Dichroism Effect Research Articles

Mie theory and the dichroic effect for spherical gold nanoparticles: an experimental approach.

The attractive optical properties of metallic nanoparticles include the optically interesting but surprisingly not well understood dichroic effect, defined in this research as when particle colloids display different colours in transmitted and reflected light. Here we use a systematic experimental approach supplemented by theoretical Mie theory analysis to study the origin of this effect. The CloudSpec spectrophotometer has been utilised to produce quantitative scattering and absorption spectra for monodisperse spherical gold nanoparticles, allowing precise links to be made between the optical spectra and the colours observed. The source of the dichroic effect has been conclusively linked to particle size with no special particle shapes or size distributions required. These results experimentally demonstrate the relationship between particle size and the ratio of scattering to absorption predicted by Mie theory, which has important implications for users of Mie theory calculations.

Chiral recognition via a stereodynamic vanadium probe using the electronic circular dichroism effect in differential Raman scattering.

Intermolecular interactions sensitive to chirality occur in many biological events. We report a complex formation between a versatile vanadium-based probe and a chiral co-ligand monitored via the combination of electronic circular dichroism (ECD) and Raman scattering. This "ECD-Raman" effect was discovered relatively recently and can be measured using a Raman optical activity (ROA) spectrometer. Simulated spectra based on experimental ECD and degree of circularity (DOC) values agree with the observed ones. Sensitive recognition of the chiral enantiopure co-ligand is thus enabled by a combination of resonance of the excitation light with the diastereoisomeric complex, co-ligand complexation, circular dichroism, and polarized Raman scattering from the achiral solvent. Relatively dilute solutions could be detected (10-4 mol dm-3), about 1000× less than is necessary for conventional ROA detection of the pure co-ligand and comparable to concentrations needed for conventional ECD spectroscopy. The results thus show that differential ECD-Raman measurements can be conveniently used to monitor molecular interactions and molecular spectroscopic properties.

Shining light on chiral inorganic nanomaterials for biological issues.

The rapid development of chiral inorganic nanostructures has greatly expanded from intrinsically chiral nanoparticles to more sophisticated assemblies made by organics, metals, semiconductors, and their hybrids. Among them, lots of studies concerning on hybrid complex of chiral molecules with achiral nanoparticles (NPs) and superstructures with chiral configurations were accordingly conducted due to the great advances such as highly enhanced biocompatibility with low cytotoxicity and enhanced penetration and retention capability, programmable surface functionality with engineerable building blocks, and more importantly tunable chirality in a controlled manner, leading to revolutionary designs of new biomaterials for synergistic cancer therapy, control of enantiomeric enzymatic reactions, integration of metabolism and pathology via bio-to nano or structural chirality. Herein, in this review our objective is to emphasize current research state and clinical applications of chiral nanomaterials in biological systems with special attentions to chiral metal- or semiconductor-based nanostructures in terms of the basic synthesis, related circular dichroism effects at optical frequencies, mechanisms of induced optical chirality and their performances in biomedical applications such as phototherapy, bio-imaging, neurodegenerative diseases, gene editing, cellular activity and sensing of biomarkers so as to provide insights into this fascinating field for peer researchers.

Coexistence of circular dichroism and asymmetric transmission in a stretchable chiral metamaterial

A stretchable chiral metamaterial with Au nanoslits and L-shaped and T-shaped Au patterns (SCMM-NLT), which can simultaneously produce circular dichroism (CD) and asymmetric transmission (AT) effects for circularly polarized waves in the mid-infrared region, is proposed. The peak values of CD and AT effects reach 20.4% and − 20.4 % at the resonance wavelength of 23.4 µm, respectively, which originate from the excitation of the bonding and antibonding modes. We use the transmission matrix to analyze the simultaneous appearance of CD and AT effects. By stretching SCMM-NLT, the bands of CD and AT occur at the redshift phenomenon, which is attributed to the decrease of Coulomb force between the positive and negative charge accumulated at both ends of the structure. All results are calculated by the FEM-based software COMSOL Multiphysics. In the future, our findings could be applied to wearable electronic devices, such as refractive index sensors.

