Polarization-resolved Spectroscopy Research Articles

Looking at Photoinduced Charge Transfer Processes in the IR: Answers to Several Long-Standing Questions.

Because of its crucial role in many areas of science and technology, photoinduced electron transfer is the most investigated photochemical reaction. Despite this, several important questions remain open. We present recent efforts to answer some of them, which concern both inter- and intramolecular processes. The decisive factor that allowed these issues to be successfully addressed was the use of time-resolved infrared (TRIR) spectroscopy. Many different transient species, such as tight and loose ion pairs (TIPs and LIPs) and exciplexes, have been invoked to explain the dynamics of intermolecular photoinduced charge separation reactions (i.e., electron transfer between two neutral species) and the production of free ions. However, their structures are essentially unknown, and their exact roles in the reaction mechanism are unclear. Indeed, the commonly used transient electronic absorption spectroscopy does not give much structural insight and cannot clearly distinguish ion pairs from free ions, at least in the visible region. Unambiguous spectral signatures of TIPs, LIPs, and exciplexes could be observed in the IR using electron donor/acceptor (D/A) pairs with adequate vibrational marker modes. The ability to spectrally distinguish these intermediates allowed their dynamics to be disentangled and their roles to be determined. Structural information could be obtained using polarization-resolved TRIR spectroscopy. Our investigations reveal that moderately to highly exergonic reactions result in the formation of both TIPs and LIPs. TIPs are not only generated upon direct charge-transfer excitation of DA complexes, as usually assumed, but are also formed upon static quenching with reactant pairs at distances and orientations enabling charge separation without diffusion. On the other hand, dynamic quenching produces primarily LIPs. In the case of highly exergonic reactions, strong indirect evidence for the generation of ion pairs in an electronic excited state was found, accounting for the absence of an inverted region. Finally, weakly exergonic reactions produce predominantly exciplexes, which can evolve further into ion pairs or recombine to the neutral ground state. The high sensitivity of specific vibrational modes to the local electronic density was exploited to visualize the photoinduced charge flow in symmetric A-(π-D)2- and D-(π-A)2-type molecules developed for their two-photon absorption properties. The electronic ground state and Franck-Condon S1 state of these molecules are purely quadrupolar, but the strong solvatochromism of their fluorescence points to a highly dipolar relaxed S1 state. This has been explained in terms of excited-state symmetry breaking induced by solvent and/or structural fluctuations. However, real-time observation of this process was missing. Direct visualization of symmetry-breaking charge transfer was achieved using TRIR spectroscopy by monitoring vibrations localized in the two arms of these molecules. A transition from a purely quadrupolar state to a symmetry-broken state on the timescale of solvent relaxation could be clearly observed in polar solvents, indicating that symmetry breaking occurs primarily via solvent fluctuations. In the case of the D-(π-A)2 molecule, this breaking results in different basicities at the two A ends and consequently in different affinities for H-bonds, which in turn leads to the formation of an asymmetric tight H-bonded complex in highly protic solvents.

Time resolved anisotropic emission from an aluminium laser produced plasma

The polarisation anisotropy of the emission from a laser produced aluminium plasma has been studied using time and polarisation resolved spectroscopy at various background pressures of air. A Wollaston prism was used to resolve the emission from the plasma into polarisation components that are parallel and orthogonal to the plasma expansion axis. Spectroscopy reveals that as the background pressure is increased, strongly polarised continuum emission dominates at early stages of the plasma formation. The results are compared and contrasted to similar experiments and discussed in the framework of a recombining plasma.

