Functionalized CdS nanospheres and nanorods

Functionalized nanoparticles are discussed. Surfaces of CdS:Mn/ZnS core/shell nanospheres (Qdots) were converted from hydrophobic to hydrophilic by growth of a SiO₂ shell. The colloidal dispersion was stabilize by adding a surfactant with a negative surface charge, and a cell-penetrating-peptide, TAT, was attached through a primary amine group. The TAT functionalized Qdots were shown to pass the blood-brain-barrier and luminescence in the infused half of the brain.In addition, nanorods of S²⁻ rich CdS were synthesized by reaction of excess S with Cd precursors in the presence of ethylene diamine. The photoluminescence (PL) peak from the S²⁻ rich CdS nanorods was broad with a maximum at ∼710 nm, which was 40 nm longer in wavelength than the PL peak from Cd²⁺ rich CdS (∼670 nm) nanorods. The influence of surface electron or hole trap states on the luminescent pathway of CdS nanorods were used to explain these shifts in wavelength. Nanocrystals of Au with ∼2 nm diameters were grown on S²⁻ rich surfaces of CdS nanorods. Significant quenching of photoluminescence was observed from Au nanocrystals on CdS nanorods due to interfacial charge separation. Charge separation by Au nanocrystals on CdS resulted in enhanced UV photocatalytic degradation of Procion red mix-5B (PRB) dye in aqueous solution.     

In situ synthesis of mesoporous CdS nanoparticles in ternary cubic phase lyotropic liquid crystal

An in situ technique for the synthesis of CdS nanoparticles in a ternary lyotropic cubic phase liquid crystal has been carried out. The extremely viscous cubic phase liquid-crystal system consists of poly(oxyethylene)₁₀ nonyl phenol ether as non-ionic surfactant, octane as oil phase and an aqueous phase containing reactant ions (Cd²⁺ and S^2-). Thioacetamide (TAA) has been utilized as a source for slow release of sulfur in the in situ synthesis of CdS. Rheological results show that CdS nanoparticle growth did not disrupt the structure of the cubic phase liquid-crystal system. This indicates that homogenous synthesis of CdS in the liquid crystal had been achieved. The final products were characterized using X-ray photoelectron spectroscopy, thermal gravimetric analysis, transmission electron microscopy and UV-visible spectroscopy. It was found that the CdS nanoparticles formed have a mesoporous structure with a size dependent on the TAA decomposition aging time. Received: 29 March 2002 / Accepted: 4 September 2002 / Published online: 17 December 2002 RID="*" ID="*"Corresponding author. Fax: +603-8921/3257, E-mail: shahidan@pkrisc.cc.ukm.my     

Preparation and characterization of CdS/Si coaxial nanowires

CdS/Si coaxial nanowires were fabricated via a simple one-step thermal evaporation of CdS powder in mass scale. Their crystallinities, general morphologies and detailed microstructures were characterized by using X-ray diffraction, scanning electron microscope, transmission electron microscope and Raman spectra. The CdS core crystallizes in a hexagonal wurtzite structure with lattice constants of a=0.4140 nm and c=0.6719 nm, and the Si shell is amorphous. Five Raman peaks from the CdS core were observed. They are 1LO at 305 cm⁻¹, 2LO at 601 cm⁻¹, A₁-TO at 212 cm⁻¹, E₁-TO at 234 cm⁻¹, and E₂ at 252 cm⁻¹. Photoluminescence measurements show that the nanowires have two emission bands around 510 and 590 nm, which originate from the intrinsic transitions of CdS cores and the amorphous Si shells, respectively.     

