Polarization mapping of nanoparticle plasmonic coupling

We propose the use of polarization mapping as a tool to better separate the effects of plasmonic coupling from the local refractive index for molecular imaging and biosensing using gold nanoparticles. Polarization mapping allows identification of the orthogonal excitation mode when the particle dimer orientation is unknown, as may be the case when using plasmonic nanoparticles for cell labeling. This information can be used to sense relative changes in the dielectric environment, or for absolute dielectric sensing with additional a priori interparticle distance information. First, the theoretical scattering by nanoparticle pairs is modeled under parallel and orthogonal polarization orientations and increasing interparticle separation. Second, polarization mapping of substrate bound nanoparticles using dark-field microspectroscopy is investigated as a method to isolate the individual plasmonic coupling modes associated with a pair of nanoparticles without reorientation of the sample. The results of this study provide useful insight toward potential avenues for monitoring distances using plasmonic nanoparticles and sensing the local refractive index using nanoparticle pairs when the pair orientation is not known, as may be the case when using nanoparticles for cell receptor labeling.     

Study on optical properties of aggregated ultra-small metal nanoparticles

We study the optical properties of dimer and septamer aggregates (in forms of being separated or merged) of ultra-small silver nanoparticles (a few nanometers in diameter) by calculating their extinction spectra and optical field distributions using the discrete dipole approximation method. Characteristics of their extinction spectra are identified due to different resonance modes dependent on the incidence states of light. Specifically, as polarization of the incidence light is perpendicular to the center-to-center lines of the nanoparticles, interaction of neighboring nanoparticles is in the “repulsive coupling mode”, which results in blue-shift of the resonance peak with decrease of the nanoparticle interspacing. While, whenever there is a projection of the polarization of incident light on the center-to-center lines of the nanoparticles, the “attractive coupling mode” between the nanoparticles dominates in their resonant interaction, which results in red-shift of the resonance peak with decrease of the nanoparticle interspacing. It is also shown that optical interaction of the ultra-small nanoparticles is only effective when their interspacings are approximately less than 15 nm, and particularly prominent when Coulomb interactions of the electronic charges of plasmons are active within a few nanometers.     

Tuning the shape anisotropy of silver nanoparticles using time-delayed laser pulse pair irradiations

Glass-embedded spherical silver nanoparticles were irradiated by pairs of delayed femtosecond laser pulses. The influence of intensity, relative polarization (parallel or orthogonal) and time delay between the pulses was investigated. We found a delay-dependent reversal of the orientation of prolate nanoparticles produced in the low-intensity regime: at very short time delays up to 10 ps between pulse pairs the polarization direction of the second-hitting pulse defines the particles’ symmetry axes; in an intermediate regime between 10 and 20 ps no optical dichroism is found at all; at more than 20 ps delay between the pulses, finally, the transformed nanoparticles are oriented along the polarization direction of the first-hitting pulse. Also, in the quite different situation of the high-intensity regime using parallel-polarized pulse pairs, where normally oblate particles are created, isotropic spectral changes (i.e., no dichroism) after irradiation were observed at delay times around 20 ps. The possible physical background of this apparently very special inter-pulse delay of around 20 ps is discussed.     

Direct observation of ferromagnetic spin polarization in gold nanoparticles

We report the first direct observation of ferromagnetic spin polarization of Au nanoparticles with a mean diameter of 1.9 nm using x-ray magnetic circular dichroism (XMCD). Owing to the element selectivity of XMCD, only the gold magnetization is explored. Magnetization of gold atoms as estimated by XMCD shows a good agreement with results obtained by conventional magnetometry. This evidences intrinsic spin polarization in nanosized gold.     

Ultrathin films of ferroelectric solid solutions under a residual depolarizing field

A first-principles-derived approach is developed to study the effects of depolarizing electric fields on the properties of Pb(Zr,Ti)O3 ultrathin films for different mechanical boundary conditions. A rich variety of ferroelectric phases and polarization patterns is found, depending on the interplay between strain and the amount of screening of surface charges. Examples include triclinic phases, monoclinic states with in-plane and/or out-of-plane components of the polarization, homogeneous and inhomogeneous tetragonal states, as well as peculiar laminar nanodomains.     

