Highly luminescent (ZnSe)ZnS core-shell quantum dots for blue to UV emission: synthesis and characterization

We synthesized nearly monodisperse bare ZnSe nanocrystallites having luminescence which ranges in wavelength from 340 to 430 nm via nucleation due to supersaturation and growth followed by size selective precipitation. Bare ZnSe dots' outermost surface is passivated with organic HDA/TOP. In order to enhance the radiative emission from the semiconductor nanocrystals, we capped the bare ZnSe quantum dots with ZnS semiconductor materials of a wider band gap and 5% of lattice mismatch and produced highly luminescent core-shell (ZnSe)ZnS quantum dots. The core-shell (ZnSe)ZnS nanocrystals show 20 times or more as greatly enhanced luminescence quantum yields as those of bare ZnSe nanocrystals. The ZnSe bare dots and the (ZnSe)ZnS core-shell dots have cubic zinc blende structures as expected from the bulk structure. The observed shapes of bare ZnSe and core-shell (ZnSe)ZnS dots are nearly spherical or ellipsoidal with the aspect ratios of 1.2 and 1.4, respectively. They are not faceted.     

MOCVD技术制备的ZnS:Mn电致发光薄膜结晶性及Mn2+分布

本文报导了用MOCVD技术制备的ZnS:Mn电致发光薄膜为立方晶相,结晶取向性好,颗粒大。从高倍率的扫描电镜拍摄的照片观察到薄膜的表面平滑。SIMS测量表明Mn2+在ZnS薄膜纵向分布均匀,但在两侧有起伏,可能的原因是在生长的初终阶段流量的突变使化合物的化学计量比偏离而产生位错,引起原子的局部堆积,并且由于初终阶段ZnS:Mn生长的衬底不同使原子堆积层厚度不同。     

The mass transfer process and the growth rate of NaCl crystal growth by evaporation based on temporal phase evaluation

The mass transfer process and the crystal growth rate have been proved to be very important in the study of crystal growth kinetics, which influence the crystal quality and morphological stability. In this paper, a new method based on temporal phase evaluation was presented to characterize the mass transfer process in situ and determine the crystal growth rate. The crystallization process of NaCl crystal growth by evaporation was monitored in situ by a Mach-Zehnder interferometer, and the absolute concentration evolution, the evaporation rate and the real-time supersaturation of solution were obtained using temporal phase analysis, which acted as a novel technique to extract phase variation along time axis recently. Based on the evaporation rate and the absolution concentration, a new method to calculate mass transfer flux during the crystal growth without the knowledge of the mass transfer coefficient was proposed, and then the crystal growth rate could also be retrieved under the hypothesis of cubic crystals. The results show that the crystal growth rate increases with the supersaturation linearly. It is in agreement with the diffusion theories, which presume that matter is deposited continuously on a crystal face at a rate proportional to the difference in concentration between the points of deposition and the bulk of solution. The method is applicable to the research of crystallization process based on evaporation or vapor diffusion of which the precise conditions of nucleation and supersaturation are usually unknown because of the complexity of the evaporation rate and crystal growth rate.     

Formation of hexagonal shaped wurtzite zinc sulphide nano rods

Zinc sulfide nanorods with good photoluminescence have been successfully fabricated using a simple sol-gel process via ultrasonication, with mercaptoethanol as capping agent. The formation of ZnS nucleation, followed by subsequent growth, is significant in obtaining highly oriented ZnS nanorods. Temperature, time, and capping agent also proved to be significant factors in the growth of ZnS nanorods and greatly affect their photo luminescent properties. X-ray diffraction (XRD) analysis, low and high-resolution transmission electron microscopy (TEM & HRTEM), selected-area electron diffraction (SAED) pattern, and scanning electron microscopy (SEM) indicated that the ZnS nanorods were single crystal in nature and that they had grown up preferentially along the [0001] direction. This simple method of nucleation, followed by their successive growth, resulted in the development of an effective and low-cost fabrication process for high-quality ZnS nanorods with good photo luminescent properties that can be applied to luminescent sensors and optoelectronic devices.     

