A study of size dependent structure, morphology and luminescence behavior of CdS films on Si substrate

Size tunable cadmium sulfide (CdS) films deposited by a dip coating technique on silicon (100) and indium tin oxide/glass substrates have been characterized using X-ray diffraction, X-ray reflectivity, transmission electron microscopy, atomic force microscopy and photoluminescence spectroscopy. The structural characterization indicated growth of an oriented phase of cadmium sulfide. Transmission electron microscopy used to calculate the particle size indicated narrow size dispersion. The tendency of nanocrystalline CdS films to form ordered clusters of CdS quantum dots on silicon (100) substrate has been revealed by morphological studies using atomic force microscopy. The photoluminescence emission spectroscopy of the cadmium sulfide films has also been investigated. It is shown that the nanocrystalline CdS exhibit intense photoluminescence as compared to the large grained polycrystalline CdS films. The effect of quantum confinement also manifested as a blue shift of photoluminescence emission. It is shown that the observed photoluminescence behavior of CdS is substantially enhanced when the nanocrystallites are assembled on silicon (100) substrate.     

Self-organized ZnSe quantum dots: synthesis and characterization

Self-organized ZnSe quantum dots (Q-ZnSe) were grown on indium tin oxide substrate using wet chemical technique without or in presence of copper and manganese dopants. The structural, morphological and luminescence properties of the as grown Q-dot films have been investigated, using X-ray diffraction, transmission electron microscopy, atomic force microscopy and optical and luminescence spectroscopy. Composition of the samples were analyzed using atomic absorption spectroscopy. The quantum dots have been shown to deposit in a compact, uniform and organized array on the indium tin oxide substrate. The size dependent blue shift in the experimentally determined absorption edge has been compared with the theoretical predictions based on the effective mass and tight binding approximations. It is shown that the experimentally determined absorption edges depart significantly from the theoretically calculated values. The photoluminescence properties of the undoped as well as doped Q-ZnSe have also been discussed.     

Effect of capping agents on optical and antibacterial properties of cadmium selenide quantum dots

Cadmium selenide quantum dots (CdSe QDs) were synthesized in aqueous phase by the freezing temperature injection technique using different capping agents (viz. thioglycolic acid, 1-thioglycerol, L-cysteine). Absorption spectra of CdSe QDs exhibited a blue shift as compared to its bulk counterpart, which is an indication of quantum confinement effect. The photoluminescence spectra of CdSe QDs confirmed that the particles are poly-dispersed and possess enhanced luminescent property, depending upon the chemical nature of capping agents. The QDs have been characterized by Fourier-transform infrared spectroscopy, atomic absorption spectroscopy and transmission electron microscopy. Further, antimicrobial activity of as-prepared QDs has also been investigated using the disk diffusion method.     

Size tuning of MAA capped CdSe and CdSe/CdS quantum dots and their stability in different pH environments

The present work reports synthesis of mercaptoacetic acid capped CdSe nanoparticles soluble in water at different temperatures and with different precursor ratios. This enabled to tune the particle size of QDs from 2.7 to 5.8 nm. The particles consist of nanocrystals; with mixed phase, hexagonal wurtzite as well as sphalerite cubic and are luminescent with quantum yield 10%. The quantum yield up to 20% has been obtained by growing a shell of CdS over the CdSe. HR-TEM images, XRD patterns and the photoluminescence excitation spectra shows epitaxial growth of CdS shell over CdSe and with average size 3.2 ± 1.2 and 4.7 ± 1.2 nm for CdSe and CdSe/CdS quantum dots respectively. FT-IR spectrum and the negative zeta potential value together confirms the attachment of mercaptoacetic acid to the QD surface, where the carboxylic acid group is facing towards solvent and provides stability due to electrostatic hindrance. Further, the QDs are checked for their stability and the luminescence in environments of different pH (4–11 pH). Both CdSe and CdSe/CdS agglomerate with total elimination of fluorescence for 4 pH medium, and no shift in the fluorescence emission peak observed for the 6–9 pH, therefore QDs can be applicable as the fluorescence tags in this specific range of pH.     

Resonant infrared matrix-assisted pulsed laser evaporation of CdSe colloidal quantum dot/poly[2-methoxy-5-(2′-ethylhexyloxy)-1,4-(1-cyano vinylene)phenylene] hybrid nanocomposite thin films

CdSe colloidal quantum dot / poly[2-methoxy-5-(2′-ethylhexyloxy)-1,4-(1-cyano vinylene)phenylene] hybrid nanocomposite thin films were deposited using resonant infrared matrix-assisted pulsed laser evaporation. The distributions of CdSe colloidal quantum dots within the polymer matrices of as-grown films were evaluated using transmission electron microscopy, and the optical properties of these films were determined by photoluminescence spectroscopy. These measurements demonstrate that: i) depending upon the deposition parameters used, the CdSe colloidal quantum dot distribution can be tuned between two morphology extremes, i.e. clustering or homogenous dispersion; and ii) the constituent materials of the nanocomposite are not damaged in any way that affects structural or optical properties by the deposition process. The demonstrated ability to control nanoparticle distribution within organic films has not been achieved by other deposition techniques and could enhance the performance of optoelectronic devices based on these materials.     

