Effect of point defects on phase transitions in ferroelectric nanocrystals

The dependences of the phase transition temperature of ferroelectric nanocrystals in a dielectric matrix on the point charged defect concentration have been obtained. The influence of point defects on the nonlinear characteristics of ferroelectric nanocrystals has been studied as a function of the strength and direction of an external electric field with the adequate inclusion of depolarizing electric fields and nonlocal effects.     

Electronic structure and absorption spectra of silicon nanocrystals with a halogen (Br,Cl) coating

Ab initio calculations of the electronic structure and frequency dependence of the imaginary part of the dielectric function for 1–2 nm silicon nanocrystals with the surface fully passivated with Cl or Br halogen atoms have been performed. According to these calculations, passivation with halogens results in the strong localization of valence electrons near the surface. As a result, the width of the band gap of a nanocrystal is noticeably narrowed and its absorptance decreases as compared to the case of hydrogen passivation. These effects are more pronounced in bromine-passivated nanocrystals.     

具有表面修饰的SnO2纳米微晶的光学性质研究

给出了裸的及包裹ＳｎＯ２纳米微晶的吸收、荧光和激发谱的实验结果。发现随着粒子尺寸的减小,包覆一层有机分子的ＳｎＯ２纳米微晶的吸收谱带边向长波方向发生位移,这与裸ＳｎＯ２纳米微晶的结果是不一致。表明纳米晶体的尺寸及其表面状态对它们的光谱性质有很大影响。从量子限域效应和介电限域效应两个方面对实验结果进行了讨论。     

Ellipsometric characterization of nanocrystals in porous silicon

Porous silicon layers (PSLs) were prepared by electrochemical etching of p-type single-crystalline silicon (c-Si) wafers having different dopant concentrations to obtain systematically changing sizes of nanocrystals (walls). The microstructure of the porous material was characterized using spectroscopic ellipsometry with multi-layer effective medium approximation (EMA) models. The dielectric function of PSL is conventionally calculated using EMA mixtures of c-Si and voids. The porosity is described by the concentration of voids. Some PSL structures can be described only by adding fine-grained polycrystalline silicon (nc-Si) reference material to the EMA model. Modified model dielectric functions (MDF) of c-Si have been shown to fit composite materials containing nanocrystalline regions, either by fitting only the broadening parameter or also other parameters of the parametric oscillator in MDF. The broadening parameter correlates with the long-range order in the crystalline material, and, as a consequence, with the size of nanocrystals. EMA and MDF models were used to describe systematically changing nanostructure of PSLs. Volume fraction of nc-Si in EMA and broadening parameter in MDF provide information on the nanocrystal size. The longer-term goal of this work is to provide a method for the quantitative characterization of nanocrystal size using quick, sensitive and non-destructive optical techniques.     

Polar optical phonons in semiconducting CdS nanocrystals

We have experimentally and theoretically studied IR-active optical phonons, which are spatially confined in the volume of semiconducting CdS nanocrystals of various shapes synthesized in a dielectric matrix (porous aluminum oxide). Within an approach admitting the mixing of all expected types of vibrations, the complete sets of phonon modes are determined for a spherical quantum dot (QD) and a cylindrical quantum wire (QW) in this matrix. Based on these results, the polarizability spectra of QDs and QWs, as well as the effective dielectric function of a composite material containing such nanoparticles, are calculated for the far-IR wavelength range. It is established that the spectrum of the dielectric function exhibits specific features in the region between the transverse and longitudinal optical phonon frequencies of the massive semiconductor material. These features explain the rather unusual structure of the IR spectra of the composite samples studied.     

Optical nanolaser on the heavy hole transition in semiconductor nanocrystals: Theory

We discuss the energy spectrum of electron–hole pairs in a quasi-zero-dimensional system consisting of spherical semiconductor nanocrystals placed in transparent dielectric matrices. We study theoretically the prospect of using hole transitions between equidistant series of quantum levels observed in nanocrystals for designing an optical nanolaser.     