KABO晶体生长形态演化机理的分析

用高温晶体生长实时观察装置，发现了KABO晶体生长形态随着生长体系过饱和度的增大从六方形态逐渐向三角形态过渡，然后又从三角形态逐渐向六方枝蔓晶形态过渡的过程.通过KABO生长溶液高温拉曼谱的测试结果，证明了溶液中存在［BO₃］^3-三角形、［AlO₄］^5-四面体生长基元.运用负离子配位多面体生长基元理论模型，分析了KABO晶体上述生长形态演化的机理.发现KABO的生长形态是由其内部结构和生长基元共同决定的，在不同过饱和度溶液中，KABO生长基元的种类和维度将会发生变化，由此相应引起了KABO的生长形态从六方形态到三角形态，又从三角形态向六方枝蔓晶形态的演变过程. 关键词： KABO晶体 负离子配位多面体 生长形态 枝蔓晶     

A phase-field/Monte-Carlo model describing organic crystal growth from solution

In this paper work we present a phase-field/Monte-Carlo hybrid algorithm for the simulation of solutal growth of organic crystals. The algorithm is subsequently used for an investigation of diffusion effects on the growth mechanisms. This method combines a two-scale phase-field model of the liquid phase epitaxial growth and a Monte-Carlo algorithm of the 2D nucleation and thus is faster than previous purely Monte Carlo simulations of crystal growth. The inclusion of supersaturation and diffusion in the method allows the study of crystal growth under various growth conditions. Parameters used in the hybrid algorithm are bound to the energetic parameters of crystal faces, which can be estimated from a detailed study of the actual crystal structure based on a connected nets analysis, which allows the prediction of the shape and morphology of real crystals. The study of the diffusion effect is carried out based on an example of a hydroquinone crystal, which grows from the water solution at various supersaturations. The dependencies of the growth rate and the nucleation rate on the supersaturation indicate the change of the growth mechanism from spiral growth to 2D nucleation. The difference in the growth rate for various faces is in agreement with the crystal morphologies derived from the attachment energy method and observed experimentally. The main result of the simulation is the evaluation of engineering limits for choosing appropriate external process conditions.     

Preparation and growth mechanism of micro spherical ammonium dinitramide crystal based on ultrasound-assisted solvent-antisolvent method

Micro-sized spherical ammonium dinitramide (ADN) crystals are successfully prepared by a facile ultrasound-assisted solvent-antisolvent recrystallization method without introducing any additives. The influences of the volume ratio of solvent to antisolvent, the antisolvent temperature and the ultrasound power on the micro-morphologies and properties of ADN crystals are studied systematically. The changes of morphology, particle size, crystal structure and melting point of the ADN crystals are characterized through scanning electron microscopy (SEM), laser particle size analyzer (LPSA), X-ray diffraction (XRD) and differential scanning calorimetry (DSC), respectively. The results show that the optimal experimental parameters for the ADN crystal of spherical morphology are as follows: the volume ratio of solvent to antisolvent is 1:50, the antisolvent temperature is 20 ℃, and the ultrasound power is 70 W. The predicted hexagonal-flake and spherical morphologies for the ADN are close to the experimental morphologies. The growth mechanism of the spherical ADN crystal changes with supersaturation of the ADN solution. As the degree of supersaturation increases, the growth models of the spherical ADN change from the spiral growth to the rough growth, and the morphologies of ADN change from the large-sized ADN ball to the small-sized ADN ball.     

A microscopic time scale approximation to the behavior of the local slope on the faceted surface under a nonuniformity in supersaturation

The morphological stability of a growing faceted crystal is discussed. We argue that the interplay between nonuniformity in supersaturation on a growing facet and anisotropy of surface kinetics derived from the lateral motion of steps leads to a faceted instability. Qualitatively speaking, as long as the nonuniformity in supersaturation on the facet is not too large, it can be compensated for by a variation of step density along the facet, and the faceted crystal can grow in a stable manner. The problem can be modeled as a Hamilton-Jacobi equation for height of the crystal surface. The notion of a maximal stable region of a growing facet is introduced for microscopic time scale approximation of the original Hamilton-Jacobi equation. It is shown that the maximal stable region keeps its shape, determined by profile of the surface supersaturation, with constant growth rate by studying large time behavior of solution of macroscopic time scale approximation. A quantitative criterion for the facet stability is given.     

