Structures,Oxidation, and Charge Transport of Phosphorus‐Doped Germanium Nanocrystals

The doping of semiconductor nanocrystals (NCs) is crucial for the optimization of the performance of devices based on them. In contrast to recent progress on the doping of compound semiconductor NCs and silicon NCs, the doping of germanium (Ge) NCs has lagged behind. Here it is shown that Ge NCs can be doped with phosphorus (P) during synthesis by a nonthermal plasma. It is found that there are more P atoms in the NC near‐surface region than in the NC core. P doping modifies the surface state of Ge NCs. Compressive strain can be incuced in Ge NCs by P which can explain the P‐doping‐enhanced oxidation resistance of Ge NCs. Stable dispersions of P‐doped Ge NCs in acetonitrile can be cast to produce films for field‐effect transistors (FETs). FET analysis shows that the electrical conductivity and electron mobility of a Ge‐NC film increase with the increase of the P doping level, although the electrical activation efficiency of P in the Ge‐NC film is low. Finally, atomic layer deposition of aluminum oxide at the surface of P‐doped Ge NCs is shown to improve the performance of the FETs.     

Automatically Purification of Aqueous CdTe Nanocrystals in Water-ethanol Co-environment

Purification is a separated post-treatment step after the synthesis of nanocrystals (NCs) in order to exclude excess ligands and monomers in NC solution. The common purification process involves many manipulations, such as concentrating, addition of anti-solvents and centrifugation, which are troublesome and time consuming. In this work, we originally integrate NC synthesis and NC purification in one-pot via selecting water-ethanol co-environment for NC synthesis and NC purification. Our research shows that NCs can grow in water-ethanol mixture. When growing into critical size, NCs will automatically precipitate from the solution. Element analysis demonstrates that precipitates fraction fits well with stoichiometric of ligand-capped NCs. Excess monomers are left in supernatant, and thus achieving automatically purification of NCs in the water-ethanol co-environment. By adjusting the volume ratios of water and ethanol in bi-solvent system, different-sized purified NCs can be controlled. Besides, this water-ethanol co-environment can be used in both thermal-promoted and hydrazine-promoted growth.     

Mechanism and enhancement of photoluminescence from silicon nanocrystals implanted in SiO2 matrix

Photoluminescence (PL) spectra of Si nanocrystals (NCs) prepared by 130 keV Si ions implantation onto SiO2 matrix were investigated as a function of annealing temperature and implanted ion dose. PL spectra consist of two PL peaks, originated from smaller Si NCs due to quantum confinement effect (QCE) and the interface states located at the surface of larger Si NCs. The evolution of number of dangling bonds (DBs) on Si NCs was also investigated. For hydrogen-passivated samples, a monotonic increase in PL peak intensity with the dose of implanted Si ions up to 3×1017 ions /cm2 is observed. The number of DBs on individual Si NC, the interaction between DBs at the surface of neighbouring Si NCs and their effects on the efficiency of PL are discussed.     

Charge retention in quantized energy levels of nanocrystals

Understanding charging mechanisms and charge retention dynamics of nanocrystal (NC) memory devices is important in optimization of device design. Capacitance spectroscopy on PECVD grown germanium NCs embedded in a silicon oxide matrix was performed. Dynamic measurements of discharge dynamics are carried out. Charge decay is modelled by assuming storage of carriers in the ground states of NCs and that the decay is dominated by direct tunnelling. Discharge rates are calculated using the theoretical model for different NC sizes and densities and are compared with experimental data. Experimental results agree well with the proposed model and suggest that charge is indeed stored in the quantized energy levels of the NCs.     