Hybrid Helix Metamaterials for Giant and Ultrawide Circular Dichroism

Circular polarization-resolved imaging and spectroscopy have versatile applications ranging from astronomy and biological and biomedical studies to remote sensing. To achieve real-time imagery with high contrast and rich information, integratable circular polarizers with high extinction ratios, broad operation bandwidths, and low insertion loss are urgently desired, while to our knowledge no structures proposed previously can balance these three vital parameters. In this paper, a concept of a hybrid helix metamaterial has been proposed to achieve ultrawide and giant circular dichroism with low insertion loss simultaneously. By coupling the localized and delocalized resonant modes, a broad and strong blocking band for unselected polarization can be realized with a pencil-like configuration. A giant extinction ratio of 5.9 × 105 can be obtained with a six-pitch hybrid single-helix array, which is almost 7 times larger than the best result reported by Behera et al. in 2015. A very high average extinction rat...

Structural colour from helicoidal cell-wall architecture in fruits of Margaritaria nobilis.

The bright and intense blue-green coloration of the fruits of Margaritaria nobilis (Phyllanthaceae) was investigated using polarization-resolved spectroscopy and transmission electron microscopy. Optical measurements of freshly collected fruits revealed a strong circularly polarized reflection of the fruit that originates from a cellulose helicoidal cell wall structure in the pericarp cells. Hyperspectral microscopy was used to capture the iridescent effect at the single-cell level.

Momentum-dependent group velocity of surface plasmon polaritons in two-dimensional metallic nanohole array.

We determine the momentum-dependent group velocities of (±1,0) and (0, ± 1) Bloch-like surface plasmon polaritons (SPPs) in two-dimensional Au nanohole array by measuring their propagation lengths and decay lifetimes at different SPP propagation length via angle- and polarization-resolved reflectivity spectroscopy and real- and Fourier-space microscopy. We find the decay length and lifetime, as well as group velocity, are highly dependent on the propagation direction. In particular, close to the Γ-M direction where two SPPs begin to interfere, the group velocity decreases due to the increase of the standing wave character. More importantly, the two SPPs are strongly interacted with each other at the Γ-M direction, resulting in forming the dark and bright modes. We find the group velocity of the dark mode is higher that of the bright mode despite its higher quality factor, or longer decay lifetime. We attribute such difference to the distinct field symmetries of dark and bright modes, yielding different effective indices. While bright mode has fields mostly concentrated at the flat metal region to produce higher effective index and therefore lower velocity, the fields of the dark mode are located near the air hole, resulting in higher velocity.

Magnetoreflection spectroscopy of monolayer transition-metal dichalcogenide semiconductors in pulsed magnetic fields

The authors describe recent experimental efforts to perform polarization-resolved optical spectroscopy of monolayer transition-metal dichalcogenide semiconductors in very large pulsed magnetic fields to 65 T. The experimental setup and technical challenges are discussed in detail, and temperature-dependent magnetoreflection spectra from atomically thin tungsten disulphide are presented. The data clearly reveal not only the valley Zeeman effect in these two-dimensional semiconductors but also the small quadratic exciton diamagnetic shift from which the very small exciton size can be directly inferred. Finally, the authors present model calculations that demonstrate how the measured diamagnetic shifts can be used to constrain estimates of the exciton binding energy in this new family of monolayer semiconductors.

Directional Emission from Leaky and Guided Modes in GaAs Nanowires Measured by Cathodoluminescence

We measure the polarization-resolved angular emission distribution from thin and thick GaAs nanowires (diameters ∼110 and ∼180 nm) with cathodoluminescence polarimetry. The nanowires, which horizontally rest on a thin carbon film, are excited by a 5 keV electron beam and emit band gap luminescence at a central wavelength of 870 nm. The emission can couple to different waveguide modes that propagate along the wire, are dependent on the wire diameter, and determine the directionality and polarization of the emission. Although each measured nanowire can support different modes, the polarized emission is dominated by the TM01 waveguide mode in all cases, independently of wire diameter. When exciting the nanowires close to the end facets, the thin and thick wires exhibit opposite directional emission. The emission from thin nanowires is dominated by a leaky TM01 mode that leads to emission toward the opposite end facet (emission to the right when exciting the left-side edge). For the thick wires, however, the TM01 mode is guided but also lossy due to absorption in the substrate. In such a case, the wires emit toward the excited end facet (to the left when exciting the left-side edge). The emission directionality switches for nanowire diameters in the range of 145–170 nm. We show that the measurements agree well with both a simple 1D current model and numerical simulations. The high spatial resolution of angle- and polarization-resolved cathodoluminescence spectroscopy provides detailed insight into the nanoscale emission and propagation of light in semiconductor nanowires.