Temperature Effect of Plasmonic Circular Dichroism in Dynamic Oligomers of AuNR@Ag Nanorods Driven by Cysteine: The Role of Surface Atom Migration

AbstractAchieving huge chiroptical responses is one of the driving forces for the applications of plasmonic metamaterials. Heat‐assisted symmetry breaking can amplify plasmonic circular dichroism (PCD) signals in Au nanorod (AuNR) oligomers; however, the PCD responses disappear on Ag‐exposed surface (AuNR@Ag core‐shell nanorods) at high temperature. Thus, the inherent reason of different chiral response between Au‐ and Ag‐surface nanorods oligomers is explored, and the chiral mechanism is further cognized. The enhanced mobility of surface Ag atoms at elevated temperatures leads to the damage of cysteine chiral networks on Ag surface. It therefore causes great reduction of chiral drive forces, thus restricting the PCD temperature amplification effect to a lower annealing temperature, compared to their Au‐exposed counterparts. In addition, the PCD signals of the AuNR@Ag oligomers show a pH‐dependent on‐off behavior, substantiating the dominant role of chiral network. In addition, density functional theory simulation and relevant experiments reveal facet‐dependent chiral response of Ag and Au oligomers. Then, Au–Ag alloy shells can suppress Ag atoms migration; the chiral network and PCD temperature amplification effect can exist in high temperature. The findings reveal the importance of understanding interface ligands, plasmonic nanoparticles, and their interactions in the rational design of chiral assemblies composed of plasmonic nano‐units.

Soft x-ray microscopy with 7 nm resolution

The availability of intense soft x-ray beams with tunable energy and polarization has pushed the development of highly sensitive, element-specific, and noninvasive microscopy techniques to investigate condensed matter with high spatial and temporal resolution. The short wavelengths of soft x-rays promise to reach spatial resolutions in the deep single-digit nanometer regime, providing unprecedented access to magnetic phenomena at fundamental length scales. Despite considerable efforts in soft x-ray microscopy techniques, a two-dimensional resolution of 10 nm has not yet been surpassed in direct imaging. Here, we report on a significant step beyond this long-standing limit by combining newly developed soft x-ray Fresnel zone plate lenses with advanced precision in scanning control and careful optical design. With this approach, we achieve an image resolution of 7 nm. By combining this highly precise microscopy technique with the x-ray magnetic circular dichroism effect, we reveal dimensionality effects in an ensemble of interacting magnetic nanoparticles. Such effects are topical in current nanomagnetism research and highlight the opportunities of high-resolution soft x-ray microscopy in magnetism research and beyond.

Photoelectron diffraction for probing valency and magnetism of 4f -based materials: A view on valence-fluctuating EuIr2Si2

We present and discuss the methodology for modeling $4f$ photoemission spectra, $4f$ photoelectron diffraction (PED) patterns, and magnetic dichroism effects for rare-earth-based materials. Using PED and magnetic dichroism in photoemission, we explore the electronic and magnetic properties of the near-surface region of the valence-fluctuating material ${\mathrm{EuIr}}_{2}{\mathrm{Si}}_{2}$. For the Eu-terminated surface, we found that the topmost Eu layer is divalent and exhibits a ferromagnetic order below 10 K. The valency of the next Eu layer, that is the fifth atomic layer, is about 2.8 at low temperature that is close to the valency in the bulk. The properties of the Si-terminated surface are drastically different. The first subsurface Eu layer (fourth atomic layer below the surface) behaves divalently and orders ferromagnetically below 48 K. Experimental data indicate, however, that there is an admixture of trivalent Eu in this layer, resulting in its valency of about 2.1. The next deeper lying Eu layer (eighth atomic layer below the surface) behaves mixed valently, but the estimated valency of 2.4 is notably lower than the value in the bulk. The presented approach and obtained results create a background for further studies of exotic surface properties of $4f$-based materials, and allow us to derive information related to valency and magnetism of individual rare-earth layers in a rather extended area near the surface.

Self-assembly of plasmonic chiral superstructures with intense chiroptical activity

Chiral nanostructures are asymmetric nanoarchitectures that cannot be superimposed with their mirrored-symmetric counterparts, which have attracted considerable attention due to their special photophysical properties and potential applications in plasmonics, spectroscopy and nanosensors. In particular, Self-Assembly of chiral nanostructures with symmetric or asymmetric objects might exhibit exceptional optical activity because those chiral superstructures can manipulate chiral states of light that leads to circular dichroism (CD) effect. This review highlights recent advances on the self-assembly of plasmonic chiral superstructures from simpler dimeric, and trimeric chiral nanoassemblies to complicated chiral nanoarchitectures, especially emphasizes the resulted superior optical activity and the corresponding principles.

