Optical gap of P-doped Si nanocrystals

The optical gap of Si nanocrystals strongly doped with phosphorus has been calculated. The energy levels of the electron and hole ground states in the Si nanocrystal were found as functions of the nanocrystal size and the P concentration in the framework of the envelope function approximation and under the assumption of uniform impurity distribution over the nanocrystal volume. It is shown that introducing phosphorus into the nanocrystal leads to a decrease in its optical gap. This decrease is related to a strong shift of the ground electron level produced by the short-range part of the Coulomb electron-P-ion interaction.     

Size- and shape-dependent energetics of nanocrystal interfaces: experiment and simulation

We study the interface energetics of Ag nanocrystals on a H-passivated Si(111) surface by a transmission electron microscopy experiment and molecular dynamics simulations. The annealed nanocrystals are oriented with Ag(111)||Si(111). Azimuthally, epitaxy is preferred for nanocrystals with an interface larger than a coincident-site-lattice (CSL) cell. The equilibrium orientation, or interface energy minimum, depends on the interface size and shape. For interfaces approaching a CSL cell in size ( approximately 2 nm nanocrystals), fluctuations of a single atom at an interface can lead to large variations in nanocrystal orientations.     

Resonant electronic energy transfer from excitons confined in silicon nanocrystals to oxygen molecules

We demonstrate efficient resonant energy transfer from excitons confined in silicon nanocrystals to molecular oxygen (MO). Quenching of photoluminescence (PL) of silicon nanocrystals by MO physisorbed on their surface is found to be most efficient when the energy of excitons coincides with triplet-singlet splitting energy of oxygen molecules. The dependence of PL quenching efficiency on nanocrystal surface termination is consistent with short-range resonant electron exchange mechanism of energy transfer. A highly developed surface of silicon nanocrystal assemblies and a long radiative lifetime of excitons are favorable for achieving a high efficiency of this process.     

Size-controllable synthesis of nanosized-TiO2 anatase using porous Vycor glass as template

In this paper we report the synthesis and characterization of TiO₂ nanocrystal dispersed into a porous Vycor glass. We have obtained very small TiO₂ nanocrystals in the anatase form. The nanocrystal size is controlled via the mass increment only thus preventing the growth through the coalescence process. The nanocrystal size was monitored through transmission electron microscope and Raman scattering. The␣coalescence control is attributed due to the obtention of nanocrystals dispersed into the host and to the terminal bonds present in the porous which act as an anchor thus resulting in a low diffusion of the nanocrystals through the porous network.     

Vanishing of the Mott transition in semiconductor nanocrystals

The dynamics of the system of photoexcited electron–hole pairs in semiconductor nanocrystals of different size with increasing excitation intensity was experimentally studied by utilizing the luminescence spectra of semiconductor-doped glasses in order to elucidate the peculiarities of many-body effects in structures approaching the zero-dimensional limit. Vanishing of effects causing the Mott transition in bulk crystals was observed with decreasing nanocrystal radius, and a new type of transformation of excitons to unbound electron–hole pairs was shown to take place in nanocrystals where the energy shift for electrons and holes due to quantum confinement becomes comparable with the exciton binding energy.     

Quantum confinement effects on the optical phonons of CdTe quantum dots

We present Raman-scattering results for CdTe nanocrystals in doped glasses which clearly show the confinement effects on the phonon spectra as a function of the quantum-dot size. We observed optical phonon modes, surface phonons and some of their overtone combinations. We show that the surface-phonon scattering intensity increases as the quantum-dot size decreases. Our results also show a decrease in the electron–phonon coupling as the nanocrystal size is decreased. These confinement effects are observed by changing the laser excitation energy, and thus by tuning to resonance with the optical transitions for quantum dots of different sizes within their broad size distribution in semiconductor-doped glasses.     