Self-assembled one-pot synthesis of red luminescent CdS:Mn/Mn(OH)2 nanoparticles

We report a novel method of growing red luminescent (635 nm) Mn-doped CdS (CdS:Mn) nanoparticles capped by an inorganic shell of Mn(OH)₂. CdSO₄, Na₂S₂O₃ and Mn(NO₃)₂ were used as the precursors, and thioglycerol (C₃H₈O₂S) was employed as the capping agent and also the catalyst of the reaction. Using these materials resulted in very slow rate of the reaction and particles growth. The self-assembled one-pot process was performed at pH of 8 and Mn:Cd ratio of 10, and took about 10 days for completion. CdS:Mn nanoparticles are slowly formed in the first day of the process; however, the luminescence is weak. After 7 days, the solution turns white turbid through the formation of additional particles, which precipitate on the walls on the next day. At this stage, a relatively strong red luminescence at 635 nm appears from transparent solution of the CdS:Mn nanoparticles. The white deposit on the walls turns to dark-brown color and luminescence increases on the 9th day. Finally, the CdS:Mn nanoparticles agglomerate and precipitate out of the solution on 10th day. X-ray diffraction and optical spectroscopy showed crystalline phase CdS nanoparticles with an average size of 3.6 nm. We explain the luminescence enhancement based on the formation of a Mn(OH)₂ shell on the surface of the CdS:Mn nanoparticles during the precipitation stage. This can passivate the S dangling bonds located on the particles surface. As the surface Cd sites are previously capped with thioglycerol molecules, a complete surface passivation is achieved and results in emergence of high-intensity luminescence.     

Effect of Si ion irradiation on polycrystalline CdS thin film grown from novel photochemical deposition technique

CdS thin films have been deposited from aqueous solution by photochemical reactions. The solution contains Cd(CH₃COO)₂ and Na₂S₂O₃, and pH is controlled in an acidic region by adding H₂SO₄. The solution is illuminated with light from a high-pressure mercury-arc lamp. CdS thin films are formed on a glass substrate by the heterogeneous nucleation and the deposited thin films have been subjected to high-energy Si ion irradiations. Si ion irradiation has been performed with an energy of 80 MeV at fluences of 1×10¹¹, 1×10¹², 1×10¹³ and 1×10¹⁴ ions/cm² using tandem pelletron accelerator. The irradiation-induced changes in CdS thin films are studied using XRD, Raman spectroscopy and photoluminescence. Broadening of the PL emission peak were observed with increasing irradiation fluence, which could be attributed to the band tailing effect of the Si ion irradiation. The lattice disorder takes place at high Si ion fluences.     

Iodine as a donor in CdS

Iodine doped single crystals of CdS were grown from the vapor phase. High temperature Hall effect measurements for the crystals equilibrated with Cd and S₂ vapors at temperatures between 700 and 1000°C gave the free electron concentration as a function of p_Cd or p_S2 and temperature. The results can be explained on the basis of a model in which the CdS is saturated with iodine at low p_Cd (=high p_S2) but unsaturated at high p_Cd.The solubility of iodine in CdS is given by c_t=1·73×10²²p_S2^?1/8 exp (?1·045 eV/kT) cm^?3 atm^?1/8=4·62×10¹⁹p_Cd^1/4 exp (?0·195 eV/kT) cm^?3 atm^1/4The formation of pairs (I_SV_Cd)′ from I_S^· and V_Cd″ is governed by the equilibrium constant K_{P(I, V)}=4 exp (≤1·1 eV/kT)If Cd diffusion occurs primarily by free vacancies, the Cd^* tracer self diffusion leads to a vacancy mobility of (1·2±0·5)×10^?5 cm² sec^?1 at 900°C, in agreement with results reported by Woodbury [12], but (7±3) times larger than reported by Kumar and Kroger [10].     

Solvothermal synthesis of CdS nanorods using hydroxyethyl cellulose as a template

CdS nanorods were solvothermally produced from Cd(CH₃COO)₂ and S powder using ethylenediamine (en) as a solvent and hydroxyethyl cellulose (HEC) as a template. The phase with hexagonal structure was detected using XRD and SAED, which is in perfect accordance with the results obtained by simulation. SEM, TEM and HRTEM revealed the development of nanorods with a number of atoms arranged in crystal lattices. When the appropriate amount of HEC was used, the longest nanorods, with preferential growth in the [0 0 1] direction, were produced. Raman spectra showed the fundamental and overtone modes at the same wavenumbers of 301 and 599 cm⁻¹, respectively. Their relative intensities at each temperature were strongly influenced by the anisotropic geometry of the products. Photoluminescence caused by electron-hole recombination was detected at 470 nm, and by surface trapping induced emission at 575 nm. The formation mechanism of CdS nanorods was also proposed based on the experimental results.     