不同温度下硒化镉(CdSe)量子点的生长及荧光性研究

研究了以氧化镉（CdO）和硒（Se）粉为前驱体,在三辛基膦（TOP）和油酸中合成无机半导体量子点（quantum dots, QDs）CdSe.研究了在不同的反应温度下粒子的生长,通过紫外吸收光谱（UV-Vis）、荧光发射光谱（PL）、透射电子显微镜（TEM）等手段跟踪反应过程并对样品性能进行了表征.实验结果表明,反应温度和反应时间对量子点的生长和荧光性能有很大的影响.     

水相中CdSe与核/壳CdSe/CdS量子点的制备与发光特性研究

以巯基乙酸为稳定剂在水相中制备了CdSe与核/壳型CdSe/CdS量子点水溶胶, 用紫外-可见吸收光谱和发射光谱研究了它们的发光特性, 并且用X射线粉末衍射(XRD)、透射电镜(TEM)和X射线光电子能谱(XPS)表征了它们的结构、形貌和化学组成, 结果表明使用该方法制备的量子点分散性良好, 而且用CdS对CdSe进行表面修饰以后的发光强度明显提高, 发射光谱和吸收光谱都有红移现象, 不同粒径颗粒的吸收峰的位置也有所不同.     

Luminescence of CdSe quantum dots near a layer of silver nanoparticles ion-synthesized in sapphire

We study the characteristics of the luminescence of composite films based on polymethyl methacrylate with CdSe quantum dots deposited from solution onto the surface of a sapphire substrate containing a preliminarily formed layer with ion-synthesized silver nanoparticles. The sapphire layer with silver nanoparticles exhibits selective plasmon absorption in the visible spectral range with a peak at 463 nm. Enhancement in the exciton luminescence intensity of quantum dots with a peak at 590 nm is observed upon excitation at wavelengths lying in the region of plasmon resonance of metal nanoparticles, as well as luminescence quenching for quantum dots located in the vicinity of silver nanoparticles.     

A study on the structural and mechanical properties of nanocrystalline CuS thin films grown by chemical bath deposition technique

We report a chemical route for the deposition of nanocrystalline thin films of CuS, using aqueous solutions of Cu(CH₃COO)₂, SC(NH₂)₂ and N(CH₂CH₂OH)₃ [triethanolamine, i.e. TEA] in proper concentrations and ratios. The films were structurally characterized using X-ray diffraction technique (XRD), field emission scanning electron microscopy (FESEM) and optical analysis [both photo luminescence (PL) and ultraviolet-visible (UV-vis)]. Optical studies showed a large blue shift in the band gap energy of the films due to quantum confinement effect exerted by the nanocrystals. From both XRD and FESEM analyses, formation of CuS nanocrystals with sizes within 10-15 nm was evident. A study on the mechanical properties was carried out using nanoindentation and nanoscratch techniques, which showed good mechanical stability and high adherence of the films with the bottom substrate. Such study on the mechanical properties of the CuS thin films is being reported here for the first time. Current-voltage (I-V) measurements were also carried out for the films, which showed p-type conductivity.     

Surfactant mediated optical properties of cytosine capped CdSe quantum dots

This letter demonstrates the use of one of the nucleobases, ‘cytosine’ as a new capping agent in controlling the size of the nanoparticles. A size dependent blue shift in optical absorption with enhanced luminescence is observed. Since the calculated density of states do not show any change in the band gap of as-prepared quantum dots after capping, the observed blue shift of the absorption peak can solely be attributed to the so-called size-effect whereas the enhancement in luminescence to surfactant mediated defect passivation. It is expected that the observed properties of the cytosine capped CdSe quantum dots would facilitate a better bio-compatibility of tailor-made nanoparticles for bio-imaging applications.     