Electron-phonon interaction in non-polar quantum dots induced by the amorphous polar environment

We propose a Fröhlich-type electron-phonon interaction mechanism for carriers confined in a non-polar quantum dot surrounded by an amorphous polar environment. Carrier transitions under this mechanism are due to their interaction with the oscillating electric field induced by the local vibrations in the surrounding amorphous medium. We estimate the corresponding energy relaxation rate for electrons in Si nanocrystals embedded in a SiO₂ matrix as an example. When the nanocrystal diameter is larger than 4 nm then the gaps between the electron energy levels of size quantization are narrow enough to allow for transitions accompanied by emission of a single local phonon having the energy about 140 meV. In such Si/SiO₂ nanocrystals the relaxation time is in nanosecond range.     

Charge storage and electron/light emission properties of silicon nanocrystals

Monodispersed silicon nanocrystals show novel electrical and optical characteristics of silicon quantum dots, such as single-electron tunneling, ballistic electron transport, visible photoluminescence and high-efficiency electron emission.Single-electron memory effects have been studied using a short-channel MOSFET incorporating Si quantum dots as a floating gate. Surface nitridation of Si nanocrystal memory nodes extends the charge-retention time significantly. Single-electron storage in individual Si dots has been evaluated by Kelvin probe force microscopy.Photoluminescence and electron emission are observed for surface-oxidized silicon nanocrystals. Efficiency of the no-phonon-assisted transition increases with decreasing core Si size. Electron emission efficiency as high as 5% has been achieved for the Si-nanocrystal-based cold electron emitter devices. The non-Maxwellian energy distribution of emitted electrons suggests that the mechanism of electron emission is due to ballistic transport through arrays of surface-oxidized Si nanocrystals. Combined with the ballistic electron emission, the quasi-direct light emission properties can be used for developing Si-based lasers.     

SiGe superlattice nanocrystal pure and doped with substitutional phosphorus single atom: Density functional theory study

Ab initio density functional theory is used to simulate electronic structure of hydrogenated SiGe nanocrystal superlattice pure and doped with substitutional P single atom. The results of electronic structure calculations are compared to the same size silicon and germanium nanocrystals. The comparison reveals that the energy gap of the three kinds of nanocrystals is nearly the same in non-relativistic and relativistic limits. Because of large width of gap in the present small nanocrystals the relativistic corrections are not as much important as in the case of bulk crystals. The doping of SiGe nanocrystal with P single atom introduced an impurity level at 4 eV below original conduction band edge. This result is much larger than comparable silicon bulk and nanocrystal doping with P atoms. Results also show that the deep internal angles and bonds in SiGe nanocrystals reach approximately the angles and structure of bulk crystals after nearly three surface layers. A double positively charged layer is located at the Ge terminated surface of SiGe nanocrystal. This layer is enhanced and is accompanied with a large increase of the dipole moment of the nanocrystal in the case of P doped nanocrystal. Due to oscillatory lattice potential in SiGe superlattice, density of states show that bands are broken up to sub-bands in comparison with silicon nanocrystal density of states especially at the conduction band.     

Photoexcited charge carrier dynamics in silicon nanocrystal/SiO2 superlattices

We report in detail on the dynamics of photoexcited charge carriers in size-controlled silicon nanocrystals in silicon nanocrystal/SiO₂ superlattices. The samples were prepared using plasma enhanced chemical vapor deposition and subsequent thermally induced phase separation. This unique approach allows preparation of well-defined Si nanocrystals. Experimental techniques of time-resolved absorption and photoluminescence were used to monitor the carrier dynamics on a wide time scale from picoseconds to milliseconds for a set of samples with different parameters (nanocrystal size, hydrogen annealing). The initial fast decay (tens of picoseconds) dependent on pump intensity for excitation levels exceeding one electron–hole pair per nanocrystal can be interpreted in terms of the bimolecular recombination with constant B=(2–3)×10⁻¹⁰ cm³ s⁻¹. The slow pump intensity independent decay (microseconds) can be reproduced well by a stretched-exponential function. The dependence of stretched-exponential parameters on photoluminescence photon energy and sample properties agrees well with the picture of trapped carriers.     

