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The thesis describes the synthesis of PbS nano-, micro-structures by colloidal and hydrothermal techniques. Size and morphology dependent luminescence studies were carried out in detail. Application oriented studies like ion sensing and modulation of luminescence are carried out on colloidal PbS QDs. Photoelectrical studies are carried out on various morphologies of PbS microstructures. We observe the persistent photoconductivity, growth and quenching of photocurrent, and a few novel phenomena in flower shaped PbS microstructures. This work is presented in eight chapters inclusive of summary and directions for future work. CHAPTER 1 provides a brief introduction to optical and photoelectrical properties of semiconductor quantum dots and hydrothermal technique in preparation of quantum structures. A review of PbS nanostructures and its technological applications are discussed. CHAPTER 2 provides the experimental techniques used in this work. First, the synthesis of PbS nano-, micro-structures by various methods, and characterization tools used in this work are briefly presented. CHAPTER 3 deals with the synthesis of PbS quantum dots in poly vinyl alcohol with various precursor concentrations to identify the surface states by temperature dependent photoluminescence (PL) measurements. Average bandgap value calculated from absorption measurements was 2.1 eV. We have observed that high-energy PL bands (>1.3 eV) are due to electron traps (Pb dangling bonds) and low-energy bands (<1 eV) are due to hole traps (S dangling bonds). By capping with thiol compounds (mercaptoethanol-C2 H5OSH), absence of the 1.67 eV band indicates the passivation of Pb dangling bonds. To explain above observed results, we propose a band diagram with distributed shallow to deep states and attributed them to the specific surface related defects (Pb or S). CHAPTER 4 discusses the ion sensing applications of PbS quantum dots. We found that the sulfur related dangling bonds are quite sensitive to different metallic ions (since mercaptoethanol passivates only Pb atoms). Sulfur related PL band (~ 1 eV) have shown an order of magnitude improvement in its intensity for Hg, Ag ions and relatively low enhancement for Zn, Cd ions at 1 µmol concentrations. However Cu quenches the luminescence. An important distinction may have to be made between PbS and Cd related quantum structures. The PbS QDs can distinguish between Cu & Hg, however Cd related QDs couldn’t distinguish between these two ions. Photo-brightening and photo-darkening is an interesting phenomena indicative of photo-induced ionic migration that either helps in enhancing the emission of sulfur related defect emission or degrades the emission properties depending on the ion concentration. This report is the first of its kind in ion sensing applications using PbS QDs. CHAPTER 5 discusses the results of duel beam excitation on trap luminescence of PbS QDs. By using different lasers simultaneously (514 nm and 670 nm), we have observed the reversible luminescence quenching of trap emission. The high-energy PL band (1.67 eV) has double the quenching effect compared to low-energy PL band (1.1 eV). The luminescence quenching mechanism is attributed to the re-emission of the charge carriers from the traps (photo-ionization) due to the simultaneous excitation with the second beam. The dependence of the temperature, the effect of two beam excitation intensities and modulation frequency dependent quenching mechanism are primarily focused in this chapter. The quenching mechanism is considered to be quite useful in the optical modulation devices. CHAPTER 6 discusses the PL results on various morphologies of PbS nano-, microstructures. Interestingly, after protecting the surface with organic ligands such as mercaptoethanol (C2 H5OSH), dendrite structures have shown high-energy bands (~ 1.0 eV) in the PL spectra, which indicate the existence of various quantum confinement regimes in different branches of dendrites. The anomalous temperature dependent behavior of PL intensity is attributed to the size distribution. CHAPTER 7 discusses the results of photoconductivity measurements on various morphologies of PbS nano-, micro-structures. Flower shaped structures have shown persistent photoconductivity (PPC). This observed PPC is attributed to the presence of potential barriers, which are created by the different confinement regimes or due to the lattice relaxation, which occurs due to the carrier trapping at surfaces. In PPC, the estimated time constants of both build up and decay transients using the stretched exponentials are of the order of few tens of seconds. In PPC measurements, we observe the PC quenching below 40 K and growth above this temperature. PC quenching is attributed to the transfer of photo-excited carriers to a metastable state. The presence of metastable state is supported by the dark conductivity measurements in flower shaped structures. CHAPTER 8 presents the summary and directions for the future work.

Solution-processed lead sulfide quantum dots (PbS QDs) are an excellent candidate for photodetector applications because they exhibit broadband absorption, a wide range of tuneable bandgaps, high stability in air, and mechanical flexibility. However, a crucial criterion for the fabrication of high-performance photodetectors is the selection of the ligands, which can facilitate charge carrier transport between the PbS QDs and passivate the surface defects. In this work, the authors have studied the effect of traps on the performance of PbS QD photodetectors that are fabricated using different types of ligands, using intensity-dependent photoresponse dynamics. The best devices with lead halide ligands show a dark current density of 5 × 10−9 A cm−2 at −0.2 V, which is one of the lowest values reported thus far for solution-processed PbS QD-based photodetectors. Moreover, these devices show a high linear dynamic range (≈90 dB) and high detectivity (>1013 Jones), in addition to an f-3 dB of greater than 100 kHz without the application of an external voltage bias at a wavelength of 784 nm. These results suggest that with an appropriate selection of ligands, solution-processed photodetectors with a lower density of traps and a better device performance can be fabricated.