Structural, Optical and Electrical Properties of ZnS/Porous Silicon Heterostructures

ZnS films are deposited by pulsed laser deposition on porous silicon （PS） substrates formed by electrochemical anodization of p-type （100） silicon wafer. Scanning electron microscope images reveal that the surface of ZnS films is unsmoothed, and there are some cracks in the ZnS films due to the roughness of the PS surface. The x-ray diffraction patterns show that the ZnS films on PS surface are grown in preferring orientation along cubic phase β-ZnS （111） direction. White light emission is obtained by combining the blue-green emission from ZnS films with the orange-red emission from PS layers. Based on the I-V characteristic, the ZnS/PS heterojunction exhibits the rectifying junction behaviour, and an ideality factor n is calculated to be 77 from the I-V plot.     

Optical Nonlinear Properties of CdSeS/ZnS Core/Shell Quantum Dots

The optical nonlinear properties of CdSeS/ZnS quantum dots (QDs) areinvestigated by Z-scan technique using fundamental harmonic generation(1064nm) of mode-locked Nd:YAG laser for the first time. The experimental results show that two photon absorptions (TPA) occur at input intensity up to 12.5GW/cm². CdSeS/ZnS QDs have an average TPA cross section of 13710GM and large nonlinear refractive index on order of 10^-7esu. The large optical nonlinearities perhaps allow the CdSeS/ZnS QDs to be one kind of candidate material for bioimaging and fluorescence label, optical limiting and all-optical switching.     

Auger process in CdS/ZnS core-shell quantum dots

Auger processes are investigated for CdS/ZnS core-shell quantum dots. Auger recombination (AR) lifetime and electron relaxation inside the core are computed. Using the effective-mass theory and by solving a three-dimension Schrödinger equation we predict the dependence of Auger relaxation on size of core-shell nanocrystals. We considered in this work different AR processes: the excited electron (EE), excited hole (EH), multiexciton AR type. Likewise, Auger multiexciton recombination rates are predicted for biexciton. Our results show that biexciton AR type is more efficient than the other AR process (excited electron (EE) and excited hole (EH)). We also found that electron Auger relaxation P→S is very efficient in core-shell nanostructures.     

Synthesis and characterization of ZnS nanoparticles in water/AOT/n-heptane microemulsions

ZnS nanoparticles were synthetized using water-containing AOT reversed micelles as nanoreactors and characterized by UV-Vis spectrophotometry, HRTEM (high-resolution transmission electron microscopy), SAED (selected-area electron diffraction), and digital image processing. The experimental data evidence a slow growing process of fractal-like ZnS nanoparticles’ coupled with a change of their photophysical properties. Both these processes are well described by power laws. The nanoparticles size is mainly controlled by the micellar size. After evaporation of the organic solvent, it has been found that the deposit is constituted by smaller and more stable ZnS nanoparticles bathed in a surfactant matrix. Received: 20 April 1999 / Accepted: 23 April 1999 / Published online: 8 September 1999     

Effect of Electrical Field on Colloidal CdSe/ZnS Quantum Dots

We fabricate the hybrid films of colloidal CdSe/ZnS quantum dots (QDs) and poly(9-vinylcarbazole) (PVK) sandwiched between two electrodes. The voltage and temperature dependences of the electroluminescence (EL) are measured. The quantum-confined Stark effect of colloidal QDs is clearly observed. To explore the mechanism in the QD EL, hybrid films are fabricated with different concentrations of colloidal QDs. Electrons and holes are proposed to be separately transported in QDs and PVK, respectively.     

Resonant Raman scattering of ZnS,ZnO, and ZnS/ZnO core/shell quantum dots

Resonant Raman scattering by optical phonon modes as well as their overtones was investigated in ZnS and ZnO quantum dots grown by the Langmuir–Blodgett technique. The in situ formation of ZnS/ZnO core/shell quantum dots was monitored by Raman spectroscopy during laser illumination.     

Nonlinear Bragg structures based on ZnS/ZnSe superlattices

Nonlinear optical response of periodic ZnSe/ZnS heterostructures is reported using interband excitation of a ZnSe sublattice by nano-, pico- and femtosecond laser pulses. A considerable shift of the reflection spectrum and large relative reflection changes were observed in a wide spectral range corresponding to the transparency region of ZnSe far from the intrinsic absorption onset. Evaluated refraction-index change is about −0.05 with the relaxation time being about 3 ps. In the case of femtosecond excitation, a wide-band nonlinear response is observed for both one-photon near-UV and two-photon near-IR excitation. The nonlinear refraction is supposed to be controlled by population-induced absorption changes in ZnSe single crystals and relevant refraction-index modification via Kramers–Kronig relations. The nonlinearity relaxation time is supposed to trace a transition from a non-equilibrium to a quasi-equilibrium distribution of electrons and holes within ZnSe conduction and valence bands, respectively, rather than the electron–hole recombination time. The nonlinearity mechanism does not reduce to just population-dependent absorption saturation, but essentially results from the specific distribution function in the first instance after excitation.     

