Optical limiting properties of CdS nanowires

Intensity-dependent nonlinear optical transmission studies of cadmium sulfide (CdS) nanowires (∼ 50-100 nm diameter) suspended in dimethylformamide have been carried out in the visible region using the Z-scan technique with 7 ns pulses from the second harmonic of an Nd:YAG laser. The optical limiting threshold of CdS nanowires suspension was determined to be 1.3 J cm^− 2, with normalized transmittance of 0.47, which is relatively lower when compared with those of many popular metal nanowire suspensions reported in the literature. Based on an effective three-photon absorption model, nonlinear absorption and nonlinear scattering were identified as the dominant processes for the measured reduced transmittance.     

Optical characterization of CdS semiconductor nanoparticles capped with starch

Starch capped cadmium sulfide (CdS) nanoparticles were synthesized by aqueous solution precipitation. Starch added during the synthesis of nanoparticles resulted in cadmium-rich nanoparticles forming a stable complex with starch. The size of the CdS quantum dots was measured using high resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD). The average diameter (d) of nanoparticles spanned the range 4.8 ± 0.4 to 5.7 ± 0.2 nm when the pH of the solution was varied within the range 10-14. The main Raman phonon of CdS, the longitudinal optical mode located around 300 cm⁻¹, softens as diameter decreases, in accordance with theoretical predictions. In addition, the largest Raman response of starch, near 478 cm⁻¹, related with the important skeletal vibration modes of the starch pyranose ring, dominates the spectra of the CdS capped nanoparticles and also softens as the size decreases. This fact indicates a strain variation on CdS as a function of d which increases as the pH increases.     

Controlled synthesis, characterization and optical properties of CdS nanocrystalline thin films via chemical bath deposition (CBD) route

In this study, the CdS nanocrystalline thin films obtained from an ammonia-free chemical bath deposition process. The crystallites with a size range of 10–20 nm in diameter with zinc blend (cubic) and wurtzite (hexagonal) crystal structure and strong photoluminescence were prepared from the mixture solutions of: cadmium chloride dihydrate as a cadmium source, thiourea as a sulfur source and sodium citrate dihydrate as a complexing agent for cadmium ions. The well-cleaned glass used as a substrate for thin films deposition. The obtained samples were characterized by the techniques such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), atomic force microscopy (AFM) and fluorescence spectroscopy. Also, the effect of two parameters such as pH and temperature of reaction on the synthesis of CdS nanocrystals was studied. Finally, it was found the CdS nanocrystals showed sharp excitation features and strong “band-edge” emission.     

Low temperature growth and dimension- dependent photoluminescence efficiency of semiconductor nanowires

Low temperature growth and dimension dependent photoluminescence (PL) efficiency of semiconductor nanowires were investigated with CdS as a model system. The CdS nanowires were prepared with a simple, low temperature metal-organic chemical vapor deposition (MOCVD) process via the vapor–liquid–solid (VLS) mechanism. The low growth temperature of 360 °C was made possible with a newly developed single-source precursor of CdS and by using sputtered Au as the catalyst for the VLS growth. The length and diameter of the nanowires were adjusted by reaction time and sputtering conditions of Au, respectively. Nanowires of up to several μm in length and 20 to 200 nm in diameter were obtained. The PL quantum yield of the nanowires was found to decrease with increasing wire length, but to increase with decreasing wire diameter. This dimension-dependent PL efficiency of one-dimensional nanostructure, unlikely resulting from the quantum size confinement effect, appears to be a new observation that carries application significance. PACS 74.25.Gz; 78.55.Et; 78.67.Lt     

Large Third-Order Optical Nonlinearity of Cadmium Sulphide Nanoparticles Embedded in Polymer Thin Films