The defect structure of silver-doped CdS

High-temperature Hall effect measurements are carried out on CdS doped with 2·5 × 10¹⁷?2·3 × 10²⁰ Ag cm^?3 under various cadmium and sulfur pressures. At high p_cd and low silver concentrations, Ag acts as a donor. At higher concentrations self compensation occurs. An anomalous variation of the Hall coefficient with p_s2 indicates that the electron concentration increases with increasing p_s2. This is attributed to the formation of anti structure defects S_cd. A complete defect model is proposed, and published solubility and diffusion data for Ag in CdS in equilibrium with (Ag, Cd) alloys are reinterpreted on the basis of this model.     

Effect of CdS nanoparticles on fluorescence from Sm doped SiO2 glass

Sm³⁺ doped CdS nanoparticles have been prepared by sol-gel method. The effect of annealing temperatures and doping concentrations of CdS on the photoluminescence spectra of Sm³⁺ were studied. From the measurement of its optical absorption, three phenomenological Judd-Ofelt intensity parameters (Ω₂, Ω₄, and Ω₆) have been computed and used to parameterize the radiative properties. The influences of CdS on Sm³⁺ ions were studied by fluorescence spectroscopy. The fluorescence spectra revealed that the emission intensity of samarium increased considerably in the presence of CdS nanoparticles. The evaluation of radiative properties of Sm³⁺ containing CdS showed that the ⁴G_5/2→⁶H_7/2 transition in silica matrix had the potential to be a laser transition.     

Room temperature magnetism of Fe doped CdS nanocrystals

Undoped and Fe doped CdS nanocrystals with Fe content of 2–5 at% of average crystallite size 1.2–2 nm have been obtained using chemical co-precipitation method with 2-mercaptoethonal as capping agent at 80 °C. X-ray diffraction (XRD) results showed that the undoped CdS nanocrystals were in mixed phase of cubic and hexagonal, where as the doped CdS nanocrystals were in hexagonal phase. Room-temperature ferromagnetism has been observed in Fe-doped CdS nanocrystals. Magnetic studies indicated diamagnetism in undoped, ferromagnetism in lightly doped (2 and 3 at%) and paramagnetism in samples of higher Fe content (4 and 5 at%). The substitutional incorporation of Fe³⁺ ion in Cd²⁺ sites was reflected in structural and electron paramagnetic resonance (EPR) measurements. Isolated as well as interacting Fe³⁺ ions are observed in EPR.     

Fabrication of well-aligned CdS nanotubes by CVD-template method

Well-aligned CdS nanotubes have been synthesized within the nanochannels of the porous anodic alumina (PAA) membranes by pyrolyzing cadmium bis(diethyldithiocarbamate) [Cd(S₂CNEt₂)₂] at 400 °C. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) show that the CdS nanotubes are highly ordered with uniform diameter in range of 80-150 nm and the length up to tens of microns. X-ray diffraction (XRD), Raman spectrum, energy-dispersive spectroscopy (EDS) and selected-area electron diffraction (SAED) demonstrate that the nanotubes are composed of pure hexagonal phase polycrystalline CdS. The synthetic route can, in principle, be extended to fabricate other nanotubes of a wide range of semiconductors.     

Luminescence of CdS:Ag Quantum Dots in a Polymethacrylate Matrix

Semiconductor quantum dots (QDs) exhibit intense luminescence and reproduce optical characteristics. Doping with metal ions has a positive effect on their properties. Introduction of QDs into polymer matrices leads to the formation of a required morphology of composites. There is a problem in synthesis of optically transparent polymer composites containing QDs of the А²В⁶ group that consists in the extremely low solubility of metal chalcogenides and most of their precursors in monomers. To solve this problem, we used colloidal synthesis. CdS QDs were synthesized by the method of appearing reagents in situ in methylmethacrylate (MMA). Doping with Ag⁺ ions was performed by adding a silver salt into the reaction mixture during the synthesis of CdS QDs. The PMMA/CdS:Ag luminescent polymer glasses were synthesized by radical block polymerization of MMA. The transparency of the composites at wavelengths exceeding 500 nm reaches 92% (5 mm). The luminescence excitation is related to the interband electron transitions in CdS crystals. Luminescence in the range of 500–600 nm is observed due to electron relaxation via a system of levels in the band gap of doped CdS crystals. The positions and intensities of the spectral bands depend on the Ag⁺ concentration, particle size, excitation wavelength, and other factors. The formation of Cd(Ag)S/Ag₂S structures at Ag⁺ concentrations higher than 5.0 × 10^–3 mol/L quenches the luminescence.     