Hydrothermal synthesis of novel sandwich-like structured ZnS/octylamine hybrid nanosheets

Novel sandwich-like structured zinc sulfide (ZnS)/octylamine (OA) hybrid nanosheets with exclusively sheet-like morphology were synthesized for the first time via a mild hydrothermal route using OA as structure-directing agent. The as-synthesized products were characterized by the X-ray diffraction, transmission electron microscopy, scan electron microscopy, energy dispersive analyses of X-rays, thermogravimetric analysis, and ultraviolet and visible absorption spectroscopy. The results showed that OA molecules were intercalated between wurtzite ZnS layers. As revealed from optical absorption measurements, the hybrid nanosheets exhibits strong quantum confinement effect with a great blue shift in the band gap.     

应变层异质结ZnS/ZnSe、ZnS/ZnS_xSe_(1-x)和ZnSe/ZnS_xSe_(1-x)价带带阶的研究

采用基于原子球近似下线性Ｍｕｆｉｎ－Ｔｉｎ轨道（ＬＭＴＯ－ＡＳＡ）的平均键能计算方法，研究了以ＺｎＳｘＳｅ１－ｘ为衬底，沿（００１）方向外延生长的应变层异质结ＺｎＳ／ＺｎＳｅ、ＺｎＳ／ＺｎＳｘＳｅ１－ｘ和ＺｎＳｅ／ＺｎＳｘＳｅ１－ｘ的价带带阶值ΔＥｖ（ｘ）．研究表明，ΔＥｖ（ｘ）值随衬底合金组分ｘ单调变化．且两者的关系是非线性的．在此计算结果与其它理论计算和实验结果符合较好．     

Temperature-dependent photoluminescence from bicrystalline ZnS (core/shell) nanocables

The experimental study of the temperature-dependent photoluminescence properties of bicrystalline ZnS core/shell nanocables under 10 K to 300 K was reported. The results show that there are two distinct peaks situated at the UV (about 372.6 nm) and green (about 500 nm) regions, respectively, and one blue-shoulder band (about 465 nm) superimposed between them for all spectra. The UV peak shows an obvious redshift with increasing temperature. The analyses of Gaussian-fitted the blue-shoulder band and the green bands from 10 K to 300 K reveal that all spectra can be well fitted by three Gaussian peaks: blue peak (B, about 2.67 eV), two green peaks (G1, about 2.47 eV and G2, about 2.42 eV). With increasing temperature, the blue band shows blueshift. The green bands show anomalous transition: green band G1 shows blueshift-redshift transition and green band G2 shows redshift-blueshift. The origins of these bands and their temperature-dependent shifts are explained based on defect levels and strong carrier localization effect at the defect levels in addition to band-gap shrinkage.     

Shell-dependent hole transport in highly luminescent CdSe-core CdS/ZnCdS/ZnS multi-shell nanocrystals

The photoinduced hole transfer dynamics from CdSe quantum dots (QDs), shelled with ZnS or CdS/CdZnS/ZnS layers, to organic hole transporting materials (HTMs) is investigated by absorption, steady-state and time-resolved photoluminescence (PL) spectroscopy. The PL intensity and lifetime of the QDs are dramatically quenched when HTMs are added into the dilute QD solution. The quenching efficiency of the QDs significantly decreases with increasing the shell thickness and increases with decreasing the oxidation potential of the HTMs. These facts are correlated with the photoinduced hole transfer from the QDs to the HTMs. The above results are helpful in understanding the photoexcitation dynamics-related phenomena of organic molecule conjugated nano-object.     

Characterization and luminescent properties of SiO2:ZnS:Mn and ZnS:Mn nanophosphors synthesized by a sol-gel method

ZnS and SiO₂-ZnS nanophosphors, with or without different concentration of Mn²⁺ activator ions, were synthesized by using a sol-gel method. Dried gels were annealed at 600 °C for 2 h. Structure, morphology and particle sizes of the samples were determined by using X-ray diffraction (XRD), highresolution transmission electron microscopy (HRTEM) and field emission scanning electron microscopy (FESEM). The diffraction peaks associated with the zincblende and the wurtzite structures of ZnS were detected from as prepared ZnS powders and additional diffraction peaks associated with ZnO were detected from the annealed powders. The particle sizes of the ZnS powders were shown to increase from 3 to 50 nm when the powders were annealed at 600 °C. An UV-Vis spectrophotometer and a 325 nm He-Cd laser were used to investigate luminescent properties of the samples in air at room temperature. The bandgap of ZnS nanoparticles estimated from the UV-Vis data was 4.1 eV. Enhanced orange photoluminescence (PL) associated with ⁴T₁→⁶A₁ transitions of Mn²⁺ was observed from as prepared ZnS:Mn²⁺and SiO₂-ZnS:Mn²⁺ powders at 600 nm when the concentration of Mn²⁺ was varied from 2-20 mol%. This emission was suppressed when the powders were annealed at 600 °C resulting in two emission peaks at 450 and 560 nm, which can be ascribed to defects emission in SiO₂ and ZnO respectively. The mechanism of light emission from Mn²⁺, the effect of varying the concentration on the PL intensity, and the effect of annealing are discussed.     