Interplay of couplings between antiferrodistortive, ferroelectric, and strain degrees of freedom in monodomain PbTiO3/SrTiO3 superlattices

We report first-principles calculations on the coupling between epitaxial strain, polarization, and oxygen octahedra rotations in monodomain (PbTiO(3))(n)/(SrTiO(3))(n) superlattices. We show how the interplay between (i) the epitaxial strain and (ii) the electrostatic conditions can be used to control the orientation of the main axis of the system. The electrostatic constrains at the interface facilitate the polarization rotation and, as a consequence, we predict large piezoelectric responses at epitaxial strains smaller than those required considering only strain effects. In addition, ferroelectric (FE) and antiferrodistortive (AFD) modes are strongly coupled. Usual steric arguments cannot explain this coupling and a covalent model is proposed to account for it. The energy gain due to the FE-AFD coupling decreases with the periodicity of the superlattice, becoming negligible for n ≥ 3.     

Raman scattering as a probe of the tensile strain distribution in GaAs grown on Si(111) by molecular beam epitaxy

Epitaxial layers of GaAs grown on Si substrates, where the layer thickness greatly exceeds any critical thickness based on mismatch in lattice constant alone, have been shown to be under tensile strain for temperature at or below 300 K. This "thermal" strain arises from the difference in thermal expansion coefficients between GaAs and Si. We have performed Raman experiments on GaAs layers grown on both Si (001) and Si (111) substrates. We have observed a shift in the optical modes towards lower frequencies which is indicative of tensile strain in the GaAs layers, this is greater in the (111) growth direction than in the (001) one. In order to investigate the strain distribution as a function of distance from the GaAs/Si interface we have measured Raman spectra after successive removing of the epitaxial layer by chemical etching. We have found out that the strain decreases with increasing distance from the interface. We have developed the theory of Cerdeira et al. (1) to determine quantitatively the strain present in the heteroepitaxial layers. We have used, for the first time, polarization selection rules to separate the various components of the optical phonon modes. According to the theory we have observed that the doubly degenerate TO phonon line exhibits both a splitting and shift with strain, while only a shift is observed for the LO phonon line. In conformity with Cerdeira we have remarked that the strain dependence of the LO phonon is equal to that of the TO phonon mode observed in crossed polarization configuration.     

Weak dependence of spontaneous polarization on epitaxial strain in ferroelectric BiAlO3: A first-principles study

We investigate the effects of epitaxial strain on the ferroelectric properties of BiAlO₃ (BAO) using first-principles calculations. We find a large polarization (P) of 72.3 μC/cm² as well as a small energy barrier of ∼0.1 eV/formula unit for coherent ferroelectric switching of unstrained BAO. Thus, this material is suitable for applications in high-speed nonvolatile memory. We study the modification of P due to epitaxial strains of −5 to +5%, where the minus and plus signs represent the compressive and tensile strains, respectively. The polarization of BAO is insensitive to epitaxial strain; the polarization change is limited to below ∼6%. The weak sensitivity of the polarization is attributed to the stereochemical activity of Bi 6s² lone pairs as well as the inertness of the B-site Al to the polarization. The strain application modifies the switching energy barrier by up to 30%, which provides guidelines for design of devices based on BAO.     

Piezoelectricity of the ice nanotube with odd side faces

The molecular dynamics (MD) simulations have been utilized to investigate the strain effect on the polarization distribution and piezoelectric coefficient of the ice nanotube (ice-NT) with odd side faces. It is found that the polarization of the system increases under the compressive strain, and decreases with the tensile strain. The piezoelectric coefficient is about 1.3 C/m² for a single 〈5, 0〉 ice-NT with its diameter of 4.34 Å, which is superior to BaTiO₃ nanowire, the ferroelectricity of the latter with the same diameter has been vanished owning to the depolarization effect. We have also considered the axial strain energy under the different strains, and found that most of the strain energy in the compressive process seems larger than that of the stretching case.     