Preparation,optical and thermal properties of CdSe–ZnS/poly(lactic acid) (PLA) nanocomposites

In this study, CdSe–ZnS/poly(lactic acid) (PLA) nanocomposite films, containing different concentrations of surface-modified CdSe–ZnS quantum dots (QDs), were prepared via a solution casting method. The optical microstructural and thermal properties of the as-prepared QDs/PLA films were investigated. The QDs/PLA films exhibited strong and stable photoluminescence (PL) intensity with concentration dependent amplitudes. The transmission electron microscopy (TEM) pictures revealed that QDs of ∼5 nm diameter were uniformly dispersed in the PLA matrix. According to the results of thermogravimetric analysis, the weight-loss onset temperature of PLA clearly decreased with the QD content. A combination of Fourier transform infrared (FT-IR) spectroscopy, X-ray diffractometry (XRD) and differential scanning calorimetry (DSC) results suggested that the QDs exhibit obvious nucleation activity on the crystallization behavior of the PLA matrix. This research provides useful information to the foundations of practical applications of QDs/PLA nanocomposites as fluorescent and biodegradable functionalized materials.     

Highly photoluminescent and photostable CdSe quantum dot-nylon hybrid composites for efficient light conversion applications

Highly photoluminescent hexadecylamine (HDA) capped core CdSe quantum dots (QDs) with fluorescent quantum yields (QYs) up to 60% were synthesized using a hot injection method and directly incorporated into nylon polymer. For the incorporation of crude CdSe QDs into nylon a simple reproducible and upscalable one pot approach was developed without the need of further purification steps. The photoluminescence (PL) properties of the core QDs and the resulting QD-polymer hybrid composites were investigated and compared. Red emitting hybrid materials exhibit a QY of 60% with a high potential for applications in direct light and energy conversion. The hybrid materials could be successfully utilized as LED conversion layers. By avoiding exposure to oxygen the hybrid films can be kept for a month without detecting a significant decrease in luminescence. Various three dimensional structures are easily available opening doors for further applications such as novel materials for fluorescence standard development in laser scanning microscopy (LSM).     

Exciton storage by Mn(2+) in colloidal Mn(2+)-doped CdSe quantum dots

Colloidal Mn (2+)-doped CdSe quantum dots showing long excitonic photoluminescence decay times of up to tau exc = 15 mus at temperatures over 100 K are described. These decay times exceed those of undoped CdSe quantum dots by approximately 10 (3) and are shown to arise from the creation of excitons by back energy transfer from excited Mn (2+) dopant ions. A kinetic model describing thermal equilibrium between Mn (2+ 4)T 1 and CdSe excitonic excited states reproduces the experimental observations and reveals that, for some quantum dots, excitons can emit with near unity probability despite being approximately 100 meV above the Mn (2+ 4)T 1 state. The effect of Mn (2+) doping on CdSe quantum dot luminescence at high temperatures is thus completely opposite from that at low temperatures described previously.     

Structural,optical and morphological studies of undoped and Zn-doped CdSe QDs via aqueous route synthesis

Undoped and Zn-doped CdSe quantum dots (QDs) were successfully synthesized by the chemical precipitation method. The structural, optical and morphological properties of the synthesized undoped and Zn-doped CdSe QDs were studied by X-ray diffraction (XRD), UV–visible absorption spectroscopy, photoluminescence (PL) spectroscopy, fluorescence lifetime spectroscopy, scanning electron microscopy (SEM), field emission transmission electron microscopy (FE-TEM) and FTIR. The synthesized undoped and Zn-doped CdSe QDs were in cubic crystalline phase, which was confirmed by the XRD technique. From the UV–visible absorption spectral analysis, the absorption wavelengths of both undoped and Zn-doped CdSe QDs show blue-shift with respect to their bulk counterpart as a result of quantum confinement effect. The highest luminescence intensity was observed for CdSe QDs doped with 4% Zn by PL studies. TEM analysis shows that the prepared QDs are spherical in shape.     

The effect of annealing and photoactivation on the optical transitions of band-band and surface trap states of colloidal quantum dots in PMMA

For optoelectronic applications, colloidal CdSe quantum dots (QDs) have been integrated into solid devices by using optically transparent polymer matrices that embedded the colloidal QDs. We systematically studied the effect of annealing and photoactivation on the band-band (BB) and surface trap state (STS) transitions of colloidal CdSe QDs embedded in polymethylmethacrylate (QDs-PMMA). The QDs-PMMA composites demonstrate enhancement of the STS emissions while their annealing leads to an intensity quench of both BB and STS emissions. The annealing process also causes the red shift of the BB emission. By contrast, photoactivation of QDs-PMMA composites results in the remarkable recovery of luminescence intensity accompanied by blue shift of the emissions. Furthermore, it is found in the photoactivation process that the STS emission can be saturated earlier than the BB emission, which renders it possible to tune the light color of the emissions. The combination of annealing and photoactivation could undoubtedly provide an effective way to precisely tune the colors of light-emitting devices that use colloidal CdSe QDs.     