Surface plasmon resonance spectroscopy of single bowtie nano-antennas using a differential reflectivity method.

We report on the structural and optical properties of individual bowtie nanoantennas both on glass and semiconducting GaAs substrates. The antennas on glass (GaAs) are shown to be of excellent quality and high uniformity reflected by narrow size distributions with standard deviations for the triangle and gap size of = 4.5 nm = 2.6 nm and = 5.4 nm = 3.8 nm, respectively. The corresponding optical properties of individual nanoantennas studied by differential reflection spectroscopy show a strong reduction of the localised surface plasmon polariton resonance linewidth from 0.21 eV to 0.07 eV upon reducing the antenna size from 150 nm to 100 nm. This is attributed to the absence of inhomogeneous broadening as compared to optical measurements on nanoantenna ensembles. The inter-particle coupling of an individual bowtie nanoantenna, which gives rise to strongly localised and enhanced electromagnetic hotspots, is demonstrated using polarization-resolved spectroscopy, yielding a large degree of linear polarization of ρmax ~ 80%. The combination of highly reproducible nanofabrication and fast, non-destructive and non-contaminating optical spectroscopy paves the route towards future semiconductor-based nano-plasmonic circuits, consisting of multiple photonic and plasmonic entities.

Polarization-resolved spectroscopy imaging of grain boundaries and optical excitations in crystalline organic thin films.

Exploration of optical properties of organic crystalline semiconductors thin films is challenging due to submicron grain sizes and the presence of numerous structural defects, disorder and grain boundaries. Here we report on the results of combined linear dichroism (LD)/ polarization-resolved photoluminescence (PL) scanning microscopy experiments that simultaneously probe the excitonic radiative recombination and the molecular ordering in solution-processed metal-free phthalocyanine crystalline thin films with macroscopic grain sizes. LD/PL images reveal the relative orientation of the singlet exciton transition dipoles at the grain boundaries and the presence of a localized electronic state that acts like a barrier for exciton diffusion across the grain boundary. We also show how this energy barrier can be entirely eliminated through the optimization of deposition parameters that results in films with large grain sizes and small-angle boundaries. These studies open an avenue for exploring the influence of long-range order on exciton diffusion and carrier transport.

Interfacial Organization in Dipolar Dye-Based Organic Nanoparticles Probed by Second-Harmonic Scattering

We have undertaken polarization-resolved SHS experiments to investigate a series of two fluorescent organic nanoparticles (FONs) made from dipolar dyes bearing a triphenylamine-donating end-group and a slightly hydrophilic acceptor end-group. The FONs, which show very large negative surface potentials, responsible for their good colloidal stability in water, are very bright SHS emitters in water, attractive for single-particle tracking and bioimaging. With the polarization-resolved SHS technique, we come up with a new and noninvasive method to gain insight into the origin of the surface potential of the FONs, as well as into their evolution upon change of ionic strength by following their multipolar response when adding salt. In pure water, the polarization-resolved SHS spectroscopy reveals the presence of a region of local polar order close to the surface (i.e., orientation of the dipolar dyes), leading to a strong dipolar contribution. Quite interestingly, when adding KCl salt, the initial two-lobe SHS ...

Probing magnetic and electric optical responses of silicon nanoparticles

We study experimentally both magnetic and electric optically induced resonances of silicon nanoparticles by combining polarization-resolved dark-field spectroscopy and near-field scanning optical microscopy measurements. We reveal that the scattering spectra exhibit strong sensitivity of electric dipole response to the probing beam polarization and attribute the characteristic asymmetry of measured near-field patterns to the excitation of a magnetic dipole mode. The proposed experimental approach can serve as a powerful tool for the study of photonic nanostructures possessing both electric and magnetic optical responses.