A simple method for synthesis of well dispersed cadmium sulphide nanoparticles embedded in a polyethylene glycol matrix （PEG 400） in thin film form is presented. The large blue shift of the band gap energy of the CdS nanoparticles compared to the bulk semiconductors is observed via UV-vis absorption spectra. Photoluminescence spectra of CdS nanocomposite films show that the emission peaks shift towards the longer wavelength with the increase of annealing temperature. Transmission electron microscopic images as well as Raman scattering studies confirm the CdS nanometer size particle formation within the polymer matrix. The particle size is about 8 nm. Selected area electron diffraction （SAED） shows the cubic zinc blende polycrystalline rings. Third-order optical nonlinearity of the CdS nanopartieles embedded in polymer thin films is studied with the Z-scan technique under 1064 nm excitation. The results show that the CdS nanocomposite film exhibits negative nonlinear refraction index and positive absorption coefficient. The film shows large optical nonlinearity, and the magnitude of the third-order nonlinear susceptibility of the film is calculated to be 1.73 × 10^-9 esu. The corresponding mechanism is discussed.     

“Anomalous” spectral photoresistive field effect in CdS crystals caused by the screening of the electron-hole interaction

The changes observed in low-temperature (T = 77 K) near-band-edge photoconductivity spectra of CdS crystals in response to an external transverse electric field applied to the sample surface have been investigated. An analysis of the “anomalous” character of these changes for a number of crystals has revealed a significant role of the near-surface effects of screening of the electron-hole interaction in the formation of near-band-edge photoconductivity spectra of CdS crystals with a technological excess of cadmium near the surface. It has been shown that the depletion (enrichment) transverse electric field leads to a weakening (enhancement) of screening effects in the photoconductivity spectra of the CdS crystals.     

Preparation, conversion, and comparison of the photocatalytic property of Cd(OH)2, CdO, CdS and CdSe

In this paper, we report the hydrothermal preparation of Cd(OH)₂ nanowires and further conversion to CdO nanobelts, CdS nanowires and CdSe nanoparticles through thermal treatment, solvothermal and mixed-solvothermal routes, respectively. The as-obtained products were characterized by means of powder X-ray diffraction (XRD), transmission electron microscopy (TEM), and field emission scanning electron microscopy (FEMSEM). Research showed that four cadmium compounds were good photocatalysts for the degradation of organic dyes such as Safranine T and Pyronine B, under irradiation of 365 nm UV light. The order of catalytic activity of different materials was found to be Cd(OH)₂<CdO<CdS<CdSe.     

无催化纳米氧化锌的制备及其光学性质研究

本文采用无催化剂直接蒸发高纯Zn粉,在800℃氧气氛条件下,在Si(111)衬底上生长得到以四角状为主的纳米ZnO(T-ZnO)。T-ZnO纳米线每个角约互成110°,长度约为1.5μm,直径100nm左右;Raman分析表明E2(H)普遍存在于各形态的ZnO;光致发光光谱表明,T-ZnO纳米线的光致发光除了与材料性质有关,还与杂质缺陷有关,蓝绿光带是ZnO的缺陷产生的。     

Microemulsion-mediated synthesis of cadmium zinc sulfide nanocrystals with composition-modulated optical properties

Cadmium zinc sulfide nanocrystals were synthesized by a microemulsion-mediated process, which involving two steps: the preparation of CdS (or ZnS) seeds and the succedent hydrothermal growth of ZnS (or CdS) component. The XRD results show that the cadmium zinc sulfide nanocrystals with CdS seeds present a hexagonally homogeneous alloyed structure, while the ones with ZnS seeds mainly take on the characteristic of hexagonal CdS nanocrystals. The intrinsic factors influencing the crystal structures were discussed. The UV-vis and photoluminescence (PL) spectra indicate that the optical properties of the obtained nanocrystals with CdS seeds can be continuously modulated by tuning their compositions, although their sizes and size distributions are not under a strict control. The composition-modulated strategy, along with the hydrothermal microemulsion process, will be an effective route to achieve semiconductor nanocrystals with tunable optical properties under more manageable conditions.     

