dependences of Photocarrier Dynamics in PdSe2 Ribbons.

Pentagonal palladium diselenide (PdSe2) stands out for its exceptional optoelectronic properties, including high carrier mobility, tunable bandgap, and anisotropic electronic and optical responses. Herein, we systematically investigate photocarrier dynamics in PdSe2 ribbons using polarization-resolved optical pump-probe spectroscopy. In thin PdSe2 ribbons with a semiconductor phase, the photocarrier dynamics are found to be dominated by intraband hot-carrier cooling, interband recombination, and the exciton effect, showing weak crystalline orientation dependences. Conversely, in thick semimetal-phase PdSe2 ribbons, the photocarrier relaxations governed by the electron-optical/acoustic phonon scattering strongly depend on the sample orientation, albeit with a degradation in in-plane anisotropy following hot-carrier cooling. Furthermore, we analyze the correlations between photocarrier dynamics and anisotropic energy dispersions of electronic structures across a wide range in k space, as well as the contributions from the anisotropic electron-phonon couplings. Our study provides crucial insights for developing polarization-sensitive photoelectronic devices based on PdSe2.

Recent Advances and Synthetic Approaches of AuNRs for Sensing Applications Based on Different Aspect Ratios

AbstractGold nanorods (AuNRs), 1D rod‐shaped nanomaterials, hold a crucial role in sensing applications due to their distinct physicochemical properties, such as high surface area, efficient mass transfer, good biocompatibility, and anisotropic optical and electronic responses. This review outlines the most recent advancements in AuNRs research, offering a comprehensive summary of synthetic strategies. Subsequently, the potential of AuNRs in sensor applications is discussed, and for the first time, an innovative analysis of their application in the sensor field based on the aspect ratio of AuNRs is proposed. These sensing systems are utilized for detecting heavy metal ions, inorganic anions, small biomolecules, protein tumor markers, enzymes, and nucleic acids. Finally, the future research directions and challenges of AuNRs are addressed.

Investigation of the nonlinear optical frequency conversion in ultrathin franckeite heterostructures

Layered franckeite is a natural superlattice composed of two alternating layers of different compositions, SnS2- and PbS-like. This creates incommensurability between the two species along the planes of the layers, resulting in spontaneous symmetry-break periodic ripples in the a-axis orientation. Nevertheless, natural franckeite heterostructure has shown potential for optoelectronic applications mostly because it is a semiconductor with 0.7 eV bandgap, air-stable, and can be easily exfoliated down to ultrathin thicknesses. Here, we demonstrate that few-layer franckeite shows a highly anisotropic nonlinear optical response due to its lattice structure, which allows for the identification of the ripple axis. Moreover, we find that the highly anisotropic third-harmonic emission strongly varies with material thickness. These features are further corroborated by a theoretical nonlinear susceptibility model and the nonlinear transfer matrix method. Overall, our findings help to understand this material and propose a characterization method that could be used in other layered materials and heterostructures to assign their characteristic axes.

Topologically Engineered Strain Redistribution in Elastomeric Substrates for Dually Tunable Anisotropic Plasmomechanical Responses.

The prompt visual response is considered to be a highly intuitive tenet among sensors. Therefore, plasmomechanical strain sensors, which exhibit dynamic structural color changes, have recently been developed by using mechanical stimulus-based elastomeric substrates for wearable sensors. However, the reported plasmomechanical strain sensors either lack directional sensitivity or require complex signal processing and device design strategies to ensure anisotropic optical responses. To the best of our knowledge, there have been no reports on utilizing anisotropic mechanical substrates to obtain directional optical responses. Herein, we propose an anisotropic plasmomechanical sensor to distinguish between the applied force direction and the force magnitude. We employ a simple strain-engineered topological elastomer to mechanically transform closely packed metallic nanoparticles (NPs) into anisotropic directional rearrangements depending on the applied force direction. The proposed structure consists of a heterogeneous-modulus elastomer that exhibits a highly direction-dependent Poisson effect owing to the periodically line-patterned local strain redistribution occurring due to the same magnitude of applied external force. Consequently, the reorientation of the self-assembled gold (Au)-NP array manifests dual anisotropy, i.e., force- and polarization-direction-dependent plasmonic coupling. The cost-effectiveness and simple design of our proposed heterogeneous-modulus platform pave the way for numerous optical applications based on dynamic transformation and topological inhomogeneities.

Nanoscrolls of Janus Monolayer Transition Metal Dichalcogenides.