Ultrafast probes of nonequilibrium hole spin relaxation in the ferromagnetic semiconductor GaMnAs

We directly measure the hole spin lifetime in ferromagnetic GaMnAs via time- and polarization-resolved spectroscopy. Below the Curie temperature Tc, an ultrafast photoexcitation with linearly-polarized light is shown to create a non-equilibrium hole spin population via the dynamical polarization of holes through p-d exchange scattering with ferromagnetically-ordered Mn spins, and we characterize their relaxation dynamics. The observed relaxation consists of a distinct three-step recovery : (i) femtosecond (fs) hole spin relaxation ~ $160-200 fs, (ii) picosecond (ps) hole energy relaxation ~ 1-2 ps, and (iii) a coherent, damped Mn spin precession with a period of ~ 250 ps. The transient amplitude of the hole spin component diminishes with increasing temperature, directly following the ferromagnetic order, while the hole energy amplitude shows negligible temperature change, consistent with our interpretation. Our results thus establish the hole spin lifetimes in ferromagnetic semiconductors and demonstrate a novel spectroscopy method for studying non-equilibrium hole spins in the presence of correlation and magnetic order.

Optical control of spin textures in quasi-one-dimensional polariton condensates

We investigate, through polarization-resolved spectroscopy, the spin transport by propagating polariton condensates in a quasi one-dimensional microcavity ridge along macroscopic distances. Under circularly polarized, continuous-wave, non-resonant excitation, a sinusoidal precession of the spin in real space is observed, whose phase depends on the emission energy. The experiments are compared with simulations of the spinor-polariton condensate dynamics based on a generalized Gross-Pitaevskii equation, modified to account for incoherent pumping, decay and energy relaxation within the condensate.

Optical spin orientation of an individualMn2+ion in a CdSe/ZnSe quantum dot

We demonstrate optical spin orientation of an individual ${\mathrm{Mn}}^{2+}$ ion embedded in a CdSe/ZnSe quantum dot. It is achieved through the injection of spin-polarized excitons to the dot under circularly polarized below-the-barrier optical excitation at energy sufficiently close to the dot emission energy. The efficiencies of both the exciton spin-transfer and optical pumping of the ${\mathrm{Mn}}^{2+}$ spin are studied by means of polarization-resolved single-dot spectroscopy performed at magnetic field in a Faraday configuration. The ion spin orientation efficiency is found to increase significantly with the magnetic field, while the spin-polarization degree of injected excitons remains constant and yields about 40%.

Spectroscopic Study of Anisotropic Excitons in Single Crystal Hexacene.

The linear optical response of hexacene single crystals over a spectral range of 1.3-1.9 eV was studied using polarization-resolved reflectance spectroscopy at cryogenic temperatures. We observe strong polarization anisotropy for all optical transitions. Pronounced deviations from the single-molecule, solution-phase spectra are present, with a measured Davydov splitting of 180 meV, indicating strong intermolecular coupling. The energies and oscillator strengths of the relevant optical transitions and polarization-dependent absorption coefficients are extracted from quantitative analysis of the data.

Determination of the absorption and radiative decay rates of dark and bright plasmonic modes

When two degenerate surface plasmon polariton (SPP) modes couple, in addition to the creation of plasmonic band gap, their respective decay rates are modified as well, resulting in the formation of a pair of dark and bright modes. We combine temporal coupled mode theory, finite-difference time-domain simulation, and angle- and polarization-resolved reflectivity spectroscopy to study the absorption and radiative decay rates of this pair in periodic system. One-dimensional metallic groove arrays are served as an example here. We find for arrays with small groove width, when approaching to the coupling of -1 and + 1 SPP modes, while the radiative decay rate of the high energy mode tends to become zero, the absorption rate decreases as well, forming a "cold" dark mode. At the same time, both the absorption and radiative decay rates of the low energy mode increase, yielding a "hot" bright mode. The situation is completely reversed when groove width increases, turning the high energy mode into a "cold" bright mode and vice versa for the low energy mode. We attribute such modifications to the interplay between the real and imaginary parts of the complex coupling constant, which are found to be highly geometry dependent. Further numerical simulations show the hybridized modes exhibits distinctive electric and magnetic field symmetries, giving rise to different surface charge distributions and Poynting vector profiles, which significantly affect the resulting absorption and radiation losses. Finally, we have measured the decay rates and the complex coupling constant of the hybridized modes and the experimental results are consistent with the analytic and numerical results.