Suppressed dependence of polarization on epitaxial strain in highly polar ferroelectrics

A combined experimental and computational investigation of coupling between polarization and epitaxial strain in highly polar ferroelectric PbZr(0.2)Ti(0.8)O3 (PZT) thin films is reported. A comparison of the properties of relaxed (tetragonality c/a approximately 1.05) and highly strained (c/a approximately 1.09) epitaxial films shows that polarization, while being amongst the highest reported for PZT or PbTiO3 in either film or bulk forms P(r) approximately 82 microC/cm(2)), is almost independent of the epitaxial strain. We attribute this behavior to a suppressed sensitivity of the A-site cations to epitaxial strain in these Pb-based perovskites, where the ferroelectric displacements are already large, contrary to the case of less polar perovskites, such as BaTiO3. In the latter case, the A-site cation (Ba) and equatorial oxygen displacements can lead to substantial polarization increases.     

Effect of electric-field-assisted thermal treatment on the strain and ferroelectric properties of (100)-oriented ferroelectric Pb(Zr0.52Ti0.48)O3 thin films

Ferroelectric Pb(Zr_0.52Ti_0.48)O₃ thin films were deposited on the Pt/Ti/SiO₂/Si substrate by a sol-gel method. As a direct electric field was applied on the films during thermal treatment, strain behavior and ferroelectric properties have been investigated. X-ray diffraction patterns show that great tensile strain exists nearby the interface of the 250 nm thin film while thermal treatment assisted with direct electric field can obviously relax it. The analysis of hysteresis loops indicates that the remnant polarization increases with the thermal treatment time. These results suggest that electric-field-assisted thermal treatment is an effective way to reduce films' tensile strain through the local plastic deformation in Pt layer and enhance the remnant polarization.     

Multipole interference in the second-harmonic optical radiation from gold nanoparticles

We provide experimental evidence of higher multipole (magnetic dipole and electric quadrupole) radiation in second-harmonic (SH) generation from arrays of metal nanoparticles. Fundamental differences in the radiative properties of electric dipoles and higher multipoles yield opposite interference effects observed in the SH intensities measured in the reflected and transmitted directions. These interference effects clearly depend on the polarization of the fundamental field, directly indicating the importance of multipole effects in the nonlinear response. We estimate that higher multipoles contribute up to 20% of the total emitted SH field amplitude for certain polarization configurations.     

Strain-induced polarization rotation in epitaxial (001) BiFeO3 thin films

Direct measurement of the remanent polarization of high quality (001)-oriented epitaxial BiFeO3 thin films shows a strong strain dependence, even larger than conventional (001)-oriented PbTiO3 films. Thermodynamic analysis reveals that a strain-induced polarization rotation mechanism is responsible for the large change in the out-of-plane polarization of (001) BiFeO3 with biaxial strain while the spontaneous polarization itself remains almost constant.     

Theoretical studies of polarization dependent electro-optical modulation in lattice matched and strained multi-quantum well structures

We report on polarization dependent optical absorption for excitonic and interband transitions in lattice matched (GaAs/AlGaAs) and strained (biaxial tensile strain - GaAsP/AlGaAs; biaxial compressive strain - InGaAs/AlGaAs) multiquantum well structures in the presence of transverse electric fields. The hole states are solved by using the Kohn-Luttinger Hamiltonian and using an eigenvalue technique. The effect of heavy-hole and light-hole mixing due to the strain, electric field and quantization is studied. Under biaxial tensile strain the heavy-hole and light-hole transition can coincide, leading to interesting polarization dependent effects. Results are presented for excitonic and interband transitions.     

The optical properties between an incident wave and the active layer of a bubble-pit AgO<Subscript>x</Subscript>-type super-resolution near-field structure

The deformation and plasmon effects of collective localized surface plasmons between incident light and bubble-pit AgO_x-type super-RENS structure have been studied using finite-difference time-domain (FDTD) method. We find that the polarization, wavelength of incident light, and particle sizes of Ag nanoparticles are sensitive to the plasma resonance. The Ag nanoparticles inside the bubble-pit AgO_x-type super-RENS structure give the additional outer boundaries to the motion of the Ag nanoparticles, and excite more evanescent field which located in the far edge of the bubble from the optical axis of the incident beam. The optical properties between active layer and incident light with polarization direction, different wavelengths, and varied particle sizes of Ag nanoparticles exhibits nonlinear optical behavior in the near field. The far-field signals of different wavelength of incident light confirm the relation between highly localized near-field distributions and enhanced resolution of far-field signals. The subwavelength recording marks smaller than the diffraction limit were distinguishable since the Ag nanoparticles with high localized fields transferred evanescent waves to detectable signals in the far field. PACS 42.79.Vb; 71.15.Rn; 72.15.Rn; 73.22.-f; 73.22.Lp; 78.67.Bf; 73.20.Mf     