Mixed-solvothermal synthesis of CdS micro/nanostructures and their optical properties

Several novel cadmium sulfide (CdS) micro/nanostructures, including cauliflower-like microspheres, football-like microspheres, tower-like microrods, and dendrites were controllably prepared via an oxalic acid-assisted solvothermal route using ethylene glycol (EG) and H₂O as pure and mixed solvents with different S sources. The as-prepared products were characterized by X-ray powder diffraction (XRD), scanning electronic microscope (SEM) and UV-vis spectrophotometer (UV). It was found that CdS micro/nanostructures can be selectively obtained by varying the composition of solvent, concentration of oxalic acid, and sulfur sources. UV-vis absorption spectra reveal that their absorption properties are shape-dependent. The possible formation process of the CdS micro/nanostructures was briefly discussed. This route provides a facile way to tune the morphologies of CdS over a wide range.     

Synthesis of cobalt-doped cadmium sulphide nanocrystals and their optical and magnetic properties

Cobalt-doped cadmium sulphide (CdS) nanocrystals (NCs) were synthesized with three different cobalt concentrations by aqueous chemical coprecipitation method. Dopant incorporation was recognised using X-ray diffraction (XRD) analysis with a shift in the diffraction peaks and compression in the lattice. The size and crystallinity of the cobalt-doped CdS NCs were studied by high resolution transmission electron microscopy (HRTEM). The blue shift in the spectra and the band gap value of Co-doped CdS NCs was estimated using reflectance UV spectrophotometer. Variation in the luminescence properties was studied by fluorescence spectroscopy. The change in the optical properties supports the Co incorporation in the CdS NCs. The BET measurement revealed that the powders had a relatively high specific surface area of 131.30, 106.93 and 102.04 m²/g for 2, 4 and 6% Co:CdS, respectively. Room temperature magnetisation was studied using vibrating sample magnetometer for both 4 and 6% cobalt-doped CdS NCs, which revealed a weak ferromagnetic signal and strong ferromagnetic hysteresis respectively.     

Tunable emission and conductivity enhancement by tellurium doping in CdS nanowires for optoelectronic applications

Improvement of the optical and electrical characteristics is essential to get advanced performance from one dimensional (1D) material. Here, we report the first synthesis of a single crystalline Te-doped CdS nanowires (NWs) by a chemical-vapor-deposition (CVD) method. Room temperature photoluminescence (PL) spectra showed that Te concentration plays an important role in tuning emission color from orange to infrared (IR). Decrease in bandgap and PL intensity with increase in Te concentration was observed as compared to undoped CdS NWs. Red and IR emissions were found at 736.5 and 881 nm for doping concentration >6.06%. To our best knowledge, IR emission band has been observed for the first time in CdS NWs. Red-shift of LO phonon mode and its overtone in Raman spectra, and lifetime of red and IR emissions are longer than bandgap of host indicating the doping effect of CdS NWs. Energy-dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD) of the Te-doped CdS NWs further confirms the presence of Te in the CdS NWs. Output characteristics confirm enhanced output current I_ds with the increase in doping concentration. A possible growth mechanism was proposed. Doping technique offers to develop high-quality, a very stable, effective, and easily-applicable way to enhance the performance of one dimensional optoelectronic devices and solar cell applications.     

Optical waveguide behavior of Se-doped and undoped CdS one-dimensional nanostructures using near-field optical microscopy

The optical waveguide behaviors of CdS and CdS _x Se_1−x nanostructures are studied using near-field optical microscopy. Optical measurements demonstrate that light may be guided on sub-wavelength scales along CdS nanoribbons in straight or bent structures. The photoluminescence (PL) spectra from nanoribbon emission using scanning near-field optical microscopy are analyzed under different incident laser intensities. The PL spectra along Se-doped and undoped CdS nanoribbons at different propagation distances are investigated. Both the guided PL spectra of Se-doped and undoped CdS nanoribbons show red-shifts because of the band-edge absorption. Our results are useful for the development of new kinds of functional nano devices. Supported by the National Natural Science Foundation of China (Grant Nos. 10574002, 90406007, and 50602015) and the National Basic Research Program of China (Grant No. 2007CB936800)     

Study of steady state and time resolved photoluminescence of thiol capped CdS nanocrystalline powders dispersed in N,N-dimethylformamide