Tubular structures of transition metal dichalcogenides (TMDCs) have attracted attention in recent years due to their emergent physical properties, such as the giant bulk photovoltaic effect and chirality-dependent superconductivity. To understand and control these properties, it is highly desirable to develop a sophisticated method to fabricate TMDC tubular structures with smaller diameters and a more uniform crystalline orientation. For this purpose, the rolling up of TMDC monolayers into nanoscrolls is an attractive approach to fabricating such a tubular structure. However, the symmetric atomic arrangement of a monolayer TMDC generally makes its tubular structure energetically unstable due to considerable lattice strain in curved monolayers. Here, we report the fabrication of narrow nanoscrolls by using Janus TMDC monolayers, which have an out-of-plane asymmetric structure. Janus WSSe and MoSSe monolayers were prepared by the plasma-assisted surface atom substitution of WSe2 and MoSe2 monolayers, respectively, and then were rolled by solution treatment. The multilayer tubular structures of Janus nanoscrolls were revealed by scanning transmission electron microscopy observations. Atomic resolution elemental analysis confirmed that the Janus monolayers were rolled up with the Se-side surface on the outside. We found that the present nanoscrolls have the smallest diameter of about 5 nm, which is almost the same as the value predicted by the DFT calculation. The difference in work functions between the S- and Se-side surfaces was measured by Kelvin probe force microscopy, which is in good agreement with the theoretical prediction. Strong interlayer interactions and anisotropic optical responses of the Janus nanoscrolls were also revealed by Raman and photoluminescence spectroscopy.

Isotropic optical response and edge plasmons in MoS[formula omitted] monolayer induced by oxygen absorption

Defects play a crucial role in altering the electronic and optical characteristics of two-dimensional (2D) semiconductors, which is highly significant for the advancement of next-generation electronic and optoelectronic devices. In this study, we employ first-principles density functional theory (DFT) and time-dependent DFT calculations to explore the impact of oxygen defects on the electronic, optical, and plasmonic properties of monolayer MoS2. Our calculations reveal that the presence of an oxygen defect in the absorption position of the MoS2 monolayer leads to a predominant photoabsorption in the visible region of the electromagnetic spectrum, as well as an isotropic optical response and the emergence of edge plasmons. Conversely, when an oxygen defect is located in the adsorption position of the MoS2 monolayer, it generates deep midgap states within the bandgap, resulting in an anisotropic optical response and the partial decay of edge plasmons. By obtaining a comprehensive understanding of the effects of defects on photoabsorption and plasmonics, our study provides valuable insights for enhancing the performance of optical and plasmonic devices based on 2D materials.

Polarization‐Sensitive Photodetectors Based on Highly In‐Plane Anisotropic Violet Phosphorus with Large Dichroic Ratio

AbstractAnisotropic 2D layered materials with distinctive anisotropic electronic band structures and optical response are promising for practical applications in polarization imaging and sensors. Nonetheless, many of the currently reported polarized photodetectors based on anisotropic 2D materials are constrained by the low polarization responsivity and low linear dichroism ratio. Here a high‐performance polarization‐sensitive photodetector based on the novel in‐plane anisotropy 2D violet phosphorus (VP) crystal is reported. The angle‐resolved polarized Raman spectroscopy (ARPRS) study and the anisotropic electrical transport measurements revealed the highly in‐plane anisotropy phonon vibration and electrical properties of VP crystal. The anisotropic ratio of electron mobility is calculated to be 2.7 at room temperature. Moreover, a polarization‐sensitive photodetector based on the VP nanosheet shows high photoresponsivity of up to 341 A W−1 and a linearly dichroic ratio of up to 3.9, which is much larger than most other anisotropic 2D materials. These results indicate that the anisotropic VP crystal would be suitable for polarization‐sensitive photodetectors, which leads to a promising perspective for future novel electronic and optoelectronic devices.

Domain-dependent strain and stacking in two-dimensional van der Waals ferroelectrics

Van der Waals (vdW) ferroelectrics have attracted significant attention for their potential in next-generation nano-electronics. Two-dimensional (2D) group-IV monochalcogenides have emerged as a promising candidate due to their strong room temperature in-plane polarization down to a monolayer limit. However, their polarization is strongly coupled with the lattice strain and stacking orders, which impact their electronic properties. Here, we utilize four-dimensional scanning transmission electron microscopy (4D-STEM) to simultaneously probe the in-plane strain and out-of-plane stacking in vdW SnSe. Specifically, we observe large lattice strain up to 4% with a gradient across ~50 nm to compensate lattice mismatch at domain walls, mitigating defects initiation. Additionally, we discover the unusual ferroelectric-to-antiferroelectric domain walls stabilized by vdW force and may lead to anisotropic nonlinear optical responses. Our findings provide a comprehensive understanding of in-plane and out-of-plane structures affecting domain properties in vdW SnSe, laying the foundation for domain wall engineering in vdW ferroelectrics.

