Linear Dichroism Effect Research Articles

Abnormal Linear Dichroism in Anisotropic Van der Waals Crystal CrOCl Revealed by Phase‐Dependent Polarized Raman Scattering

AbstractWithin angle‐resolved polarized Raman spectroscopy (ARPRS) experiments, ensuring accurate configurations is crucial for obtaining reliable results, especially when dealing with anisotropic materials like CrOCl with anisotropic crystal structure and phonon properties. However, comprehensive understanding of phase‐dependent ARPRS and the calibration of phase angle on anisotropic phonon modes from a crystallographic perspective are still lacking. Herein, detailed investigation on phase‐dependent ARPRS and looked into the anisotropic photo‐phonon interaction in CrOCl through in situ ARPRS is conducted. The Raman tensors and crystal orientation are acquired under two typical configurations. Phase‐dependent ARPRS are thoroughly analyzed for the calibration of analyzer deviation. The anomalous anisotropic response in phase‐dependent ARPRS is closely related to the intrinsic linear dichroism (LD) effect in CrOCl, which is further confirmed by angle‐resolved polarization absorption. Moreover, the strong localized rules for various parallel energy bands of CrOCl have generated anomalous LD conversion effect near 470 nm, which expands the potential application of CrOCl in polarization‐wavelength selected devices. This findings can offer in‐depth comprehension on the anisotropic phonon physics of CrOCl and a feasible approach to utilize phase‐dependent ARPRS for probing the undiscovered abundant photo‐induced effects in low‐symmetry 2D materials.

Plasticizer-Induced Enhancement of Mesoscale Dissymmetry in Thin Films of Chiral Polymers with Variable Chain Length.

Conjugated polymers with chiral side chains are of interest in areas including chiral photonics, optoelectronics, and chemical and biological sensing. However, the low dissymmetry factors of most neat polymer thin films have limited their practical application. Here, a robust method to increase the absorption dissymmetry factor in a poly-fluorene-thiophene (PF8TS series) system is demonstrated by varying molecular weight and introducing an achiral plasticizer, polyethylene mono alcohol (PEM-OH). Extending chain length within the optimal range and adding this long-chain alcohol significantly enhance the chiroptical properties of spin-coated and annealed thin films. Mueller matrix spectroscopic ellipsometry (MMSE) analysis shows good agreement with the steady-state transmission measurements confirming a strong chiral response (circular dichroism (CD)and circular birefringence (CB)), ruling out linear dichroism, birefringence, and specific reflection effects. Solid-state NMR studies of annealed hybrid chiral polymer systems show enhancement of signals associated with aromatic π-stacked backbone and the ordered side-chain conformations. Further studies using Raman spectroscopy, X-ray diffraction (XRD), differential scanning calorimetry (DSC), atomic force microscopy (AFM), and polarized optical microscopy (POM) indicate that PEM-OH facilitates mesoscopic crystal domain ordering upon annealing. This provides new insights into routes for tuning optical activity in conjugated polymers.

Unveiling Chiral Perovskite CD Signal Scaling: Discerning Authentic and Counterfeit Signals through Sample-State Analysis.

Circular dichroism (CD) spectroscopy is a well-known and powerful technique widely used for distinguishing chiral enantiomers based on their differential absorbance of the right and left circularly polarized light. With the increasing demand for solid-state chiral optics, CD spectroscopy has been extended to elucidate the chirality of solid-state samples beyond the traditional solution state. However, due to the sample preparation differential, the CD spectra of the same compound measured by different researchers may not be mutually consistent. In this study, we employ solution, powder, thin-film, and single-crystal samples to explore the challenges associated with CD measurements and distinguish between genuine and fake signals. Rational fabrication of the solid-state samples can effectively minimize the macroscopic anisotropic nature of the samples and thereby mitigate the influence of linear dichroism (LD) and linear birefringence (LB) effects, which arise from anisotropy-induced differences in the absorbances and refractive indices. The local anisotropic and overall isotropic features of the high-quality thin-film sample achieve an optically isotropic state, which exhibits superior CD signal repeatability at the front and back sides at different angles by rotating the sample along the light path. In addition, sample thickness-induced CD signal overload and absorption saturation pose more severe challenges than the LBLD-induced amplified CD signal but are rarely focused on. The CD signal overload in the deep UV region leads to the presence of fake signals, while absorption saturation results in a complete loss of the CD signal. These findings help obtain accurate CD signals by a well-fabricated optically isotropic sample to avoid LDLB and optimize the sample thickness to avoid fake signals and no signals.