Boron‐ and Phosphorus‐Hyperdoped Silicon Nanocrystals

Hyperdoping silicon nanocrystals (Si NCs) to a concentration exceeding the solubility limit of a dopant may enable their novel applications. Here, the successful hyperdoping of Si NCs with boron (B) and phosphorus (P) is demonstrated, which are the most important dopants for Si. Despite the hyperdoping, the diamond structure of Si NCs is hardly modified. There are both electrically active B and P in hyperdoped Si NCs. It is proposed that the hyperdoping is made possible mainly by the kinetics in the nonthermal plasma synthesis of Si NCs. Collision between Si NCs and B or P atoms and the binding energy of B or P at the NC surface are critical to the understanding on the differences in the doping efficiency and dopant distribution between B and P. B‐hyperdoping‐induced tensile stress needs to be taken into account in the investigation on the doping and oxidation of Si NCs.     

Deciphering the Structure and Chemical Composition of Drug Nanocarriers: From Bulk Approaches to Individual Nanoparticle Characterization

Drug nanocarriers (NCs) with sizes usually below 200 nm are gaining increasing interest in the treatment of severe diseases such as cancer and infections. Characterization methods to investigate the morphology and physicochemical properties of multifunctional NCs are key in their optimization and in the study of their in vitro and in vivo fate. Whereas a variety of methods has been developed to characterize “bulk” NCs in suspension, the scope of this review is to describe the different approaches for the NC characterization on an individual basis, for which fewer techniques are available. The accent is put on methods devoid of labelling, which could lead to artefacts. For each characterization method, the principles and approaches to analyze the data are presented in an accessible manner. Aspects related to sample preparation to avoid artefacts are indicated, and emphasis is put on examples of applications. NC characterization on an individual basis allows gaining invaluable information in terms of quality control, on: i) NC localization and fate in biological samples; ii) NC morphology and crystallinity; iii) distribution of the NC components (drugs, shells), and iv) quantification of NCs’ chemical composition. The individual characterization approaches are expected to gain increasing interest in the near future.     

Surface-enhanced emission from single semiconductor nanocrystals

The fluorescence behavior of single CdSe(ZnS) core-shell nanocrystal (NC) quantum dots is dramatically affected by electromagnetic interactions with a rough metal film. Observed changes include a fivefold increase in the observed fluorescence intensity of single NCs, a striking reduction in their fluorescence blinking behavior, complete conversion of the emission polarization to linear, and single NC exciton lifetimes that are >10(3) times faster. The enhanced excited state decay process for NCs coupled to rough metal substrates effectively competes with the Auger relaxation process, allowing us to observe both charged and neutral exciton emission from these NC quantum dots.     

High efficiency carrier multiplication in PbSe nanocrystals: implications for solar energy conversion

We demonstrate for the first time that impact ionization (II) (the inverse of Auger recombination) occurs with very high efficiency in semiconductor nanocrystals (NCs). Interband optical excitation of PbSe NCs at low pump intensities, for which less than one exciton is initially generated per NC on average, results in the formation of two or more excitons (carrier multiplication) when pump photon energies are more than 3 times the NC band gap energy. The generation of multiexcitons from a single photon absorption event is observed to take place on an ultrafast (picosecond) time scale and occurs with up to 100% efficiency depending upon the excess energy of the absorbed photon. Efficient II in NCs can be used to considerably increase the power conversion efficiency of NC-based solar cells.     

Electroluminescence of single CdSe nanocrystals induced by scanning tunneling microscope

Electroluminescence intensity of single CdSe nanocrystals (NCs) excited by the tunnel current of a scanning tunneling microscope (STM) was measured. Samples with NCs do not exhibit plasmon emission. This enables one to measure pure emission from a single NC. Electroluminescence, measured in time, differs considerably from that of photoluminescence in similar NCs. This difference in temporal behavior results from the difference in physical conditions of experiments on photo- and electroluminescence.     