Quantum confinement in layer-by-layer deposited colloidal HgTe nanocrystals determined by spectroscopic ellipsometry

We report spectroscopic ellipsometry studies in the energy range of 0.5-5 eV on samples of 1-10 bilayers of polymer and HgTe nanocrystals, which exhibit strong transitions at higher critical points in the dispersion relation. We show that the dispersion relation for nanocrystals can be modelled with the same concepts for critical points as used in semiconductor bulk optics. We find an energy shift of up to 0.4 eV of the critical points to higher energies compared to the HgTe bulk properties, caused by quantum confinement in the nanocrystals, which increases with decreasing nanocrystal size.     

Size, shape and structure dependent cohesive energy and phase stability of metallic nanocrystals

A model to account for the size, shape and structure dependent cohesive energy of metallic nanocrystals is developed in this contribution. It is predicted that the cohesive energy of nanocrystals decreases with decreasing the crystal size in specific shape, and decreases with increasing the shape factor in specific size. Furthermore, the model can be applied to predict the size and shape dependent phase stability of nanocrystal. To take Cr nanocrystal as an example, we found that there exists FCC structure for Cr crystal (the bulk structure is BCC) when the crystal size is small enough, and critical size of phase transition ranges from 249 to 824 atoms due to crystal shape variation, which is consistent with the corresponding experimental results.     

玻璃中CdSSe纳米晶体的光谱性能

对掺有镉、硒、硫的玻璃在650—800℃退火4?h，生长了不同尺寸的CdS0.13Se0.87纳米晶体，测量了纳米晶体的吸收光谱、光致发光（PL）谱和电调制光谱，确定了纳米晶体部分电子态的能量，讨论了CdSSe纳米晶体的光学性质与其尺寸之间的依赖关系.随着纳米晶体尺寸的增大，对应激子的吸收峰、PL峰及电吸收信号发生红移，表现出明显的量子尺寸效应.小尺寸纳米晶体的电吸收表现为量子受限的Stark效应，而大尺寸纳米晶体的电吸收线形与体材料的相似；随着纳米晶体尺寸的增大，电吸收信号增强.所有尺寸的纳米晶体都表现 关键词： CdSSe纳米晶体 吸收光谱 光致发光谱 电光响应     

Luminescence of ZnO nanopowders

The luminescence of ZnO nanocrystals prepared by different methods was studied under pulsed electron beam excitation. It is shown that the luminescence intensity depends on the nanocrystal sintering conditions and does not depend on the nanocrystal size within the range 10–50 nm. The relative luminescence intensities for the 3.32 eV (free exciton) and 3.20 eV (bound exciton) bands showed a dependence on nanocrystal size. The role of the nanocrystal surface in excitonic luminescence is discussed.     

纳米多晶体的热力学函数及其在相变热力学中的应用

以往关于纳米材料热力学的研究，绝大多数以界面的热力学函数表征整体纳米材料的热力学性质，这种近似处理，对于尺寸超过几十纳米的较粗纳米材料，在相变热力学中对特征转变温度和临界尺寸等重要参量的预测，将导致很大误差. 应用“界面膨胀模型”和普适状态方程，研究了纳米晶界的热力学特性，进一步发展了纳米晶整体材料热力学函数的计算模型，给出了单相纳米多晶体的焓、熵和吉布斯自由能随界面过剩体积、温度，以及晶粒尺寸发生变化的明确表达式. 以Co纳米晶为例，分析了界面与整体纳米多晶体热力学函数的差异，确定了相变温度与晶粒尺寸的依赖关系，以及一定温度下可能发生相变的临界尺寸. 关键词： 纳米多晶体 热力学函数 相变热力学     