Near-edge X-ray absorption fine structure spectroscopy in studies of self-assembled monomolecular films

This article reviews the application of near-edge X-ray absorption fine structure (NEXAFS) spectroscopy to characterization of self-assembled monolayers (SAMs) which are an important part of modern nanotechnology, being particular useful in context of surface and interface engineering. NEXAFS spectroscopy provides information about the electronic structure of the SAMs, which allows to recognize specific functional groups and building blocks of the SAM-forming molecules. Due to the linear dichroism effects in X-ray absorption, this technique is also capable to give insight into orientational order and molecular orientation in the SAMs, both overall and building-block-specific. To illustrate the above points, a variety of representative examples for different classes of SAMs is provided, accompanied by the information about the general aspects of the technique and the description of suitable data evaluation procedures. Finally, it is shown that the application of NEXAFS spectroscopy to SAMs is not only limited by their characterization but is also useful to monitor chemical and physical processes involving these systems.

Laser‐Induced Creation of Antiferromagnetic 180‐Degree Domains in NiO/Pt Bilayers

AbstractThe antiferromagnetic order in heterostructures of NiO/Pt thin films can be modified by optical pulses. After the irradiation with laser light, the optically induced creation of antiferromagnetic domains can be observed by imaging the created domain structure utilizing the X‐ray magnetic linear dichroism effect. The effect of different laser polarizations on the domain formation can be studied and used to identify a polarization‐independent creation of 180° domain walls and domains with 180° different Néel vector orientation. By varying the irradiation parameters, the switching mechanism can be determined to be thermally induced. This study demonstrates experimentally the possibility to optically create antiferromagnetic domains, an important step towards future functionalization of all optical switching mechanisms in antiferromagnets.

Tailorable exchange bias and memory of frozen antiferromagnetic spins in epitaxial CoO(1 1 1)/Fe(1 1 0) bilayers

We report on exchange bias and interfacial antiferromagnetic spin orientation in epitaxial CoO(111)/Fe(110) bilayers. Our X-ray magnetic linear dichroism and magneto-optic Kerr effect results show that exchange bias sets on in the zero-field-cooled system and is governed by in-plane magnetic state Fe(110) sublayer above Néel temperature of CoO. Uniaxial magnetic anisotropy of Fe layer determines the direction of interfacial frozen antiferromagnetic CoO spins within CoO(111)//Fe(110) sample plane. Choice of the particular magnetic state of Fe sublayer, when passing Néel temperature of CoO, determines both the axis and direction of interfacial antiferromagnetic spins after the sample is cooled and allows for imprinting their +/- 90° and 0/180° alignment within the sample plane.

Large ultrafast-modulated Voigt effect in noncollinear antiferromagnet Mn3Sn

The time-resolved magneto-optical (MO) Voigt effect can be utilized to study the Néel order dynamics in antiferromagnetic (AFM) materials, but it has been limited for collinear AFM spin configuration. Here, we have demonstrated that in Mn3Sn with an inverse triangular spin structure, the quench of AFM order by ultrafast laser pulses can result in a large Voigt effect modulation. The modulated Voigt angle is significantly larger than the polarization rotation due to the crystal-structure related linear dichroism effect and the modulated MO Kerr angle arising from the ferroic ordering of cluster magnetic octupole. The AFM order quench time shows negligible change with increasing temperature approaching the Néel temperature (TN), in markedly contrast with the pronounced slowing-down demagnetization typically observed in conventional magnetic materials. This atypical behavior can be explained by the influence of weakened Dzyaloshinskii–Moriya interaction rather than the smaller exchange splitting on the diminished AFM order near TN. The temperature-insensitive ultrafast spin manipulation can pave the way for high-speed spintronic devices either working at a wide range of temperature or demanding spin switching near TN.