温度对Si衬底上低压MOCVD外延生长ZnS薄膜质量的影响

用低压MOCVD系统在(111)Si衬底上,用两步生长方法(改变/流量比)在300～400℃时外延生长了ZnS单晶薄膜。随着衬底温度的降低,ZnS薄膜结晶质量提高,并在300℃生长时获得结晶完整性较好的(111)ZnS单晶薄膜。文中讨论了衬底温度对薄膜质量的影响。     

Middle-infrared random lasing of Cr doped ZnSe, ZnS, CdSe powders, powders imbedded in polymer liquid solutions, and polymer films

Room temperature (RT) middle-infrared (Mid-IR) random lasing of chromium- (Cr) doped ZnSe, ZnS, and CdSe powders, powders imbedded in perfluorocarbon liquid polymer solutions, and fluorocarbon polymer films is reported. Laser active powders were prepared without a stage of bulk crystal growth by annealing of starting chemicals (pure, mixed ZnSe:CrSe; ZnS:CrS; CdSe:CrSe). Mixture of the different semiconductor hosts allows tuning oscillation wavelength from 2240 to 2630 nm.     

Growth of single-crystal ZnS nanobelts through a low-temperature thermochemistry route and their optical properties

ZnS nanobelts have been synthesized on a large scale using a simple thermochemistry method where the sources were Zn and ammonium polysulphide. The nanobelts had a uniform single-crystal hexagonal wurtzite structure with width ranging from 50 to 150 nm and length up to several tens of micrometers. The growth of ZnS nanobelts is controlled by vapor-solid (VS) crystal growth mechanism. Photoluminescence (PL) measurement shows that the nanobelts have a strong blue emission at about 450 nm and a green light emission at 530 nm. PACS 73.61.Ga; 78.55.Et; 81.15.Gh; 68.37.Hk; 68.37.Lp     

激活剂Cu和Mn对ZnS相变和微结构的影响

为了深入研究交流粉末电致发光粉的发光机理,增加对荧光粉激发能量的输入,提高它的发光亮度,研究这种材料的微结构极为必要。但要在原子尺度上研究材料的结构和成分,目前仍十分困难。至今,人们对电致发光机理还没有统一认识,不能不说与此有关。     

Weakly nonlinear analysis of the morphological stability of a two-dimensional cylindrical crystal

We present the first weakly nonlinear analysis of the morphological stability of a two-dimensional cylindrical crystal growing from solution in an arbitrary regime (with the growth rate proportional to supersaturation). A quadratic (with respect to the perturbation amplitude) correction to the critical radius of a stable crystal determined in the linear theory is obtained in an analytical form and studied as a function of the per-turbation frequency and the growth regime. It is established that an increase in the perturbation amplitude vir-tually always leads to a decrease in the critical radius. Factors accounting for this nontrivial effect are consid-ered.     

Lasing characteristics and growth of CdS epitaxial thin-films excited by second harmonic Nd: YAG laser radiation at 473 nm

The first experimental study on CdS epitaxial thin-film lasers with ZnS substrates is reported. For the first time single crystal layers of CdS have been grown on the (111) faces of ZnS substrate by the hydrogen transport method. Laser emission at 491.8 nm has been observed from these layers cooled near liquid-nitrogen temperature. Optical pumping is performed by the second harmonic of a Q-switched Nd: YAG laser operated at 473 nm, the energy of which exceeds slightly the band-gap energy of the cooled epitaxial CdS layer. The measured optical gain for these CdS thin-films compared with that for platelet CdS single crystals reveals that the optical confinement inside the epitaxial layer increases the optical gain by a factor of about two.     

Controlled extracellular biosynthesis of ZnS quantum dots by sulphate reduction bacteria in the presence of hydroxypropyl starch as a mediator

Metal sulphide quantum dots (QDs) have broad applications. Sulphate-reducing bacteria (SRB) have been recognized as synthesizers of metal sulphides, with the characteristics of a high-production efficiency and easy product harvest. However, SRB are incapable of synthesizing metal sulphide QDs. In the present study, cheap hydroxypropyl starch (HPS) was used to assist SRB in manufacturing the ZnS QDs. The results exhibited that the HPS accelerated the growth of SRB and reduction of SO₄ ²⁺ into S^2?, while it blocked the precipitation between S^2? and Zn²⁺ to control the nucleation and growth of ZnS, resulting in the formation of ZnS QDs. When the HPS concentration increased from 0.2 to 1.6 g/L, the average crystal size (ACS) of ZnS QDs dropped from 5.95 to 3.34 nm, demonstrating the controlled biosynthesis of ZnS QDs. The ZnS QDs were coated or adhered to by both HPS and proteins, which played an important role in the controlled biosynthesis of ZnS QDs. The remarkable blue shift of the narrow UV absorption peak was due to the quantum confinement effect. The sequential variation in the colour of the photoluminescence spectrum (PL) from red to yellow suggested a tunable PL of the ZnS QDs. The current work demonstrated that SRB can fabricate the formation of ZnS QDs with a controlled size and tunable PL at a high-production rate of approximately 8.7 g/(L × week) through the simple mediation of HPS, with the yield being 7.46 times the highest yield in previously reported studies. The current work is of great importance to the commercialization of the biosynthesis of ZnS QDs.     