Ultrasound-assisted synthesis of nanocomposites based on aromatic polyamide and modified ZnO nanoparticle for removal of toxic Cr(VI) from water

In this study, novel nanocomposites (NCs) of aromatic polyamide (PA) and surface modified ZnO nanoparticle with s-triazine heterocyclic ring was introduced for efficient removal of toxic hexavalent chromium (VI) from aqueous solution. The surface of ZnO nanoparticle was modified by s-triazine core silane coupling agent (ZnO-TSC) and PA/ZnO-TSC NCs with different amount of ZnO-TSC nanoparticles (0, 5, 10 and 15 wt%) were prepared by ultrasonic irradiation. The synthesized PA/ZnO-TSC NCs were characterized by FT-IR, XRD, FE-SEM, TEM and TGA methods. TEM images showed that ZnO nanoparticles were dispersed homogeneously in the polymer matrix. The adsorption experiments were carried out in batch mode to optimize various parameters like contact time, pH and concentration of metal ion that influence the adsorption rate. The maximum uptakes of Cr(VI) at pH 4.0 was 72%, 81%, 89% and 91% for pure PA, NC5%, NC10% and NC15%, respectively. The kinetic of adsorption was investigated and the pseudo second-order model is an appropriate model for interpretation of adsorption mechanism of Cr(VI) ions.     

Extrinsic Magnetoelectricity in Barium Titanate/Nickel Nanocomposites: Effect of Compaction Pressure on Interfacial Anisotropy

The dynamic control of the dielectric response in magnetoelectric (ME) nanocomposites (NCs) renders an entire additional degree of freedom to the functionality of miniaturized magnetoelectronics and spintronics devices. In composite materials, the ME effect is realized by using the concept of product properties. Through the investigation of the microwave properties of a series of BaTiO₃/Ni NCs fabricated by compaction of nanopowders, we present experimental evidence that the compaction (uniaxial) pressure in the range of 33–230 MPa significantly affects the ME features. We report here data for only one composition (17.1 vol.% of Ni in the BaTiO₃/Ni NC sample). Our findings revealed that the ME coupling coefficient exhibits a large enhancement for specific values of the Ni volume fraction and compaction pressure. Overall, these observations are considered to be evidence of stress-induced microstructural changes under pressure that strongly affect the elastic interaction between the magnetostrictive and piezoelectric phases in these NCs. These results have a potential technological impact for designing precise tunable ME NCs for microwave devices such as tunable phase shifters, resonators, and delay lines.     

Origins of visible-light emissions in hydrogen-coated silicon nanocrystals: Role of passivating coating

We present a theoretical investigation of the electronic and optical properties of hydrogen-coated silicon nanocrystals (Si:H NCs). On one hand, the density-functional theory (DFT) is used to both calculate the total energy and relax the NCs. On a second hand, the tight-binding method, which includes the minimal sp³-basis set within the second-nearest-neighbor interaction scheme, is applied to calculate the electronic structures, oscillator strength (OS) and recombination rate (RR) versus the NC size, coating and atomic relaxation. Three main findings are reported: (i) The quantum confinement in these NCs do follow similar rule to the case of a single-particle in a box, where the confinement energy decays in power-law with the increasing NC's size. (ii) The coating is shown to play the essential role in creation of large band-gap energy lying within the visible-light energy spectrum. (iii) The surface atomic relaxation is found to reduce the band-gap energy by about 150 meV and enhance both OS and RR. Our claims are corroborated by the available experimental data.     

Photoluminescence polarization of semiconductor nanocrystals

We review the polarization properties of photoluminescence (PL) in nanocrystals (NCs) from both theoretical and experimental points of view. We show that, under linearly polarized excitation, NCs emit partly polarized light owing to their uniaxial structure or their anisotropic shape. In elongated NCs, the anisotropy may have two origins, the electronic confinement or the effect of depolarizing field created by the light-induced charges on the interfaces. Results of polarization studies in porous silicon are presented. They are explained by the shape of the Si NCs. Experiments in CdSe NCs reveal the fine structure of the excitonic levels and show evidence of the enhancement of the electron-hole exchange energy with decreasing NC size. Spin orientation in wurtzite-type NCs is achieved by optical pumping with circularly polarized light. The effect of a magnetic field on the degree of circular polarization and the mechanisms of spin relaxation are discussed. Results in large-size NCs are presented.     