The microwave (MW) assisted synthesis of thiol capped cadmium sulfide (CdS) nanocrystallites/quantum dots (QDs) was performed through the reaction of cadmium acetate with thiourea in N,N-dimethylformamide (DMF) by keeping the MW irradiation time fixed (40 s) in the presence of a thiol containing capping agent. Three capping agents, namely, benzyl mercaptan (BM), 1-butanethiol (BT) and 2-mercaptoethanol (ME) were used. The concentration of the precursors was varied to check the change in the average size of the thiol capped CdS nanocrystals formed. The nanocrystallites were characterized by usual procedure. The UV-vis absorption spectra and the photoluminescence (PL) spectra of the CdS nanocrystalline powders dispersed in DMF were studied. It was observed that with increase in concentration of the capping agent (BM), there is a shift in the nature of emission (PL) from trap associated PL to the band edge luminescence in the case of BM capped CdS nanocrystalline powders dispersed in DMF possibly due to better surface passivation. The relative PL quantum yield of the thiol capped CdS nanocrystalline powders dispersed in DMF was calculated under various experimental conditions. Time-correlated single-photon counting experiments were performed to study the time-resolved photoluminescence of the CdS nanocrystalline powders dispersed in DMF. The observed emission decay profiles have been simulated using the multiexponential model. The emission decay profiles for thiol capped CdS nanocrystalline powders dispersed in DMF depend on the nature of the capping agents (thiols) used to passivate the CdS nanocrystallites. The time resolved PL studies show that the average values of PL lifetime are related to the size and size distribution of the prepared thiol capped CdS nanocrystallites.     

Controlling morphology and structure of nanocrystalline cadmium sulfide (CdS) by tailoring solvothermal processing parameters

Cadmium sulfide (CdS) with different morphologies was successfully prepared by solvothermal process by controlling the processing parameters, including nature of precursor and solvent, reaction temperature and process time. X-ray diffraction patterns revealed that, in all cases highly pure and crystallized CdS with hexagonal structure were obtained. In addition, it was found that the processing parameters influence on preferable growth direction of CdS nanostructures. Field emission scanning electron microscope analysis showed that CdS nanowires with different aspect ratios were obtained (depending upon the reaction temperature and process time) in presence of sulfur powder and ethylenediamine, whereas CdS nanoparticles were produced by sulfur powder and ethanolamine. Moreover, CdS nanorods were prepared using thiourea and ethylenediamine. Transmission electron microscope image confirmed that CdS nanowire with one of the highest aspect ratio reported in the literature (i.e., 255) was achieved using sulfur powder and ethylenediamine at 200 °C reaction temperature for 72 h process time. UV–Vis absorption spectra of CdS nanostructures prepared under different conditions displayed a blue shift relative to that of bulk CdS due to the quantum size effect.     

An approach to hybrid inorganic nanoparticles in reactive PS-b-PMSMA amphiphilic copolymers

A series of well-defined amphiphilic poly(styrene)-block-poly 3-(trimethoxysilyl) propyl methacrylate (PS-b-PMSMA) copolymers with controlled molecular weight and block length were prepared by the atom transfer free radical polymerization. The cadmium sulfide (CdS) nanoparticles were fabricated in the spherical micelles self-assembled from these prepared PS-b-PMSMA copolymers. Then, the CdS/PS-b-PMSMA films were obtained by spin coating the CdS/PS-b-PMSMA solution on silicon wafer. The experimental results showed the addition of Cu(II) could decrease the value of polydispersity index for the prepared copolymers. Nuclear magnetic resonance and Fourier transform infrared spectra showed the synthesis of PS-b-PMSMA copolymer. The average roughness and mean square roughness of the prepared CdS/PS-b-PMSMA films obtained from the atomic force microscopy analysis were 3.0–3.4 nm and 1.7–2.0 nm, respectively, indicating the excellent surface planarity. On the other hand, the ratio of block length between PS and PMSMA had a great influence on the micelle size. The larger ratio of PS to PMSMA block length resulted in the larger size of micelles and CdS nanoparticles that caused a red-shift of ultraviolet–visible and photoluminescence spectra. The red-shift of spectra was explained by the quantum confinement effect associated with the tiny size of the CdS nanoparticles.     