嵌埋Ni颗粒的BaTiO_3/SrTiO_3薄膜的相变特性

采用高温X射线原位衍射和变温介电谱对SrTiO3基底上外延生长的BaTiO3(嵌埋Ni颗粒)薄膜进行了相变特性分析。从X射线衍射和介电谱的分析结果得出,BaTiO3的相变温度点转变为弥散的温度区间。在这个弥散的相变温度区间内,由于基底和薄膜之间的失配,以及嵌埋Ni颗粒的应力作用,薄膜的介电响应弥散剧烈,并偏离德拜弛豫。分析Cole-Cole图获知,BaTiO3薄膜在四方相转变为立方相的相变过程中同时存在几种极化机制,在高温状态下介电损耗随温度增大而增大。降温过程中,薄膜没有立即恢复四方相,可能是基底和Ni颗粒的共同作用影响了相变弛豫。     

Femtosecond light transmission and subradiant damping in plasmonic crystals

We report the first observation of subradiance in plasmonic nanocrystals. Amplitude- and phase-resolved ultrafast transmission experiments directly reveal the coherent coupling between surface plasmon polaritons (SPPs) induced by periodic variations in the dielectric function. This interaction results in the formation of plasmonic band gaps and coupled SPP eigenmodes with different symmetries, as directly shown by near-field imaging. In antisymmetric modes, radiative SPP damping is strongly suppressed, increasing the SPP lifetime from 30 fs to more than 200 fs. The findings are analyzed within a coupled resonance model.     

Phase transition in ferroelectric nanocrystals of the poly(vinylidene fluoride-trifluoroethylene) copolymer

The dielectric dispersion of nanocrystals of the poly(vinylidene fluoride-trifluoroethylene) copolymer with the 70/30 composition has been studied. It has been found that the phase transition in ferroelectric nanocrystals takes place at T = 100°C. The observed broad temperature hysteresis indicates the occurrence of a first-order phase transition.     

Preparation and characterization of poled nanocrystal and polymer composite PZT/PC films

Pb(Zr_0.52Ti_0.48)O₃ (PZT) nanocrystals and transparent polycarbonate (PC) composite thin films with useful properties for ferroelectric, piezoelectric and electro-optic devices were prepared by a spin-coating technique. Ultra-fine PZT (∼40–50 nm) nanocrystals with pure perovskite tetragonal phase were synthesized by a hydrothermal method. The structure and morphology of the composite thin films were studied by means of X-ray diffraction and scanning electron microscopy. To obtain the optimum electro-optic properties of poled composite films, the poling condition under an external electric field was optimized through the dielectric properties of PZT and PC polymer and effective field intensity theory. The electro-optic coefficient of the poled PZT/PC composite film is estimated to be 30.5 pm/V. The transparency spectra were measured and the optical band gaps of the unpoled, poled at 145 °C and poled at 165 °C composite thin films are estimated to be 4.26 eV, 4.21 eV and 4.18 eV, respectively. The measured dielectric constants of PZT/PC are in good agreement with the calculated values for the composite with a very small PZT volume fraction, based on the Onsager effective-field theory. This offers a reliable and indirect way to predict the dielectric constant of nanocrystals. PACS 81.40.Tv; 78.66.Sq; 78.66.Vs     

Phase transitions in ultrathin ferroelectric polymer films and nanocrystals

The dielectric dispersion of nanocrystals of vinylidene fluoride—trifluoroethylene copolymer of 70/30 composition was investigated. A phase transition was revealed in ferroelectric nanocrystals at T = 100°C. A wide temperature hysteresis was observed, indicating a first-order phase transition.     

Luminescence of Nanocrystalline Si in (Si + CaF2)/CaF2 Structures in the Visible Range of the Spectrum

Russian Physics Journal - Photoluminescence from Si nanocrystals embedded in a CaF2 dielectric matrix and formed on the surface of a Si(111) substrate is demonstrated. The photoluminescence was...     

Optimal conditions for exciting long-lived photon echo signals in impurity nanocrystals

The specific features of the formation of long-lived photon echo signals in dielectric nanocrystals doped with rare earth ions have been considered. It is shown that the optimal situation for observing long-lived photon echo signals in impurity nanocrystals is the absence of resonance between the vibrational modes of the nanomatrix and the impurity-ion electronic transitions, contributing to the spin-phonon relaxation.     

Excitation of erbium in the heterogeneous nanocrystalline matrix of amorphous silicon

The erbium photoluminescence decay kinetics at a wavelength of 1.54 μm in amorphous hydrogenated silicon films obtained at high oxygen concentrations in a magnetron gas discharge is investigated. Optically active erbium is found to exist both in the semiconducting matrix of amorphous silicon and in dielectric nanocrystals of erbium silicate, which are formed in this case. The concentration ratio of excited erbium in amorphous silicon and in the nanocrystals is determined, as well as the time of excitation transfer from erbium in amorphous silicon to erbium in the nanocrystals. The mechanism of erbium excitation in this heterogeneous system is considered. The external quantum yield of erbium photoluminescence measured at a wavelength of 1.54 μm and room temperature is found to be 0.3–0.4%.     