Nonlinear electric transport in odd-parity magnetic multipole systems: Application to Mn-based compounds

Violation of parity symmetry gives rise to various physical phenomena such as nonlinear transport and cross-correlated responses. In particular, the nonlinear conductivity has been attracting a lot of attentions in spin-orbit coupled semiconductors, superconductors, topological materials, and so on. In this paper we present theoretical study of the nonlinear conductivity in odd-parity magnetic multipole ordered systems whose $\mathcal{PT}$-symmetry is essentially distinct from the previously studied acentric systems. Combining microscopic formulation and symmetry analysis, we classify the nonlinear responses in the $\mathcal{PT}$-symmetric systems as well as $\mathcal{T}$-symmetric (non-magnetic) systems, and uncover nonlinear conductivity unique to the odd-parity magnetic multipole systems. A giant nonlinear Hall effect, nematicity-assisted dichroism and magnetically-induced Berry curvature dipole effect are proposed and demonstrated in a model for Mn-based magnets.

Magnetic and structural properties of CoFeB thin films grown by pulsed laser deposition

The emergence of thin film CoFeB has driven research and industrial applications in the past decades, with the magnetic random access memory (MRAM) the most prominent example. Because of its beneficial properties, it fulfills multiple functionalities as information-storing, spin-filtering, and reference layer in magnetic tunnel junctions. In future, this versatility can be exploited beyond the traditional applications of spintronics by combining with advanced materials, such as oxide-based materials. Pulsed laser deposition (PLD) is their predominant growth-method, and thus the compatibility of CoFeB with this growth technique will be tested here. This encompasses a comprehensive investigation of the structural and magnetic propoperties. In particular, we find a substantial ‘dead’ magnetic layer and confirm that it is caused by oxidation employing the x-ray magnetic circular dichroism (XMCD) effect. The low damping encountered in vector network analyzer-based ferromagnetic resonance (VNA-FMR) renders them suitable for magnonics applications. These findings demonstrate that CoFeB thin films are compatible with emergent, PLD-grown materials, ensuring their relevance for future applications.

Simulation and Fabrication of Nanoscale Spirals Based on Dual-Scale Self-Assemblies.

Archimedean spirals in nanometer scale have shown remarkable plasmonic responses derived from their linear and rotational asymmetry. Despite the unique optical properties of nanoscale spirals, their applications have been limited due to the difficulty in fabricating large-scale arrays with uniform and systematic control of the morphology. Here, we report simulation results of spiral morphologies, which are used to design a scalable fabrication process for nanoscale spirals and predict their plasmonic responses. First, self-consistent field theory (SCFT) simulations were performed to design optimal templates to guide self-assembly into spiral morphologies. Using the SCFT results, we developed a scalable fabrication process, which is based on the micron-scale assembly of microspheres combined with glancing angle deposition and nanoscale assembly of block copolymers, to induce the formation of uniform nanospirals with diverse size, handedness, orientation, and winding number. Finally, finite-difference time-domain simulation results show linear dichroism and electric field intensity enhancement effects of these nanospirals, which are highly dependent on the winding number of the spirals, indicating the importance of precise control of the structural parameters.

Temperature-dependent chirality of cholesteric liquid crystal for terahertz waves.

Recently, the terahertz (THz) chiral field control opens a new window to THz devices and their applications. In this Letter, the active manipulation for THz chiral states based on the cholesteric liquid crystal (CLC) has been demonstrated by THz time domain cross-polarization spectroscopy. The results show that the CLC has strong THz optical activity and circular dichroism (CD) effect, and the strongest THz CD of 22 dB and a polarization rotation angle of 88.4° occur around the phase transition temperature TS-N=250K. Rising to a room temperature of 300 K, the CLC turns from a chiral state to an isotropic state for THz waves with the phase transition processes of CLC molecules. Therefore, this CLC device can be performed as a thermally active THz circular polarizer, which brings potential applications in THz polarization imaging, broadband communication, and spectroscopy.

Orientation dichroism effect of proton scattering on deformed nuclei * * Supported by the National Natural Science Foundation of China (11875174, 11890712, 11965004, 11947413, U1867212, 11711540016), Natural Science Foundation of Guangxi (2016GXNSFFA380001, 2017GXNSFGA198001), Foundation of Guangxi innovative team and distinguished scholar in institutions of higher education

Proton-induced scattering of 238U nuclei, with spheroidal deformations at beam energies above 100 MeV, is simulated using an improved quantum molecular dynamics model. The angular distribution of the deflected protons is highly sensitive to the orientation of the symmetrical long axis of the target nuclei with respect to the beam direction. As a result, in reverse kinematic reactions, an orientation dichroism effect is predicted, implying that the absorption rate of the 238U beam by a proton target discerns between the parallel and perpendicular orientations of the deformed 238U nuclei.