Calculations of the complete morphological phase diagram for nonequilibrium growth of a spherical crystal under arbitrary surface kinetics

Complete morphological diagrams (with stable, metastable, and absolutely unstable regions) were calculated for the problem of morphology selection under the conditions of nonequilibrium growth of a spherical crystal taking into account arbitrary kinetic process rates at the boundary and a linear dependence of the growth rate on supersaturation. The consideration was performed by jointly using linear stability analysis and the principle of maximum entropy production. The principal difference between kinetically and diffusion-controlled crystal growth is the possibility of the coexistence of three or more morphological phases under the same conditions in the former case. It was shown that, at the transition point, the rate of accretion of the growing crystal mass increased in a jump. The jump value was studied as a function of the parameters of the problem.     

The kinetics of the anomalous state formation and the growth of helium crystals at high supersaturation

The kinetics of the formation of an anomalous state of a helium crystal with a fast-growing surface are investigated. It is demonstrated experimentally that it is external supersaturation that is the determining factor of formation of an anomalous state. The dependence of the time of formation of anomalous state on temperature and initial supersaturation is measured. The problem of crystal growth with the excitation of the first-sound wave in the container is solved. This solution is used to determine the dependence of the kinetic coefficient of growth of anomalous facets on temperature and initial supersaturation. It is demonstrated that the kinetic coefficient of facet growth decreases on approaching the boundaries of the region of the existence of an anomalous state. The kinetic coefficient of growth of atomically rough surfaces in an anomalous state is determined by the damping of pressure oscillation. It is found that the value of the latter coefficient is three-four times that of the respective value for the facets but is considerably, by an order of magnitude, less than the value of the coefficient of growth of such surfaces in the normal state. Phenomena are treated which accompany the spiral growth of facets, namely, the excitation of oscillations of a screw dislocation during spiral rotation and the emergence of vortex rings in superfluid helium. The effect of these phenomena on the kinetics of facet growth and on the formation of an anomalous state is discussed.     

The formation of a dislocation spiral on the (101) face of a monoclinic lysozyme crystal: High-resolution experiments

The elementary processes of crystal growth in the case of a low kink density on step edges have been studied by in situ atomic force microscopy. High-resolution images of the first turn of the polygonal dislocation spiral on the (101) face of monoclinic lysozyme crystals, which allow one to discern separate crystal cells, have been obtained. It has been shown that the dependence of the spiral segment velocity on its length is inconsistent with the Gibbs-Thomson law and is represented by several rectilinear sections. The results were explained by taking into account the features of the growth of crystals with a low kink density at low supersaturation.     

Thermoelektronen- und induzierte Photoelektronenemission bei Zinksulfid

Thermo-electron-emission (TE), thermo-luminescence (TL), and induced photoelectron-emission (IPE) of ZnS were investigated after electron bombardment. In contrary to other substances TE and TL of ZnS are of different origin. TL is caused by traps within the forbidden energy gap in the interior of the crystal, whereas a sorption layer on the crystal surface is responsible for TE. IPE is caused by a third mechanism.     

Highly oriented electrospun polycaprolactone micro/nanofibers prepared by a field-controllable electrode and rotating collector

Novel ZnO tetrapod-shaped nanostructures with pearl-necklace-shaped arms were successfully synthesized using mixture of Zn, ZnO, and carbon powder as source. The definite supersaturation ratio provided by Zn, ZnO, and carbon powder was considered as the crucial factor of determining the formation of this kind of structure, and a negative feedback growth model combined with octahedral nucleation mechanism was proposed. Two other comparative experiments were also conducted to study the growth behavior of reagent species under different supersaturation ratios. Our experiments provided a beneficial experimental exploration in controlled growth of nanostructures through modulating supersaturation ratio by source, and these obtained novel nanostructures were also expected to have potential application as functional blocks in nanodevices. Furthermore, the study of photoluminescence indicated that the physical properties were strongly dependent on the crystal structure.