SELF-ASSEMBLY AND POLARIZABILITY OF CAPPED CdS NANOCRYSTALS ON SILICON SURFACES

The zinc-blende CdS nanocrystals with particle size less than 10nm were prepared in solution with a molecular surfactant. The particle surface was modified with capping molecules, bis(2-ethylhexyl) sulfosuccinate disodium salt (AOT) or hexametaphosphate (HMP). The colloid solution was deposited on silicon wafer and the assembly of these nanocrystals was studied by atomic force microscopy. It was found that the CdS/AOT formed a monolayer by simply dropping the colloid solution on silicon surface, while CdS/HMP exhibited 3D structure with prefered orientation in the similar deposition process. A dynamic electric force microscopy was performed and the polarizability was measured from the resonance of cantilever under applied alternating voltage between tip and substrate. The dielectric constant of CdS nanocrystal was estimated by comparing the different electric capacitance of Au and CdS nanocrystals.     

Surface-enhanced Raman spectroscopy of semiconductor nanostructures

We review our recent results concerning surface-enhanced Raman scattering (SERS) by confined optical and surface optical phonons in semiconductor nanostructures including CdS, CuS, GaN, and ZnO nanocrystals, GaN and ZnO nanorods, and AlN nanowires. Enhancement of Raman scattering by confined optical phonons as well as appearance of new Raman modes with the frequencies different from those in ZnO bulk attributed to surface optical modes is observed in a series of nanostructures having different morphology located in the vicinity of metal nanoclusters (Ag, Au, and Pt). Assignment of surface optical modes is based on calculations performed in the frame of the dielectric continuum model. It is established that SERS by phonons has a resonant character. A maximal enhancement by optical phonons as high as 730 is achieved for CdS nanocrystals in double resonant conditions at the coincidence of laser energy with that of electronic transitions in semiconductor nanocrystals and localized surface plasmon resonance in metal nanoclusters. Even a higher enhancement is observed for SERS by surface optical modes in ZnO nanocrystals (above 10⁴). Surface enhanced Raman scattering is used for studying phonon spectrum in nanocrystal ensembles with an ultra-low areal density on metal plasmonic nanostructures.     

Multiferroic magnetoelectric coupling and relaxor ferroelectric behavior in 0.7BiFeO3-0.3BaTiO3 nanocrystals

The structural, microstructural, polarization, magnetization, dielectric constant, and relaxor characteristics of 0.7BiFeO₃-0.3BaTiO₃ (BF-BT) nanocrystals have been studied. BF-BT nanocrystals were prepared by a chemical route using polyvinyl alcohol as surfactant. The phase structure is confirmed by X-ray diffraction and average particle size by transmission and scanning electron microscopy. The magnetoelectric coupling is studied by polarization hysteresis loops under the influence of applied magnetic field and the phase transition anomaly. The diffuse phase transition is studied by modified Curie-Weiss law and relaxor characteristics by Vogel-Fulcher relation.     

Temperature dependent optical properties of Si nanocrystals embedded in SiO2 matrix

The optical properties of Si nanocrystals (nc-Si) with different sizes (2～5 nm) embedded in a SiO₂ matrix synthesized by the SiO _x /SiO₂ superlattice approach were studied in a temperature range from room temperature to 600 K by spectroscopic ellipsometry. The Maxwell–Garnett effective medium approximation and Lorentz oscillator model were employed to extract the dielectric function of nc-Si. The results show that the temperature dependence of optical properties of nc-Si is sensitive to its size. An empirical expression of Varshni approximation was obtained to characterize the band-gap energy change of nc-Si at different temperatures.     

Effect of dielectric confinement on optical properties of colloidal nanostructures

We review the effects caused by a large difference in the dielectric constants of a semiconductor and its surrounding in colloidal semiconductor nanostructures (NSs) with various shapes, e.g., nanocrystals, nanorods, and nanoplatelets. The difference increases the electron–hole interaction and consequently the exciton binding energy and its oscillator transition strength. On the other hand, this difference reduces the electric field of a photon penetrating the NS (the phenomenon is called the local field effect) and reduces the photon coupling to an exciton. We show that the polarization properties of the individual colloidal NSs as well as of their randomly oriented ensemble are determined both by the anisotropy of the local field effect and by the symmetry of the exciton states participating in optical transitions. The calculations explain the temperature and time dependences of the degree of linear polarization measured in an ensemble of CdSe nanocrystals.     

Preparation of size controllable copper nanocrystals for nonvolatile memory applications

A method of fabricating Cu nanocrystals embedded in SiO2 dielectric film for nonvolatile memory applications by magnetron sputtering is introduced in this paper. The average size and distribution density of Cu nanocrystal grains are controlled by adjusting experimental parameters. The relationship between nanocrystal floating gate micro-structure and its charge storage capability is also discussed theoretically.