Exchange-coupled donor dimers in nanocrystal quantum dots

Doping of semiconductor nanocrystals (NCs) is expected to enable the control of key NC properties, yet its practical exploitation requires an understanding of exchange interactions when multiple dopants are incorporated in a single NC. Here, we experimentally probe the exchange of donor dimers in NCs via a deviation of their triplet-state magnetic resonance from Curie paramagnetism. We show that the exchange coupling of the closely spaced donors can be well described by effective mass theory, which allows the consideration of statistical effects crucial in NC ensembles. While a dimer induces discrete states in a NC, their energy splitting differs by up to 3 orders of magnitude for randomly placed dimers in a NC ensemble, due to an enormous dependence of the exchange energy on the dimer configuration.     

复合荧光CdSe量子点-脂质体的制备与表征

通过脂质体方法成功地将三辛基氧化膦(TOPO)包覆的CdSe发光量子点从非极性有机溶剂转移到生物相容性的水溶液中.分别通过透射电镜(TEM)、荧光Mapping图像,以及光致发光(PL)光谱进行表征.TEM照片显示制备的CdSe核量子点为球形,具有良好的单分散特性,平均粒径约为3nm.CdSe-脂质体复合体的平均尺寸大约20nm,TEM清楚地显示了CdSe量子点被诱捕在脂质体中.荧光Mapping显示了CdSe-脂质体复合体的发光强度分布.脂质体方法转移TOPO包覆的CdSe量子点,借助了磷脂的双分子链与CdSe表面的TOPO配体之间的疏水相互作用,在CdSe的第一配体层外部形成第二配体层,保留了CdSe的存在环境,光致发光光谱表明,量子点-脂质复合体基本保持了CdSe核量子点的发射效率.     

Interfaces under ion irradiation: growth and taming of nanostructures

We have investigated the synthesis of nanostructures, as well as the control of their size and location by means of ion beams. The phase separation and interface kinetics under ion irradiation give new possibilities for controlling the growth of nanostructures. Additionally, the chemical decomposition of the host matrix by collisional mixing can contribute to the self-organization of nanostructures, especially at interfaces. It is shown how collisional mixing during ion implantation affects nanocrystal (NC) synthesis and how ion irradiation through NCs modifies their size and size distribution. An analytical expression for solute concentration around an ion-irradiated NC was found, which may be written like the well-known Gibbs–Thomson relation. However, parameters have modified meanings, which has a significant impact on the evolution of NC ensembles. “Inverse Ostwald ripening” of NCs, resulting in an unimodal NC size distribution, is predicted, which has been confirmed experimentally for Au NCs in SiO₂ and by kinetic lattice Monte Carlo simulations. At interfaces, the same ion-irradiation-induced mechanism may result in self-organization of NCs into a thin δ-layer. Collisional decomposition of SiO₂ may enhance the NC δ-layer formation in SiO₂ at the Si/SiO₂ interface. The distance of the self-organized NC δ-layer from the SiO₂/Si interface renders the structure interesting for non-volatile memory applications. Received: 11 November 2002 / Accepted: 12 November 2002 / Published online: 4 April 2003 RID="*" ID="*"Corresponding author. Fax: +49-351-260-3285, E-mail: K.-H.Heinig@fz-rossendorf.de     

Disclination Mechanism of Plastic Deformation of Nanocrystalline Materials

A model describing mechanical behaviour of nanocrystalline materials (NC) obtained by crystallization from amorphous precursor is presented. In the framework of this model a structure of such NCs is represented as a composite consisting of amorphous matrix and absolutely rigid inclusions corresponding to crystalline phase. Dependencies of stress concentration coefficient and yield stress of NCs on the average grain size are obtained. It is shown that the dependence of the yield stress has a point of inflection at the critical grain size in the range of 20–25 nm and is inverse to the Hall-Petch relationship at grain sizes smaller than the critical one. The model predicts a formation of a superlattice from disclinations located in triple junctions of grains on the stage of NC plastic flow. A process of the plastic flow of NC's amorphous matrix and amorphous metallic alloys is described as a go-ahead mechanism of dislocation movement, which includes emission, absorption and reemission of dislocations by disclinations.     