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.

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.

Interpretation of linear dichroism at S L2,3 x-ray absorption edges of small organic molecules at surfaces

Resonant soft x-ray absorption was applied at the S L2,3 (2p) edges of thin films of 1,4-benzenedimethanethiol (BDMT) on gold and of sexithiophene (6 T) on flat and patterned CaF2 surfaces. Linear dichroism effects were clearly observed depending on the orientation of the electric field vector of the incoming radiation. They were related to the organization of the molecules. For the interpretation of the angular dependencies of the spectral features, density functional theory (DFT) simulations of the absorption cross sections were calculated. It was possible to confirm the generally accepted chemisorption geometry of BDMT on Au(111), composed of molecules nearly vertical at the surface with one of the S atoms participating in the bonding with Au and the other left pending at the outermost surface and contributing mostly to the measured x-ray absorption. For 6 T on CaF2 a new chemisorption phase was identified on ridge-patterned CaF2(110), coexisting with a previously known phase given by 6 T crystallites highly oriented along the ridges. The new phase being composed of molecules oriented perpendicular to the ridges and lying on their edges.

Magneto-optical probe of ultrafast spin dynamics in antiferromagnetic CoO thin films

The probe of antiferromagnetic (AFM) spin dynamics in thin films has traditionally relied on the short x-ray pulses based on the magnetic dichroism or diffraction effect. Here, we demonstrate the direct optical probe of ultrafast laser-induced AFM spin dynamics of thin AFM CoO films using time-resolved magnetic linear dichroism effect in reflection geometry. The ultrafast laser excitation of the CoO film leads to the quench of AFM order, manifested as large polarization rotations of the reflected probe light. Far below the N\'eel temperature $({T}_{\mathrm{N}})$, the quench of the AFM order occurs within 300 fs, which is faster than the lattice thermalization $(\ensuremath{\sim}1\phantom{\rule{0.16em}{0ex}}\mathrm{ps})$ via electron-lattice scattering. This AFM quench process, however, slows down near ${T}_{\mathrm{N}}$, where an additional slower quench process with the time constant longer than 20 ps is emergent. Such an AFM spin dynamics is dramatically different than the transient reflectivity dynamics which is nearly invariant in a wide temperature range across ${T}_{\mathrm{N}}$. We attribute the quench of AFM order in CoO to the charge-transfer excitation and thermal effect, but the latter mechanism only plays a significant role near ${T}_{\mathrm{N}}$.

Growth and Optical Properties of LixNa1-xBa12(BO3)7F4 Fluoride Borates with "Antizeolite" Structure.

Studied LixNa1-xBa12(BO3)7F4 (P42bc) solid solution belongs to the new class of "antizeolite" borates with [Ba12(BO3)6]6+ cation pattern, which contains channels filled by anionic clusters. Optical-quality crystals were grown from the compositions with different sodium-lithium ratio. The results of Rietveld refinement based on powder data demonstrate linear increase of parameter a and unit cell volume with Na/(Na + Li) ratio in cation site. Parameter c is less sensitive to the changes in stoichiometry, which is consistent with channel topology of LixNa1-xBa12(BO3)7F4 structure. Distinctive feature of LixNa1-xBa12(BO3)7F4 crystals is their deep purple color, which is due to both hole-type and electron-type centers. Crystals are characterized by linear dichroism effect.