Photoelectric effect with a twist

Photons have fixed spin and unbounded orbital angular momentum (OAM). While the former is manifested in the polarization of light, the latter corresponds to the spatial phase distribution of its wavefront1. The distinctive way in which the photon spin dictates the electron motion upon light–matter interaction is the basis for numerous well-established spectroscopies. By contrast, imprinting OAM on a matter wave, specifically on a propagating electron, is generally considered very challenging and the anticipated effect undetectable2. In refs. 3,4, the authors provided evidence of OAM-dependent absorption of light by a bound electron. Here, we seek to observe an OAM-dependent dichroic photoelectric effect, using a sample of He atoms. Surprisingly, we find that the OAM of an optical field can be imprinted coherently onto a propagating electron wave. Our results reveal new aspects of light–matter interaction and point to a new kind of single-photon electron spectroscopy. The findings that the spatial distribution of an optical field with vortex phase profile can be imprinted coherently onto a propagating electron wave reveal new aspects of light–matter interactions and will help develop future single-photon electron spectroscopy.

Understanding angle-resolved polarized Raman scattering from black phosphorus at normal and oblique laser incidences

The selection rule for angle-resolved polarized Raman (ARPR) intensity of phonons from standard group-theoretical method in isotropic materials would break down in anisotropic layered materials (ALMs) due to birefringence and linear dichroism effects. The two effects result in depth-dependent polarization and intensity of incident laser and scattered signal inside ALMs and thus make a challenge to predict ARPR intensity at any laser incidence direction. Herein, taking in-plane anisotropic black phosphorus as a prototype, we developed a so-called birefringence-linear-dichroism (BLD) model to quantitatively understand its ARPR intensity at both normal and oblique laser incidences by the same set of real Raman tensors for certain laser excitation. No fitting parameter is needed, once the birefringence and linear dichroism effects are considered with the complex refractive indexes. An approach was proposed to experimentally determine real Raman tensor and complex refractive indexes, respectively, from the relative Raman intensity along its principle axes and incident-angle resolved reflectivity by Fresnel’s law. The results suggest that the previously reported ARPR intensity of ultrathin ALM flakes deposited on a multilayered substrate at normal laser incidence can be also understood based on the BLD model by considering the depth-dependent polarization and intensity of incident laser and scattered Raman signal induced by both birefringence and linear dichroism effects within ALM flakes and the interference effects in the multilayered structures, which are dependent on the excitation wavelength, thickness of ALM flakes and dielectric layers of the substrate. This work can be generally applicable to any opaque anisotropic crystals, offering a promising route to predict and manipulate the polarized behaviors of related phonons.

Study of Fe ions in aquamarine and the effect of dichroism as seen using UV–Vis, NIR and x-ray

The oxidation states and coordination environment of Fe in 4 aquamarine samples with different color shades were studied. The C axis along with plane A and plane C of the samples were identified and the measurements were made with plane A oriented facing incoming beam and plane C oriented facing incoming beam. NIR and Raman spectroscopy were employed to confirm the structure of the samples. XRD was used to confirm the polished faces. UV–Vis and X-ray absorption near edge structure (XANES) were used to identify the presence of both Fe2+ and Fe3+ in the samples. The results indicated that Fe resided predominantly in 6-fold coordinated sites and the deep blue shade depended on the amount of Fe2+ in 6-fold coordinated sites. The effect of dichroism was noticeable in NIR, Raman spectroscopy, UV–Vis and XANES. Clearer Raman bands were observed when samples were oriented with plane A facing laser source. NIR and UV–Vis analysis could benefit from the complementarity of spectra measured from both orientations. Discrepancies between XANES spectra measured from the two orientations could lead to uncertainties in obtained values of oxidation states.