Birefringence after Tellurium Nanosheets and Copper Intercalation

Symmetry-deficient two-dimensional (2D) layered materials induce a highly anisotropic optical response due to the anisotropy in their crystal structure, facilitating their application in polarized nanodevices. Intercalation is a new way to tune the optoelectronic properties of materials by inserting guest atoms into layered host materials, and 2D layered structures stacked with van der Waals gaps are a prerequisite for this phase of the technique. In this paper, 2D tellurium nanosheets were synthesized with a hydrothermal method, and copper atoms were inserted with a wet chemical method. The widening of the crystal plane spacing proves the introduction of copper atoms, and polarization−related second-harmonic-generation (SHG) studies reveal the intrinsic anisotropic modes of the two samples, and birefringent properties are found with polarizing light microscopy. We further investigated the electrical properties of the samples, and the embedding of the copper atoms caused the samples to exhibit higher currents, but their devices lost the gate control effect.

An anisotropic van der Waals dielectric for symmetry engineering in functionalized heterointerfaces

Van der Waals dielectrics are fundamental materials for condensed matter physics and advanced electronic applications. Most dielectrics host isotropic structures in crystalline or amorphous forms, and only a few studies have considered the role of anisotropic crystal symmetry in dielectrics as a delicate way to tune electronic properties of channel materials. Here, we demonstrate a layered anisotropic dielectric, SiP2, with non-symmorphic twofold-rotational C2 symmetry as a gate medium which can break the original threefold-rotational C3 symmetry of MoS2 to achieve unexpected linearly-polarized photoluminescence and anisotropic second harmonic generation at SiP2/MoS2 interfaces. In contrast to the isotropic behavior of pristine MoS2, a large conductance anisotropy with an anisotropy index up to 1000 can be achieved and modulated in SiP2-gated MoS2 transistors. Theoretical calculations reveal that the anisotropic moiré potential at such interfaces is responsible for the giant anisotropic conductance and optical response. Our results provide a strategy for generating exotic functionalities at dielectric/semiconductor interfaces via symmetry engineering.

(Invited) Anisotropy in Complex Refractive Index Spectra of Single-Chirality-Enriched Carbon Nanotube Films

Toward macroscopic applications of exceptional optical properties of single-walled carbon nanotubes (SWCNTs), we reported in-plane complex refractive index spectra [1] of various single-chirality-enriched [2] SWCNTs films in which the SWCNTs are mostly oriented in two dimensions parallel to the film surface. However, in order to describe the anisotropic optical responses of such SWCNT films for incident light from all the directions, out-of-plane refractive index spectra are also required, in addition to the in-plane ones. We will report complete broadband complex refractive index spectra of single-chirality-enriched SWCNTs films for in-plane and out-of-plane optical responses. [1] T. Nishihara, A. Takakura, M. Shimasaki, K. Matsuda, T. Tanaka, H. Kataura, and Y. Miyauchi, Nanophotonics 11, 1011 (2022). [2] Y. Yomogida, T. Tanaka, M. Zhang, M. Yudasaka, X. Wei, and H. Kataura, Nat. Commun. 7, 12056 (2016).

Anisotropic optical response of the cuticle of arthropods

Anisotropic optical response of the cuticle of arthropods

Near-90° Switch in the Polar Axis of Dion-Jacobson Perovskites by Halide Substitution.

Ferroelectricity in two-dimensional hybrid (2D) organic-inorganic perovskites (HOIPs) can be engineered by tuning the chemical composition of the organic or inorganic components to lower the structural symmetry and order-disorder phase change. Less efforts are made toward understanding how the direction of the polar axis is affected by the chemical structure, which directly impacts the anisotropic charge order and nonlinear optical response. To date, the reported ferroelectric 2D Dion-Jacobson (DJ) [PbI4]2- perovskites exhibit exclusively out-of-plane polarization. Here, we discover that the polar axis in ferroelectric 2D Dion-Jacobson (DJ) perovskites can be tuned from the out-of-plane (OOP) to the in-plane (IP) direction by substituting the iodide with bromide in the lead halide layer. The spatial symmetry of the nonlinear optical response in bromide and iodide DJ perovskites was probed by polarized second harmonic generation (SHG). Density functional theory calculations revealed that the switching of the polar axis, synonymous with the change in the orientation of the sum of the dipole moments (DMs) of organic cations, is caused by the conformation change of organic cations induced by halide substitution.