Flexible Chirality in Self‐Assembled N‐Annulated Perylenedicarboxamides

N-annulated perylenedicarboxamides 1-3 form supramolecular polymers with a strong tendency to aggregate. The bundles of fibers formed generate a spontaneous anisotropy that conditions the chiroptical features of the described molecules in solution; a strong linear dichroism effect accompanies the circular dichroism (CD) outcome. There is no influence of the point chirality existing at the side chains of 1 and 2, and these molecules present the same chiroptical features as achiral 3. Mechanical rotary stirring increases the CD response and the sign of the dichroic signal changes with the stirring direction. Theoretical calculations indicate that the self-assembly of 1-3 in helical columnar stacks generates atropisomers by the restricted rotation of the H-bonded benzamide units. Molecular mechanics/molecular dynamics calculations predict a feasible intrastack stereomutation of the helical aggregates due to the rapid rupture/formation of the amide H-bonds. This oscillating helicity, together with the fact that right- and left-handed helices are predicted to be mostly isoenergetic, justifies the negligible contribution of the molecular chirality embedded in the paraffinic side chains of 1 and 2. The reported CD behavior contributes to shed light on the physical processes promoting flexible macroscopic chirality that, in turn, can be utilized for the spectroscopic visualization of torsional flows generated in a vortex.

Electronic Structures of Ferromagnetic CeAgSb2: Soft X-ray Absorption, Magnetic Circular Dichroism, and Angle-Resolved Photoemission Spectroscopies

We report a combined study for the electronic structures of ferromagnetic CeAgSb$_2$ using soft X-ray absorption (XAS), magnetic circular dichroism (XMCD), and angle-resolved photoemission (ARPES) spectroscopies. The Ce $M_{4, 5}$ XAS spectra show very small satellite structures, reflecting a strongly localized character of the Ce $4f$ electrons. The linear dichroism effects in the Ce $M_{4, 5}$ XAS spectra demonstrate the ground state Ce $4f$ symmetry of $\Gamma{_6}$, the spatial distribution of which is directed along the $c$-axis. The XMCD results give support to the picture of local-moment magnetism in CeAgSb$_2$. Moreover it is also found that the theoretical band dispersions for LaAgSb$_2$ provides better description of the ARPES band structures than those for CeAgSb$_2$. Nevertheless, ARPES spectra at the Ce $3d$-$4f$ resonance show the momentum dependence for the intensity ratio between Ce $4f^{1}_{5/2}$ and $4f^{1}_{7/2}$ peaks in a part of the Brillouin zone, suggesting the non-negligible momentum dependent hybridization effect between the Ce $4f$ and the conduction electrons. This is associated with the moderate mass enhancement in CeAgSb$_2$.

Photocontrolled On-Surface Pseudorotaxane Formation with Well-Ordered Macrocycle Multilayers.

The photoinduced pseudorotaxane formation between a photoresponsive axle and a tetralactam macrocycle was investigated in solution and on glass surfaces with immobilized multilayers of macrocycles. In the course of this reaction, a novel photoswitchable binding station with azobenzene as the photoswitchable unit and diketopiperazine as the binding station was synthesized and studied by NMR and UV/Vis spectroscopy. Glass surfaces have been functionalized with pyridine-terminated SAMs and subsequently with multilayers of macrocycles through layer-by-layer self assembly. A preferred orientation of the macrocycles could be confirmed by NEXAFS spectroscopy. The photocontrolled deposition of the axle into the surface-bound macrocycle-multilayers was monitored by UV/Vis spectroscopy and led to an increase of the molecular order, as indicated by more substantial linear dichroism effects in angle-resolved NEXAFS spectra.

Growth and dichroic properties of LiBa12(BO3)7F4 crystal

The bulk crystals of LiBa12(BO3)7F4 were obtained from two flux compositions by the top seeded solution growth method. Crystals grown from BaCO3:BaF2:H3BO3:Li2CO3 = 3:3:3:1 charge were found to have a distinct linear dichroism effect at 0.35–0.65 and around 0.73 μm. This suggests application of the material in the production of polarizing filters and attenuators for visible range lasers.

Antiferromagnetic proximity effect in epitaxial CoO/NiO/MgO(001) systems.