A new and straightforward synthesis route for preparing Cds quantum Dots

In this work, highly stable, soluble and luminescent CdS quantum dots (QDots) with a narrow size distribution were synthesized in ethylene glycol using the polyol process and the solvothermal technique. In this case instead of using a conventional highly toxic sulfur source like H₂S, we use elemental sulfur dissolved in ethylene glycol to perform the reaction. When the solvent reaches its boiling point inside the autoclave, sulfur is reduced to S^?2 and reacts with Cd⁺² ions to form CdS nanocrystals. Analysis of the spectroscopic and TEM measurements showed that 3 nm monodispersed CdS QDots were synthesized and exhibited high photoluminescence (PL) in the blue green region of the spectra when excited with 355 nm.     

Temperature dependence of the luminescence of nanocrystalline CdS/Mn

The temperature dependence of the luminescence properties of nanocrystalline CdS/Mn²⁺ particles is investigated. In addition to an orange Mn²⁺ emission around 585 nm a red defect related emission around 700 nm is observed. The temperature quenching of both emissions is similar (T_q≈100 K). For the defect emission the reduction in the lifetime follows the temperature dependence of the intensity. For the Mn²⁺ emission however, the intensity decreases more rapidly than the lifetime with increasing temperature. To explain these observations a model is proposed in which the Mn²⁺ ions are excited via an intermediate state involving shallowly trapped (≈40 meV) charge carriers.     

Optimisation of the CBD CdS deposition parameters for ZnO/CdS/CuGaSe2/Mo solar cells

We present an optimisation of our recipe for the CdS chemical bath deposition process as applied to solar cells based on polycrystalline CuGaSe₂ (CGSe) absorber layers prepared in two stages by physical vapour deposition. We investigate the influence of the ammonia (NH₃) and the thiourea (H₂NCSNH₂) concentration, both being constituents of the chemical bath deposition (CBD) solution, at a deposition temperature of 80 °C on the microstructural and optical properties of CdS layers and on ZnO/CdS/CuGaSe₂/Mo device parameters. The composition of the CdS layers and their thickness were determined using X-ray Fluorescence Analysis. Transmission and reflection measurements performed at 300 K were used for the calculation of absorption and optical band gap energy (E_g). The E_g values of the films varied from 2.41 to 2.46 eV depending on deposition conditions. Cubic phase of the as-grown layers was identified by X-ray diffraction analysis. An improvement in the investigated solar cells efficiency was achieved when the ammonia concentration was increased and the thiourea concentration was reduced, compared to the previously used standard HMI recipe. The influence of the CBD CdS preparation recipe on the ZnO/CdS/CuGaSe₂/Mo electrical and photoelectrical properties is discussed.     

Synthesis of CdS nanocrystals by a microwave activated method and investigation of the photoluminescence and electroluminescence properties

We have synthesized CdS nanocrystals (NCs) by a microwave activated method. CdSO₄ and Na₂S₂O₃ were used as the precursors and thioglycolic acid (TGA) was used as capping agent molecule. The aqueous synthesis was based on the heat sensitivity of Na₂S₂O₃. In this method, microwave irradiation creates the activation energy for dissociation of Na₂S₂O₃ and leads to the CdS NCs formation. X-ray diffraction (XRD) and transmission electron microscopy (TEM) analyses demonstrated hexagonal phase CdS NCs with an average size around 3 nm for sample prepared at 5 min irradiation time. A band gap range of 3.38-2.89 eV was possible only by increasing the microwave irradiation time, corresponding to a 2.7-3.7 nm size. Photoluminescence (PL) spectra showed a white emission between 400 and 750 nm. The best attained PL quantum yield (QY) of the NCs was about 10%. Synthesized NCs were used as emissive layer in a light emitting device (LED) with ITO/PEDOT:PSS/PVK/CdS-NCs/AL structure. Turn on voltage of fabricated device was about 7 V. The CIE color coordinate of the LED at (0.34, 0.43) demonstrated a near white light LED with an emission on green-yellow boundary of white.     