Preparation and characterization of ZnS/CdS bi-layer for CdTe solar cell application

In this work, bilayer ZnS/CdS film was prepared as an improved window layer of CdTe solar cell. TEM was used to observe the cross section of the bilayer structure. The total thickness of ZnS/CdS film was about 60 nm, which could allow more photons to pass through it and contribute to the photocurrent. Optical properties of the bilayers were investigated using UV–vis spectroscopy. Compared with poor transmission of standard CdS film in the short wavelength range of 350–550 nm, the transmission of ZnS/CdS was improved and reached above 50%. The ZnS/CdS was annealed with CdCl₂. X-ray photoelectron spectroscopy (XPS) was used to investigate its chemical properties. A possible diffusion between CdS and ZnS was observed after annealing. The efficiency of standard CdS/CdTe solar cell was 9.53%. The device based on ZnS/CdS window layer had a poor 6% efficiency. With annealing treatment on ZnS/CdS layer, the performance was improved and reached 10.3%. In addition, the homogeneity of solar cell performance was improved using ZnS/CdS window layer. A thin ZnS layer was quite effective to reduce the possible shunt paths and short parts of window layer and consequently contributed to fabrication of a homogeneous CdTe solar cell.     

Parameter-dependent photon echo induced in CdSe/ZnS quantum dot quantum well

The two pulse photon echo (2PPE) phenomena induced by the 1s-1s electronic transition in CdSe/ZnS quantum dot quantum well (QDQW) has been studied by employing semiconductor Bloch equations. The energy eigenvalues and eigenfunctions of electrons and holes have been obtained by solving the stationary Schrödinger equation under effective-mass approximation. The Coulomb interaction, which changes with the size variation of QDQW, has been calculated and analyzed as a perturbation. The variations of the electric transition dipole moment and the energy interval with the changing of the size and structure of the QDQW have also been obtained. It has been shown from the numerical calculation results that the efficiency of 2PPE can be controlled by the variation of the size and structure of the QDQW and the mechanism has been explained in terms of the quantum size confined effect (QSCE) theory.     

Preparation, characterization and study of optical properties of ZnS nanophosphor

In this work the preparation, characterization and photoluminescence studies of pure and copper-doped ZnS nanophosphors are reported, which are prepared by using solid-state reaction technique at a temperature of 100 °C. The as-obtained samples were characterized by X-ray diffraction (XRD) and UV-VIS Reflectance spectroscopy. The XRD analysis confirms the formation of cubic phase of undoped as well as Cu²⁺-doped ZnS nanoparticles. Furthermore it shows that the average size of pure as well as copper-doped samples ranges from 15 to 50 nm. The room-temperature PL spectra of the undoped ZnS sample showed two main peaks centered at around 421 and 450 nm, which are the characteristic emissions of interstitial zinc and sulfur vacancies, respectively. The PL of the doped sample showed a broad-band emission spectrum centered at 465 nm accompanied with shoulders at around 425, 450 and 510 nm, which are the characteristic emission peaks of interstitial zinc, sulfur vacancies and Cu²⁺ ions, respectively. Our experimental results indicate that the PL spectrum confirms the presence of Cu²⁺ ions in the ZnS nanoparticles as expected.     

Growth and optical characterization of single quantum well structure of submonolayer ZnS/ZnTe

Single quantum wells of submonolayer ZnS/ZnTe were grown between ZnTe layers using hot wall epitaxy method with fast-movable substrate configuration. As ZnS well widths decrease from 1 to 0.15 monolayer, the photoluminescence peaks shift to higher energies from 2.049 to 2.306 eV, and the photoluminescence intensities increase. As ZnS well width decrease, the PL spectra show the lower-energy tails and consequently the increased PL FWHMs. This is a result of a convolution of two PL peaks from two-dimensional and zero-dimensional quantum islands, supported by a still lived lower-energy peaks of zero-dimensional quantum islands above 50 K. The energy shift in the power dependence of photoluminescence spectra is proportional to the third root of the excitation density. These behaviors can be described by the formation of submonolayer type-II ZnS/ZnTe quantum well structure, and the coexistence of two-dimensional and one-dimensional islands in ZnS layers.     

Synthesis of ZnS nanorods by annealing precursor ZnS nanoparticles in NaCl flux

ZnS nanorods were fabricated by annealing precursor ZnS nanoparticles, which were prepared by one-step, solid-state reaction of ZnCl₂ and Na₂S through grinding by hand at ambient temperature, in NaCl flux. The as-prepared ZnS nanorods have diameters of 40-80 nm, and lengths up to several micrometers. The structural features and chemical composition of the nanorods were investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED), high-resolution transmission electron microscopy (HRTEM), and Raman spectra.     

Water-induced stabilization of ZnS nanoparticles

Surface states become important in particles with reduced size as the surface to volume ratio increases. Here we provide direct evidence of water-induced structure buildup and stabilization of nanocrystalline ZnS. The ZnS nanoparticles, prepared employing a non-equilibrium route, provide an ideal platform to investigate microscopic details of water induced structural transformation and thus demonstrate the role of S-H interactions in the time-evolution of crystalline behaviour in these particles. The colossal changes observed make these materials ideal for water sensing.