Dichroic Sb2O3/Ag/Sb2O3 Electrodes for Colorful Semitransparent Organic Solar Cells

The pace of advancement and increasing power conversion efficiencies (PCEs) have provided the possibility for organic solar cells (OSCs) to be commercialized in a variety of applications, including semitransparent photovoltaics. The application of dielectric–metal–dielectric (DMD) transparent electrodes to OSCs is an effective way to achieve semitransparent OSCs with different colors. Herein, a DMD multilayer structure based on two Sb2O3 layers and silver (Ag) thin films as the top electrode is introduced. An ultrathin Sb2O3 layer is deposited between the electron transport layer and the Ag film as a bottom layer for the Sb2O3/Ag/Sb2O3 electrode; this layer inhibits Ag atom diffusion and aggregation, which leads to uniform formation of ultrathin Ag films. The thickness of the middle metal layer influences fill factor and short‐circuit current density values, which correlate well with device resistance and light reflection. For the top Sb2O3 layer, the thickness allows the selective transmittance of specific wavelengths of visible light while reflecting wavelengths that are not transmitted, creating a dichroic effect. OSCs are successfully fabricated using three kinds of colorful active layers in conjunction with Sb2O3/Ag/Sb2O3 electrodes, resulting in vividly colored devices with PCE of 6.33–7.88% and average visible transmittances of 23–30%.

Unraveling VEALYL Amyloid Formation Using Advanced Vibrational Spectroscopy and Microscopy

Intermediate species are hypothesized to play an important role in the toxicity of amyloid formation, a process associated with many diseases. This process can be monitored with conventional and two-dimensional infrared spectroscopy, vibrational circular dichroism, and optical and electron microscopy. Here, we present how combining these techniques provides insight into the aggregation of the hexapeptide VEALYL (Val-Glu-Ala-Leu-Tyr-Leu), the B-chain residue 12–17 segment of insulin that forms amyloid fibrils (intermolecularly hydrogen-bonded β-sheets) when the pH is lowered below 4. Under such circumstances, the aggregation commences after approximately an hour and continues to develop over a period of weeks. Singular value decompositions of one-dimensional and two-dimensional infrared spectroscopy spectra indicate that intermediate species are formed during the aggregation process. Multivariate curve resolution analyses of the one and two-dimensional infrared spectroscopy data show that the intermediates are more fibrillar and deprotonated than the monomers, whereas they are less ordered than the final fibrillar structure that is slowly formed from the intermediates. A comparison between the vibrational circular dichroism spectra and the scanning transmission electron microscopy and optical microscope images shows that the formation of mature fibrils of VEALYL correlates with the appearance of spherulites that are on the order of several micrometers, which give rise to a “giant” vibrational circular dichroism effect.

Multifunctional Chiral π‐Conjugated Polymer Microspheres: Production and Confinement of NLO signal, Detection of Circularly Polarized Light, and Display of Laser‐Triggered NLO Emission Shifts

AbstractTwo chiral π‐conjugated polymers with optical nonlinearity (NLO), abbreviated as R‐ and S‐BP, are prepared by copolymerization of R‐ and S‐6,6'‐dibromo‐2,2'‐diethoxy‐1,1'‐binaphthyl with 1,4‐diethynyl‐2,5‐bis(octyloxy)benzene by Sonogashira coupling. The R‐ and S‐BP copolymers self‐assemble in a tetrahydrofuran/H2O/ethanol mixture producing microspherical particles. Remarkably, the obtained polymer microspheres support excitation of whispering gallery mode resonances (500–720 nm) in one‐ and two‐photon excited luminescence or two‐photon luminescence (TPL) with a quality factor (Q) of up to ≈700. As a result of a high Q value, a single (R‐ or S‐BP) microsphere displays a circular dichroism (CD) effect in the TPL signal. At high laser pump‐power (≥10 mW), the TPL spectral features of microspheres change significantly, suggesting alterations of the polymer packing. Similar spectral variations are observed for microspheres heated thermally or with high power continuous‐wave laser. Photoluminescence lifetime imaging microscopy down to the single microsphere level corroborate transformations of polymer packing from a J type to a mixture of J, H, and H‐like (with disordered side chains) types. This work demonstrates the tremendous potential of tailor‐made chiral polymer microspheres exhibiting multifunctional properties, such as i) light‐confinement, ii) NLO‐CD, and iii) laser‐driven optical emission shifts, useful for many optoelectronic and photonic device applications.

Probing structural chirality of crystals using high-order harmonic generation in solids

Structural chirality plays an important role in solid state physics and leads to a variety of novel physics. The feasibility of probing structural chirality of crystals using high harmonic generation in solids is explored in this work. Through first-principles calculations based on the time-dependent density functional theory framework, we demonstrate that evident circular dichroism (CD) effects can be induced in the high harmonic spectra from a chiral crystal -- bulk tellurium. The CD signal reverses for crystals with opposite structural chirality. Besides, the high harmonic spectroscopy also provides an all-optical method for probing lattice symmetry properties and determining orientation of the tellurium crystal.