Structural and Upconversion Studies of Er3+ Codoped with CdS Nanoparticles in Sol-Gel Glasses

The Er³⁺ codoped with CdS nanoparticles in sol-gel glass with an average particle size of about 10 nm have been synthesized by sol-gel method. The green and red up-conversion emissions centered at about 534, 560 and 680 nm, corresponding to the ²H_11/2→⁴I_15/2, ⁴S_3/2→⁴I_15/2 and ⁴F_9/2→⁴I_15/2 transitions of Er³⁺, respectively; were detected by a 800 nm excitation. The two-photon absorption process is involved in the green and red up-conversion emissions.     

溶剂热再结晶合成由纳米颗粒自组装成的一维CdS纳米棒

采用两种不同的溶剂热路径合成出了不同形貌和尺寸的CdS纳米晶, 一种是以无水乙二胺(en) 为溶剂, CdCl₂·2.5H₂O和硫脲(H₂NCSH₂N) 为镉源和硫源, 在不同反应温度(160 ℃-220 ℃ 下制备出了CdS纳米晶, 讨论温度对CdS纳米晶生长的影响; 另一种是以en为溶剂, 将在160 ℃下合成的产物在200 ℃下原位再结晶生长2-8 h, 分析原位生长时间对CdS纳米晶生长的影响. 通过X射线衍射(XRD)、 扫描电子电镜(SEM) 和透射电子电镜(TEM) 等表征产物的物相、 形貌和微结构, 分析可知: 两种路线合成的产物均为六方相CdS; 当温度为160 ℃时, 产物形貌为纳米颗粒状, 当温度高于160 ℃时, 产物为CdS纳米棒状; 同时, 在200 ℃下原位再结晶生长不同时间后发现产物形貌由纳米颗粒转变为纳米棒, 通过场发射扫描电镜(HRTEM) 分析可知: 纳米棒是由零维纳米颗粒自组装而成. 最后, 讨论了影响产物CdS纳米晶形貌转变的因素和纳米棒的生长机理.     

Optical and IR study of CdS nanoparticles dispersed in a new confined p-phenylenevinylene

In the present study we have synthesized CdS semiconducting quantum dots by reverse micelle method using dodecanthiol (C₁₂H₂₆S) as the capping agent. The synthetic medium consists of a quaternary water/Sodium dodecyl sulfate (SDS)/buta-1-ol/hexane microemulsion. The size of the particles was controlled by changing the molar ratio W=[H₂O]/[SdS], where [H₂O] and [SdS] are the molar concentrations in hexane of water and SdS respectively. The CdS nanoparticles were embedded in a new PPV derivate named Fluorinated Bisphenol A P-phenylenevinylene (BPAF-PPV). Fourier transform infrared spectroscopy (FT-IR) showed a strong interaction of thiol groups with CdS nanoparticles. Blue shift of the optical absorption onset is observed due to quantum size effect. The band gap and particle sizes of the nanoparticles were deduced from optical absorption spectra and the use of an effective mass approximation (EMA) model. Photoluminescence spectroscopy evidenced a charge transfer process via the interface between BPAF-PPV/CdS nanoparticles.     

Investigations on structural, vibrational, morphological and optical properties of CdS and CdS/Co films by ultrasonic spray pyrolysis

CdS and CdS/Co films have been deposited on glass substrates by an ultrasonic spray pyrolysis method. The effects of Co incorporation on the structural, optical, morphological, elemental and vibrational properties of these films were investigated. XRD analysis confirmed the hexagonal wurtzite structure of all films and had no impurity phase. While CdS film has (0 0 2) as the preferred orientation, CdS/Co films have (1 1 0) as the preferred orientation. The direct optical band gap was found to decrease from 2.42 to 2.39 eV by Co incorporation. The decrease of the direct energy gaps by increasing Co contents is mainly due to the sp-d exchange interaction between the localized d-electrons of Co²⁺ ions and band electrons of CdS. After the optical investigations, it was seen that the transmittance of CdS films decreased by Co content. The Raman measurements revealed two peaks corresponding to the 1LO and 2LO modes of hexagonal CdS. The vibrational modes of Cd-S were obtained in the wavenumber range (590-715 cm⁻¹) using Fourier transform infrared spectroscopy (FTIR). The elemental analysis of the film was done by energy dispersive X-ray spectrometry.