Magnetic proximity effect between two magnetic layers is an important focus of research for discovering new physical properties of magnetic systems. Antiferromagnets (AFMs) are fundamental systems with magnetic ordering and promising candidate materials in the emerging field of antiferromagnetic spintronics. However, the magnetic proximity effect between antiferromagnetic bilayers is rarely studied because detecting the spin orientation of AFMs is challenging. Using X-ray linear dichroism and magneto-optical Kerr effect measurements, we investigated antiferromagnetic proximity effects in epitaxial CoO/NiO/MgO(001) systems. We found the antiferromagnetic spin of the NiO underwent a spin reorientation transition from in-plane to out-of-plane with increasing NiO thickness, with the existence of vertical exchange spring spin alignment in thick NiO. More interestingly, the Néel temperature of the CoO layer was greatly enhanced by the adjacent NiO layer, with the extent of the enhancement closely dependent on the spin orientation of NiO layer. This phenomenon was attributed to different exchange coupling strengths at the AFM/AFM interface depending on the relative spin directions. Our results indicate a new route for modifying the spin configuration and ordering temperature of AFMs through the magnetic proximity effect near room temperature, which should further benefit the design of AFM spintronic devices.

Magnetic linear dichroism of photoemission from ultrathin manganese films on silicon

The magnetic linear dichroism (MLD) effect in photoemission of Mn 3p electrons was used to study magnetic properties of Mn films (to 2.5 nm thick) grown on the Si(111)-(7 × 7) surface at room temperature and manganese silicide films grown by solid-phase epitaxy. The experiments were performed using linearly polarized light with a photon energy of 130 eV, incident at an angle of 30° to the sample surface. Photoelectron spectra were measured in a narrow solid angle focused along the normal to the surface for two opposite sample magnetization directions in the surface plane, perpendicular to the polarization vector of the light wave. It was shown that the MLD effect characteristic of films with high-temperature ferromagnetism appears after depositing ∼2 nm Mn. The formation of manganese silicides upon annealings of the sample with deposited 2.5 nm Mn results in the disappearance of the MLD effect.

Dynamic phase reversal of photo-induced precession of magnetization in ferromagnetic (Ga,Mn)As thin film

Ultrafast laser-triggered coherent magnetization dynamics in ferromagnetic (Ga,Mn)As films have been investigated by time-resolved magneto-optical spectroscopy . Dynamic phase reversal in the magnetic precession process is observed when the ambient temperature or the external magnetic field is varied. This phenomenon is found to be sensitive to the spontaneous magnetization orientation, and is attributed to the giant magnetic linear dichroism (MLD) effect in (Ga,Mn)As. Our findings suggest that this effect will enable the sensitive measurement of the dynamic phase of in-plane magnetization precession on picosecond time scale in the collective spin excitation in (Ga,Mn)As, thus enabling efficient and ultrafast magneto-optical detection for magnetization dynamics in ferromagnetic semiconductor-based spintronic devices. ● Laser-triggered coherent magnetization dynamics study in (Ga,Mn)As by TR-MOKE. ● Dynamic phase reversal of magnetization precession is observed by giant MLD effect. ● Dynamic phase reversal is sensitive to modulation of the effective magnetic fields. ● Demonstrates an efficient method to visualize the magnetization reorientation.

Coupled molecular switching processes in ordered mono- and multilayers of stimulus-responsive rotaxanes on gold surfaces.

Interfaces provide the structural basis for function as, for example, encountered in nature in the membrane-embedded photosystem or in technology in solar cells. Synthetic functional multilayers of molecules cooperating in a coupled manner can be fabricated on surfaces through layer-by-layer self-assembly. Ordered arrays of stimulus-responsive rotaxanes undergoing well-controlled axle shuttling are excellent candidates for coupled mechanical motion. Such stimulus-responsive surfaces may help integrate synthetic molecular machines in larger systems exhibiting even macroscopic effects or generating mechanical work from chemical energy through cooperative action. The present work demonstrates the successful deposition of ordered mono- and multilayers of chemically switchable rotaxanes on gold surfaces. Rotaxane mono- and multilayers are shown to reversibly switch in a coupled manner between two ordered states as revealed by linear dichroism effects in angle-resolved NEXAFS spectra. Such a concerted switching process is observed only when the surfaces are well packed, while less densely packed surfaces lacking lateral order do not exhibit such effects.