Highly anisotropic transient optical response of charge density wave order in ZrTe3

Low dimensionality in CDW systems leads to anisotropic optical properties, in both equilibrium and non-equilibrium conditions. Here we perform polarized two-color pump probe measurements on a quasi-1D material ZrTe$_3$, in order to study the anisotropic transient optical response in the CDW state. Profound in-plane anisotropy is observed with respect to polarization of probe photons. Below $T_\mathrm{CDW}$ both the quasi-particle relaxation signal and amplitude mode (AM) oscillation signal are much larger with $\mathbf{E}_\mathrm{pr}$ nearly parallel to $a$ axis ($\mathbf{E}_\mathrm{pr} \parallel a$) than for $\mathbf{E}_\mathrm{pr}$ parallel to $b$ axis ($\mathbf{E}_\mathrm{pr} \parallel b$). This reveals that $\mathbf{E}_\mathrm{pr} \parallel a$ signal is much more sensitive to the variation of the CDW gap. Interestingly, the lifetime of the AM oscillations observed with $\mathbf{E}_\mathrm{pr} \parallel b$ is longer than $\mathbf{E}_\mathrm{pr} \parallel a$. Moreover, at high pump fluence where the electronic order melts and the AM oscillations vanish for $\mathbf{E}_\mathrm{pr} \parallel a$ , the AM oscillatory response still persists for $\mathbf{E}_\mathrm{pr} \parallel b$. We discuss possible origins that lead to such unusual discrepancy between the two polarizations.

Mid‐infrared dual‐comb polarimetry of anisotropic samples

AbstractThe mid‐infrared (mid‐IR) anisotropic optical response of a material probes vibrational fingerprints and absorption bands sensitive to order, structure, and direction‐dependent stimuli. Such anisotropic properties play a fundamental role in catalysis, optoelectronic, photonic, polymer and biomedical research and applications. Infrared dual‐comb polarimetry (IR‐DCP) is introduced as a powerful new spectroscopic method for the analysis of complex dielectric functions and anisotropic samples in the mid‐IR range. IR‐DCP enables novel hyperspectral and time‐resolved applications far beyond the technical possibilities of classical Fourier‐transform IR approaches. The method unravels structure–spectra relations at high spectral bandwidth up to 90 cm−1 and short integration times of 65 μs, with previously unattainable time resolutions for spectral IR polarimetric measurements for potential studies of noncyclic and irreversible processes. The polarimetric capabilities of IR‐DCP are demonstrated by investigating an anisotropic inhomogeneous freestanding nanofiber scaffold for neural tissue applications. Polarization sensitive multi‐angle dual‐comb transmission amplitude and absolute phase measurements (separately for ss‐, pp‐, ps‐, and sp‐polarized light) allow the in‐depth probing of the samples’ orientation‐dependent vibrational absorption properties. Mid‐IR anisotropies can quickly be identified by cross‐polarized IR‐DCP polarimetry.Key points A novel dual‐comb laser‐based technique is established for polarization‐dependent mid‐infrared spectroscopy. Independent measurements of spectral s‐ and p‐polarized transmission amplitudes and phases in the μs range. Visualization of the anisotropy of nanofiber scaffolds as used for neural tissue applications.

Anisotropic optical and magnetic response in self-assembled TiN–CoFe2 nanocomposites

Transition metal nitrides (e.g., TiN) have shown tremendous promise in optical metamaterials for nanophotonic devices due to their plasmonic properties comparable to noble metals and superior high temperature stability. Vertically aligned nanocomposites (VANs) offer a great platform for combining two dissimilar functional materials with a one-step deposition technique toward multifunctionality integration and strong structural/property anisotropy. Here, we report a two-phase nanocomposite design combining ferromagnetic CoFe2 nanosheets in the plasmonic TiN matrix as a new hybrid plasmonic metamaterial. The hybrid metamaterials exhibit anisotropic optical and magnetic responses, as well as a pronounced magneto-optical coupling response evidenced by Magneto-optic Kerr Effect measurement, owing to the novel vertically aligned structure. This work demonstrates a new TiN-based metamaterial with anisotropic properties and multifunctionality toward light polarization modulation, optical switching, and integrated optics.

Strong anisotropic optical response in two-dimensional Mo-VIA and Mo-VIIA monolayer binary materials

Two-dimensional binary materials based on transition metals have attracted much research attention because of their intriguing physical properties owing to their crystalline structure. The optical response of these compounds paves a way to manipulate the optical and electronic properties for optical and electronic device applications. Here, the frequency-dependent anisotropic linear optical response of eight molybdenum (Mo)-based binary materials from the VIA (i.e., O, S, Se, and Te) and VIIA (i.e., F, Cl, Br, and I) groups are systematically investigated using first-principles density functional theory. These binary materials exhibit strong linear anisotropic dielectric and optical behavior in the low energy range and become isotropic at high energies. The linear anisotropy in optical functions can be attributed to the intralayer excitonic behavior. The phenomenon of birefringence is the main characteristic of anisotropic materials. The dichroic ratio determines the degree of anisotropy. Among these binary materials, MoS2 and MoCl2 show large birefringence in the visible and far-infrared regions. The birefringence in these materials is also compared with other reported materials. Birefringence is critical for light manipulation during propagation through media. The present results provide insight into the linear optical anisotropies of the binary materials considered. Furthermore, the results suggest that these Mo-based binary materials could be potential candidates for developing optical instruments, optoelectronic, and photonic device applications.