Fluctuations of electroluminescence intensity of single CdSe nanocrystals excited by scanning tunneling microscope current

Electroluminescence from single CdSe nanocrystals (NCs) excited by tunneling current of scanning tunneling microscope (STM) has been measured. Two types of samples with low and high concentration of CdSe NCs deposited on the gold substrate have been prepared. Both types of samples had no plasmon emission. It enabled one to detect pure electroluminescence from single CdSe NCs. Samples with low concentration of NCs exhibit an intensive short-term luminescence of NCs for several seconds. Samples with high concentration of NCs exhibit a weak fluctuating long-term luminescence for thousand seconds. Fluctuations of NC electroluminescence differ considerably from those detected recently in photoluminescence of CdSe NCs embedded in polymer films. The difference in fluctuations results from the difference in physical conditions existing in electro- and photoluminescence. The distribution of photons w(N, T) emitted in time interval T has been found from statistical treating of fluctuating luminescence. Due to weakness of the pure signal, we paid a special attention to allowing for photomultiplier tube noise while treating these fluctuations. The photon distribution in pure signal is one of super-Poisson type, i.e. it is broader than Poisson distribution. A dynamical model for an absorber–emitter excited by tunneling current of STM has been offered. The model takes into account the thermal drift of STM tip.     

Superior dielectric properties and bandgap modulation in hydrothermally grown Gr/MgO nanocomposite

MgO nanoparticles (NPs) and Gr/MgO nanocomposite (NC) have been synthesized by hydrothermal route. X-ray diffraction (XRD) analysis confirmed the crystalline cubic phase of MgO and Gr/MgO NC. Raman spectroscopy was used to study the defects in the NCs. Electron microscopy study display spherical NPs of MgO on graphene sheets. UV-visible spectroscopy shows a red shift in the absorption band and a significant reduction in the bandgap for Gr/MgO NC. The improvements in dielectric properties of NC can be ascribed to interfacial polarization between rGO and MgO. The rGO in the NCs supports the electron transfer and improves the electrical conductivity.     

Resonant Raman scattering in CdSxSe1−x nanocrystals: effects of phonon confinement,composition, and elastic strain

Optical phonon modes, confined in CdS_xSe_1−x nanocrystal (NC) quantum dots (≈2 nm in radius) grown in a glass matrix by the melting‐nucleation method, were studied by resonant Raman scattering (RRS) spectroscopy and theoretical modeling. The formation of nanocrystalline quantum dots (QDs) is evidenced by the observation of absorption peaks and theoretically expected resonance bands in the RRS excitation spectra. This system, a ternary alloy, offers the possibility to investigate the interplay between the effects of phonon localization by disorder and phonon confinement by the NC/matrix interface. Based on the concept of propagating optical phonons, which is accepted for two‐mode pseudo‐binary alloys in their bulk form, we extended the continuous lattice dynamics model, which has successfully been used for nearly spherical NCs of binary materials, to the present case. After determining the alloy composition for NCs (that was evaluated with only 2–3% uncertainty using the bulk longitudinal optical phonon wavenumbers) and the NC size (using atomic force microscopy and optical absorption data), the experimental RRS spectra were described rather well by this theory, including the line shape and polarization dependence of the scattering intensity. Even though the presence of a compressive strain in the NCs (introduced by the matrix) masks the expected downward shift owing to the phonons' spatial quantization, the asymmetric broadening of both Raman peaks is similar to that characteristic of NCs of pure binary materials. Although with some caution, we suggest that both CdSe‐like and CdS‐like optical phonon modes indeed are propagating within the NC size unless the alloy is considerably heterogeneous. Copyright © 2011 John Wiley & Sons, Ltd.