Ion probing with Luminescent PbS Quantum dots in PVA

The PbS quantum dots synthesized in PVA are used to investigate their photoluminescence (PL) response to various ions such as Zn, Cd, Hg, Ag, Cu, Fe, Mn, Co, Cr and Ni ions. The enhancement in the photoluminescence intensity is observed with specific ions namely Zn, Cd, Hg and Ag. Among these four ions, the PL response to Hg and Ag even at sub-micro-molar concentrations is quite high, approximately an order of magnitude higher than Zn and Cd. It is interesting to observe that the change in Pb and S molar ratio has profound effect on the selectivity of these ions. The samples prepared under excess of S are quite effective compared to Pb. Indeed, the later one has hardly any effect on the photoluminescence response. These results also indicate that the sensitivity of these QDs could be fine-tuned by controlling the S concentration at the surface. Contrary to the above, Cu, Fe and Co quenches the photoluminescence. Another interesting property of PbS in PVA observed is photo-brightening mechanism due to the curing of the polymer with laser. However, the presence of excess ions at the surface changes its property to photo-darkening/brightening that depends on the direction of carrier transfer mechanism (from QDs to the surface adsorbed metal ions or vice-versa), which is an interesting feature for metal ion detectivity

Temperature and capping dependence of NIR emission from PbS nano-microcrystallites with different morphologies

We have prepared various morphological PbS nano–microcrystallites by three different techniques namely, facile hydrothermal technique, chemical bath deposition and surfactant-assisted solution growth. This is the first report on the photoluminescence emission bands around 0.60 eV and their evolution with temperature in dendrite/rod shaped PbS microstructures. The 0.60 eV band, which is common to all our samples, quenches at low temperatures up to 60–70 K. However, after surface capping with mercaptoethanol (C2H5OSH), a new band around 1.0 eV appears and evolves with temperature, indicating bimodal size distribution in these dendritic nanostructures. On the other hand, the samples grown by chemical bath deposition exhibited this bimodal size distribution even without surface capping. However, after surface is protected with mercaptoethanol, enhancement in 0.60 eV band intensity (4–5 times) with lowering temperature is a specific characteristic of these samples. Anomalous temperature dependence of photoluminescence intensity with corresponding changes in full width at half maxima is an interesting behaviour that indicates thermalization of the carriers in nano-particles of different sizes. We note that the surface capping is an important step in understanding the bimodal nature of hydrothermal grown nanostructure and microstructure. The present results indicate the ossibility of white light emission from dendritic structures

Two beam photoluminescence of PbS quantum dots in polyvinyl alcohol

We report the effect of dual beam excitation on the photoluminescence (PL) from PbS quantum dots in polyvinyl alcohol by using two excitation lasers, namely Ar+ (514.5 nm) and He-Ne laser (670 nm). Both sources of excitation gave similar PL spectra around 1.67 eV (related to shallow traps) and 1.1 eV (related to deep traps). When both lasers were used at the same time, we found that the PL induced by each of the lasers was partly quenched by the illumination of the other laser. The proposed mechanism of this quenching effect involves traps that are populated by one specific laser excitation, being photo-ionized by the presence of the other laser. Temperature, laser intensity and modulation frequency dependent quenching efficiencies are presented in this paper. This reversible modulation has potential for optical switching and memory device applications. (C) 2010 Elsevier B.V. All rights reserved

Identification of surface states in PbS quantum dots by temperature dependent photoluminescence

We report the type and nature of the surface states in PbS quantum dots grown in poly vinyl alcohol by the colloidal technique. Mercaptoethanol $(C_2H_5OSH)$ capping and the molar ratio of Pb:S were used as parameters to understand the origin of the surface state related photoluminescence. From absorption and photoluminescence measurements, it was observed that increasing Lead concentration resulted in bigger nanoparticles with broad size distribution. However, the increase in sulfur concentration helped in the formation of smaller nanoparticles with narrow size distribution. Passivation studies also revealed that the origin of the bands below 1.1 eV was sulfur related. Thus these experiments indicated that sulfur played an important role, not only in size selectivity, but also in controlling defects in PbS quantum structures. Temperature dependent PL studies on different samples with various Pb:S molar ratios and with mercaptoethanol treated gave an insight into the nature of the surface states. Based on these results, we explain the origin of the surface states and proposed a model for different PL bands. The observed temperature-dependent trends of PL intensity (decreasing in Pb:S::1:1, increasing in S terminated and anomalous behavior in samples with excess of Pb) is attributed to the dominant midgap states and the results are consistent with carrier redistribution and recombination statistics involved in the quantum structures

Efficient Hg and Ag ion detection with luminescent PbS quantum dots grown in poly vinyl alcohol and capped with mercaptoethanol