Spin glass behaviour and extrinsic origin of magnetodielectric effect in non-multiferroic La(2)NiMnO(6) nanoparticles

We report magnetization, dielectric and dc transport properties of La(2)NiMnO(6) nanoparticles. Both dc and ac magnetization measurements indicated a metastable magnetic behaviour with random ferromagnetic and antiferromagnetic interactions below 110 K; critical slow-down, memory and rejuvenation properties signify the spin glass nature. The dc resistivity shows a semiconducting nature but the temperature dependent magnetoresistance (MR) shows a peak at the spin glass transition. The colossal dielectric property and its frequency dependence were interpreted using the Maxwell-Wagner (MW) interfacial polarization model. Impedance analysis along with magnetodielectric (MD) and magnetoresistance (MR) indicates that the observed MD originates from the combined effect of MR and MW interfacial polarization.     

Possible ferromagnetism in MgO

We study the impact of vacancies on the magnetism of MgO and TiO₂ nanoparticles, and develop fist-principle calculations to ascertain the origin of the induced polarization. Theoretically, we expect ferromagnetism only for the case of MgO with cation defects. Experimentally, we observed a small magnetic signal probably due to imperfections in the lattice order, perhaps at the nanoparticles surface.     

Increase of photoinduced birefringence in a new type of anisotropic nanocomposite: azopolymer doped with ZnO nanoparticles

We report a significant increase of about 50% of the photoinduced birefringence in nanocomposite films of azopolymers doped with ZnO nanoparticles compared with samples made from nondoped azopolymers. This increase is most pronounced at small concentrations of the nanoparticles of 0.5% and for the amorphous polymers used in our study. We observe also an improvement of the response time of more than 25% in some of the polymers, which allows for faster and more effective polarization optical recording.     

Limit on the detectability of the energy scale of inflation

We show that the polarization of the cosmic microwave background can be used to detect gravity waves from inflation if the energy scale of inflation is above 2x10(15) GeV. These gravity waves generate polarization patterns with a curl, whereas (to first order in perturbation theory) density perturbations do not. The limiting "noise" arises from the second-order generation of curl from density perturbations, or rather residuals from its subtraction. We calculate optimal sky coverage and detectability limits as a function of detector sensitivity and observing time.     

Observation of relaxor ferroelectricity and multiferroic behaviour in nanoparticles of the ferromagnetic semiconductor La(2)NiMnO(6)

We report a diffuse phase transition (extending over a finite temperature range of ～50?K) in sol-gel derived nanoparticles (～25?nm) of the ferromagnetic double perovskite La(2)NiMnO(6). The macroscopic polarization (P-E hysteresis loop), validity of the Vogel-Fulcher relation and high dielectric permittivity (～9?×?10(2)) confirm relaxor ferroelectric phenomena in these magnetic nanoparticles. Compared to the corresponding bulk sample, appreciably large enhancement of the magnetocapacitive effect (MC ～?30%) is observed even under low magnetic field (0.5?T) around the broad relaxor dielectric peak temperature (～220?K), which is close to the ferromagnetic transition temperature (θ(f)?～?196?K). All of these features establish the multiferroic character of the La(2)NiMnO(6) nanoparticles. The inhomogeneities arising from chemical and valence mixing in the present La(2)NiMnO(6) nanoparticles and the inter-site, Ni/Mn-site disorder along with surface disorder of the individual nanoparticles resulting in local polar regions are attributed to the observed dielectric behaviour of the nanoparticles. The wave vector dependent spin-pair correlation is considered to be the plausible cause of the colossal magnetocapacitive response near the transition temperature. High permittivity and large magnetocapacitive properties make these ferromagnetic La(2)NiMnO(6) nanoparticles technologically important.