Spectral properties of multiply charged semiconductor quantum dots

Spectrally resolved fluorescence imaging of single CdSe/ZnS quantum dots (QDs), charged by electrospray deposition under negative bias has revealed a surprising net blue shift (～60 meV peak-to-peak) in the distribution of center frequencies in QD band-edge luminescence. Electrostatic force microscopy (EFM) on the electrospray QD samples showed a subpopulation of charged QDs with 4.7 ± 0.7 excess electrons, as well as a significant fraction of uncharged QDs as evidenced by the distinct cantilever response under bias. We show that the blue-shifted peak recombination energy can be understood as a first-order electronic perturbation that affects the band-edge electron- and hole-states differently. These studies provide new insight into the role of electronic perturbations of QD luminescence by excess charges.     

Size-dependent optical and dielectric properties of nanocrystalline ZnS thin films synthesized via rf-magnetron sputtering technique

Nanocrystalline ZnS thin films have been synthesized by radio frequency magnetron sputtering technique on glass and Si substrates at a substrate temperature 300 K. X-ray diffraction and selected area electron diffraction studies confirmed the formation of nanocrystalline cubic phase of ZnS in the films, although the target material was hexagonal ZnS. The particle size, calculated from the XRD patterns of the thin films was found in the range 2.06-4.86 nm. TEM micrographs of the thin films revealed the manifestation of ZnS nanoparticles with sizes in the range 3.00-5.83 nm. UV-vis-NIR spectrophotometric measurements showed that the films were highly transparent (∼90%) in the wavelength range 400-2600 nm with a blue shift of the absorption edge. The direct allowed bandgaps have been calculated and they lie in the range 3.89-4.44 eV. The particle size, calculated from the shift of direct bandgap, due to quantum confinement effect lying in the range 3.23-5.60 nm, well support the TEM results. The room temperature photoluminescence spectra of the films showed two peaks centered around 315 and 450 nm. We assigned the first peak due to bandgap transitions while the latter was due to sulfur vacancy in the films. The composition analysis by energy dispersive X-rays also supported the existence of sulfur deficiency in the films. The dielectric property study showed high dielectric constant (85-100) at a higher frequency (>5 kHz).     

Study on the photoluminescence character of water-soluble CdSe nanocrystals under ambient conditions

Water soluble, thioglycolic acid (TGA) modified CdSe nanocrystals (NCs) have been prepared in aqueous media by the reaction between Cd2+ and NaHSe. Although initially these quantum dots (QDs) display photoluminescence (PL) with very low quantum yields (QY), upon prolonged exposure to ambient light, a strong PL enhancement by illumination is observed which leads to water soluble QDs with high luminescence. This result may have important application potential in biological or other fields. The primary reason for the luminescence enhancement is concluded to be the incorporation of sulfide ions from TGA into the lattice of CdSe NCs and the subsequent formation of alloy structures. Moreover, the CdSe/CdS core-shell structured QDs synthesized in aqueous solutions also consolidate this conclusion.     

圆偏振光诱导CdTe量子点再生长及其对光致发光的影响

实验研究了以3-巯基丙酸为配体合成的水溶性CdTe量子点经过非偏振光与圆偏振光照射处理后, 量子点的再生长变化规律。采用光致发光谱、紫外-可见吸收光谱、透射电子显微镜与X射线衍射等表征手段分析表明: 非偏振光会促进CdTe量子点的光氧化, 导致量子点尺寸缩小, 荧光发光峰位蓝移, 且发光效率降低; 而圆偏振光增强了配体的光氧化, 在量子点表面形成CdS层, 导致量子点尺寸进一步增大, 荧光发光峰红移, 且发光效率提升。进一步讨论了CdTe量子点与配体之间的键合作用, 相关光化学反应机制及其对量子点光致发光性质的影响。     

Self-assembled InAs/GaAs quantum dots covered by different strain reducing layers exhibiting strong photo- and electroluminescence in 1.3 and 1.55 microm bands

The effect of different InGaAs and GaAsSb strain reducing layers on photoluminescence and electroluminescence from self-assembled InAs/GaAs quantum dots grown by metal-organic vapour phase epitaxy was investigated. The aim was to shift their luminescence maximum towards optical communication wavelengths at 1.3 or 1.55 microm. Results show that covering by InGaAs strain reducing layer provides stronger shift of photoluminescence maximum (up to 1.55 microm) as compared to GaAsSb one with similar strain in the structure. This is caused by the increase of quantum dot size during InGaAs capping and reduction of quantum confinement of the electron wave function which spreads into the cap. Unfortunately, the weaker electron confinement in quantum dots is a reason of a considerable blue shift of electroluminescence from these InGaAs structures since optical transitions move to InGaAs quantum well. Although strong electroluminescence at 1300 nm was achieved from quantum dots covered by both types of strain reducing layers, the GaAsSb strain reducing layer is more suitable for long wavelength electroluminescence due to higher electron confinement potential allowing suppression of thermal carrier escape from quantum dots.