PbS quantum dots capped with mercaptoethanol (C2H5OSH) have been synthesized in poly vinyl alcohol and used to investigate their photoluminescence (PL) response to various ions such as zinc (Zn), cadmium (Cd), mercury (Hg), silver (Ag), copper (Cu), iron (Fe), manganese (Mn), cobalt (Co), chromium (Cr) and nickel (Ni). The enhancement in the PL intensity was observed with specific ions namely Zn, Cd, Hg and Ag. Among these four ions, the PL response to Hg and Ag even at sub-micro-molar concentrations was quite high, compared to that of Zn and Cd. It was observed that the change in Pb and S molar ratio has profound effect on the sensitivity of these ions. These results indicate that the sensitivity of these QDs could be fine-tuned by controlling the S concentration at the surface. Contrary to the above, Cu quenched the photoluminescence. In Cd based QDs related ion probing, Hg and Cu was found to have quenching properties, however, our PbS QDs have quenching property only for Cu ions. This was attributed to the formation HgS at the surface that has bandgap higher than PbS. Another interesting property of PbS in PVA observed is photo-brightening mechanism due to the curing of the polymer with laser. However, the presence of excess ions at the surface changes its property to photo-darkening/brightening that depends on the direction of carrier transfer mechanism (from QDs to the surface adsorbed metal ions or vice-versa). which is an interesting feature for metal ion detectivity

Defect related luminescence in Hg0.2Cd0.8Te nano- and micro-crystals grown by the solvothermal method

The photoluminescence (PL) properties of nano- and micro-crystalline Hg1-xCdxTe (x approximate to 0.8) grown by the solvothermal method have been studied over the temperature range 10-300 K. The emission spectra of the samples excited with 514.5 nm Ar+ laser consist of five prominent bands around 0.56, 0.60, 0.69, 0.78 and 0.92 eV. The entire PL band in this NIR region is attributed to the luminescence from defect centers. The features like temperature independent peak energy and quite sensitive PL intensity, which has a maximum around 50 K is illustrated by the configuration coordinate model. After 50 K, the luminescence shows a thermal quenching behavior that is usually exhibited by amorphous semiconductors, indicating that the defects are related to the compositional disorder. (C) 2010 Elsevier B.V. All rights reserved

Size and temperature dependence of the photoluminescence properties of NIR emitting ternary alloyed mercury cadmium telluride quantum dots

Exciton-phonon coupling and nonradiative relaxation processes have been investigated in near-infrared (NIR) emitting ternary alloyed mercury cadmium telluride (CdHgTe) quantum dots. Organically capped CdHgTe nanocrystals of sizes varying from 2.5-4.2 nm have been synthesized where emission is in the NIR region of 650-855 nm. Temperature-dependent (15-300 K) photoluminescence (PL) and the decay dynamics of PL at 300 K have been studied to understand the photophysical properties. The PL decay kinetics shows the transition from triexponential to biexponential on increasing the size of the quantom dots (QDs), informing the change in the distribution of the emitting states. The energy gap is found to be following the Varshni relation with a temperature coefficient of 2.1-2.8 x 10(-4) eV K-1. The strength of the electron-phonon coupling, which is reflected in the Huang and Rhys factor S, is found in the range of 1.17-1.68 for QDs with a size of 2.5-4.2 nm. The integrated PL intensity is nearly constant until 50 K, and slowly decreases up to 140 K, beyond which it decreases at a faster rate. The mechanism for PL quenching with temperature is attributed to the presence of nonradiative relaxation channels, where the excited carriers are thermally stimulated to the surface defect/trap states. At temperatures of different region (<140 K and 140-300 K), traps of low (13-25 meV) and high (65-140 meV) activation energies seem to be controlling the quenching of the PL emission. The broadening of emission linewidth is found to due to exciton-acoustic phonon scattering and exciton-longitudinal optical (LO) phonon coupling. The exciton-acoustic phonon scattering coefficient is found to be enhanced up to 55 MU eV K-1 due to a stronger confinement effect. These findings give insight into understanding the photophysical properties of CdHgTe QDs and pave the way for their possible applications in the fields of NIR photodetectors and other optoelectronic devices

Interactions between photoexcited NIR emitting CdHgTe quantum dots and graphene oxide

Hydrothermally grown mercury cadmium telluride quantum dots (CdHgTe QDs) are decorated on graphene oxide (GO) sheets through physisorption. The structural change of GO through partial reduction of oxygen functional groups is observed with X-ray photoelectron spectroscopy in GO-QDs composites. Raman spectroscopy provides relatively a small change (similar to 1.1 times) in D/G ratio of band intensity and red shift in G band from 1606 cm(-1) to 1594 cm(-1) in GO-CdHgTe QDs (2.6 nm) composites, which indicates structural modification of GO network. Steady state and time resolved photoluminescence (PL) spectroscopy shows the electronic interactions between photoexcited near infrared emitting CdHgTe QDs and GO. Another interesting observation is PL quenching in the presence of GO, and it is quite effective in the case of smaller size QDs (2.6 nm) compared to the larger size QDs (4.2 nm). Thus, the observed PL quenching is attributed to the photogenerated electron transfer from QDs to GO. The photoexcited electron transfer rate decreases from 2.2 x 10(9) to 1.5 x 10(8) s(-1) with increasing particle size from 2.6 to 4.2 nm. Photoconductivity measurements on QDs-GO composite devices show nearly 3 fold increase in the current density under photo-illumination, which is a promising aspect for solar energy conversion and other optoelectronic applications. (C) 2016 AIP Publishing LLC