Hydration dynamics of aqueous glucose probed with polarization-resolved fs-IR spectroscopy.

The dynamics of water in aqueous solutions of glucose have been investigated using polarization-resolved femtosecond infrared spectroscopy of the hydroxyl stretch vibrations of water and glucose. Using reference measurements on solutions of glucose in dimethylsulfoxide and a spectral decomposition model, we are able to distinguish the reorientation dynamics of the glucose and water hydroxyl groups. We find that the water reorientation dynamics strongly slow down in the presence of glucose.

Insights into the Excitonic States of Individual Chlorosomes from Chlorobaculum tepidum

Green-sulfur bacteria have evolved a unique light-harvesting apparatus, the chlorosome, by which it is perfectly adapted to thrive photosynthetically under extremely low light conditions. We have used single-particle, optical spectroscopy to study the structure-function relationship of chlorosomes each of which incorporates hundreds of thousands of self-assembled bacteriochlorophyll (BChl) molecules. The electronically excited states of these molecular assemblies are described as Frenkel excitons whose photophysical properties depend crucially on the mutual arrangement of the pigments. The signature of these Frenkel excitons and its relation to the supramolecular organization of the chlorosome becomes accessible by optical spectroscopy. Because subtle spectral features get obscured by ensemble averaging, we have studied individual chlorosomes from wild-type Chlorobaculum tepidum by polarization-resolved fluorescence-excitation spectroscopy. This approach minimizes the inherent sample heterogeneity and allows us to reveal properties of the exciton states without ensemble averaging. The results are compared with predictions from computer simulations of various models of the supramolecular organization of the BChl monomers. We find that the photophysical properties of individual chlorosomes from wild-type Chlorobaculum tepidum are consistent with a (multiwall) helical arrangement of syn-anti stacked BChl molecules in cylinders and/or spirals of different size.

Probing the plasmonic band structure of an optical metamaterial

Knowledge of the plasmonic band structure is crucial for the fundamental understanding and better control of electromagnetic waves in periodic optical metamaterials. Here, we probe the plasmonic band structure of the important fishnet metamaterial by angle- and polarization-resolved optical spectroscopy. We show that multiple ``magnetic'' plasmon bands exist in the fishnet metamaterial, and they display interesting dispersion behavior. We can understand the plasmon bands qualitatively using a band-structure zone-folding picture. Interestingly, some plasmon resonances have wave-vector-dependent coupling, and the corresponding plasmon bands exhibit anticrossing behavior due to hybridization of the plasmonic waves.

Polarized emission in polariton condensates: Switching in a one-dimensional natural trap versus inversion in two dimensions

We perform polarization resolved spectroscopy of two- and one-dimensional microcavity-polariton condensates, which are formed by exciting the system in the optical parametric oscillator configuration. We observe polarization inversion for linearly polarized pumping parallel to the wire in both the 1D and 2D systems. As the polarization plane of the pump is rotated, the degree of linear polarization of the 2D system oscillates between orthogonal polarizations with the same period as that of the pump. However, the 1D system switches abruptly between two states of high degree of linear polarization with half the period. Two complementary models, based on semiclassical Boltzmann kinetic equations and the Gross-Pitaevskii equation, respectively, obtain an excellent agreement with the experimental results, providing a deep insight into the mechanisms responsible for the polarization switching.