Orientation and ellipticity dependence of high-order harmonic generation in nanowires

It has been predicted that high-order harmonic generation (HHG) in nanowires has the potential to scale up photon energy and harmonic yield. However, studies on HHG in nanowires are still theoretical and no relevant experimental results have been reported as yet. Our experimental observation of the high-order harmonic in cadmium sulfide nanowires (CdS NWs) excited by a mid-infrared laser is, to our knowledge, the first of such study, and it verifies some of the theoretical results. Our experimental results show that the observed harmonics are strongest when a pump laser is parallel to the nanowires. Therefore, the theoretical prediction that harmonics are strongest under the nanowires parallel to the laser field is confirmed experimentally, and this can be used to determine the orientation of the nanowire. In addition, harmonics are sensitive to the variation of pump light ellipticities. This orientation dependence opens new opportunities to access the ultrafast and strong-field physics of nanowires.     

Cadmium (II) pyrrolidine dithiocarbamate complex as single source precursor for the preparation of CdS nanocrystals by microwave irradiation and conventional heating process

The complex of cadmium with pyrrolidine dithiocarbamate Cd(pdtc)₂ has been used as single source precursor for the synthesis of CdS nanoparticles. The formation of CdS nanostructures was achieved by thermal decomposition of the complex under microwave irradiation and conventional heating in presence of hexadecylamine. The CdS nanoparticles with disordered close-packed structure were obtained under microwave irradiation, whereas wurtzite hexagonal phase CdS nanorods were obtained by conventional heating method (up to 150 °C). Scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and high resolution transmission electron microscopy (HRTEM) studies also were carried out to study the structure and morphology of nanoparticles. The optical property of the CdS nanoparticles was studied by UV-visible and fluorescence emission spectral studies. Fluorescence measurements on the CdS nanoparticles show a strong emission spectrum with two sub bands that are attributed to band-edge and surface-defect emissions. The reduction of a suitable cadmium metal complex is considered to be one of the single pot methods to generate CdS semiconductor nanoparticles with different shapes and high yield.     

掺杂Mn2+的浓度对CdS纳米颗粒光致发光的影响

采用反胶束法,合成了硅土包裹的掺有不同浓度的Mn2 的CdS纳米颗粒.高分辨电镜表明这些颗粒的直径小于5 nm.仅仅改变Mn2 的掺杂浓度,研究了这些颗粒的光致发光谱和光致发光激发谱,结果表明:Mn2 浓度的大小对掺杂CdS纳米颗粒的发光产生了重要的影响.通过电子顺磁共振谱的测量和分析揭露了Mn2 浓度影响这些掺杂颗粒发光效率的原因.     

Ammonia-free method for synthesis of CdS nanocrystalline thin films through chemical bath deposition technique

The preparation of thin films of CdS by chemical bath deposition is mostly based on the utilisation of ammonia as a complexing agent for cadmium ions. Here we report on a technique based on sodium citrate dihydrate that eliminates the problems of ammonia volatility and toxicity. The crystallites with a size range of 10–20 nm in diameter with zinc blend (cubic) and wurtzite (hexagonal) crystal structures and strong photoluminescence were prepared from the mixture solutions of: cadmium chloride dihydrate as a cadmium source, thiourea as a sulfur source and sodium citrate dihydrate as a complexing agent for cadmium ions. The well-cleaned glass used as a substrate for thin film deposition. The obtained samples were characterized by the techniques such as transmission electron microscopy (TEM), X-ray diffraction (XRD), atomic force microscope (AFM) and fluorescence spectroscopy. Also, the effect of two operating conditions, (i) pH, and (ii) the temperature of reaction on the synthesizing of CdS nanocrystals was examined. Finally, it was found that the CdS nanocrystals showed sharp excitation features and strong ”band-edge” emission.