CuCl nanocrystals in alkali-halide matrices under hydrostatic pressure

CuCl nanocrystals in crystalline alkali-halide matrices have been investigated under hydrostatic pressures up to 18 GPa. The pressures of structural phase transitions in CuCl have been determined both for different nanocrystal sizes and for different matrices (NaCl, LiCl, KCl). For CuCl nanocrystals in NaCl an increase of the transition pressure with decreasing nanocrystal size is observed, which is explained by the increasing importance of surface pressure for small nanocrystals. We found higher transition pressures for the LiCl matrix than for the NaCl matrix. The reason for this is that the pressure which acts on the nanocrystal differs from the external pressure. A simple elastic model describes the effective pressure transmitted from the matrix to the nanocrystal. With CuCl nanocrystals embedded in KCl we have studied the behavior of nanocrystals during a phase transition of the matrix. Additionally we have determined the pressure coefficients of the exciton energies of the CuCl nanocrystals, which depend on the elastic properties of the matrix. Received 4 March 1999     

Dependence of the surface energy on the size and shape of a nanocrystal

An expression is derived for the surface energy σ as a function of the size and shape of a nanocrystal. It is shown that the wider the deviation of the shape parameter f from unity, the more pronounced the decrease in the surface energy σ with a decrease in the number N of atoms in the nanocrystal. The dependences of the average coordination number, the surface energy, and the melting temperature on the number N exhibit an oscillatory behavior with maxima at points corresponding to numbers of atoms forming a defect-free cube. The surface energy decreases with an increase in the temperature T. It is found that the smaller the nanocrystal size or the greater the deviation of the nanocrystal shape from the thermodynamically most stable shape (a cube), the larger the quantity-(dσ/dT). It is established that the nanocrystal undergoes melting when the surface energy decreases to a value at which it becomes independent of the nanocrystal size and shape. The conditions providing fragmentation and dendritization of the crystal are discussed. It is demonstrated that, at N>1000, the dependence σ(N) coincides, to a high accuracy, with the dependence of the surface tension of the nanocrystal on N. The inference is made that bimorphism is characteristic of nanocrystals. This implies that nanocrystals can have platelike and rodlike shapes with equal probability.     

A detailed study of physical properties of ZnS quantum dots synthesized by reverse micelle method

In this article, zinc sulfide nanocrystal quantum dots were synthesized by reverse micelle method using polyvinyl pyrrolidone as surfactant. The various crystallite properties of these nanocrystals such as, size, d-spacing, lattice parameter, microstrain, intrinsic stress, X-ray density, specific surface area, dislocation density, porosity, and agglomeration number have been analyzed using X-ray diffraction spectrum. The transmission electron microscopy was used to calculate the size and monitoring morphology of the nanocrystals, while the scanning electron microscopy was utilized to investigate the surface morphology of nanoclusters. The various optical properties of zinc sulfide quantum dots such as absorption coefficient, extinction coefficient, optical band gap energy, Urbach energy, and threshold wavelength have been analyzed using UV-visible data. The photoluminescence was used to study the emission spectra of produced ZnS quantum dots. Moreover, Furrier Transform-Infrared studies revealed that ZnS quantum dots are pure.     

Formation and structure of nanocrystals in an Al86Ni11Yb3 alloy

The formation and structure of the nanocrystalline phase in the Al₈₆Ni₁₁Yb₃ alloy are investigated using differential scanning calorimetry (DSC), transmission electron and high-resolution electron microscopy, and x-ray diffraction. The nanocrystalline phase is formed upon controlled crystallization of the amorphous alloy prepared by quenching of the melt on a rapidly moving substrate. It is revealed that the nanocrystalline alloy consists of aluminum nanocrystals (5–12 nm in size) randomly distributed in the amorphous matrix. The maximum fraction of the nanocrystalline phase does not exceed 25%. The nanocrystal size substantially increases at the initial stage of isothermal treatment (at 473 K) and then changes insignificantly. It is found that nanocrystals are usually free of defects. However, some nanocrystals have a more complex microstructure with twins and dislocations. The size distributions of nanocrystals are determined at several durations of isothermal treatment. It is demonstrated that the nucleation of nanocrystals predominantly occurs through the heterogeneous mechanism. The experimental distributions are compared with those obtained from a computer simulation. The activation energy of crystallization, the time-lag, and the coefficient of ytterbium diffusion in the alloy are estimated