Currently conventional sources like coal, petroleum and natural gas meet the energy requirements of developing and undeveloped countries. Over a period of time there is high risk of these energy sources getting depleted. Hence an alternate source of energy i.e. renewable energy is the need of the hour. The advantages of renewable energy like higher sustainability, lesser maintenance, low cost of operation, and minimal impact on the environment make the role of renewable energy sources significant. Out of the various renewable energy sources like solar energy, wind energy, hydropower, biogas, tidal and geothermal, usage of solar energy is gradually increasing. Among various solar energy sources, Photovoltaics has dominated over the past two decades since it is free clean energy and availability of abundant sunlight on earth. Over the past few decades, thin film solar cells (TFSC) have gained considerable interest as an economically feasible alternative to conventional silicon (Si) photovoltaic devices. TFSCs have the potential to be as efficient as Si solar cells both in terms of conversion efficiency as well as cost. The advantages of TFSC are that they are easy to prepare, lesser thickness, requires lesser materials, light weight, low cost and opto-electronic properties can be tuned by varying the process parameters. The present study is focused on the fabrication of AgInS2/ZnS heterojunction thin film solar cell. AgInS2 absorber layer is deposited using both vacuum (sputtering/sulfurization) and non-vacuum (ultrasonic spray pyrolysis) techniques. ZnS window layer is prepared using thermal evaporation technique, detailed experimental investigation has been conducted and the results have been reported in this work. The thesis is divided into 6 chapters. Chapter 1 gives general introduction about solar cells and working principle of solar cell. It also discusses thin film solar cell technology and its advantages. Layers of thin film solar cell structure, Significance of each layers and possible materials to be used are emphasized. A detailed overview of the available literature on both AgInS2 absorber layer and ZnS window layer has been presented. Based on the literature review, objectives of the present work are defined. Chapter 2 explains the theory and experimental details of deposition techniques used for the growth of AgInS2 and ZnS films. Details of characterization techniques to study film properties are described in detail. Chapter 3 presents a systematic study of AgInS2 thin films deposited by sulfurization of sputtered Ag-In metallic precursors. Initially, AgInS2 films are deposited by varying the substrate temperature and properties of as-deposited films are characterized. Structural, morphological, electrical and optical properties of AgInS2 films are explained. From these studies, samples with better properties at particular substrate temperature are optimized. By fixing the substrate temperature, deposition time of silver is varied by keeping other deposition conditions same and the properties of films are discussed. It was observed that deposition time of silver doesn’t have much impact on structural properties of AgInS2 films. However, opto-electric properties of AgInS2 films are enhanced. Based on characterization studies, deposition time of silver is optimized. Deposition time of indium is varied by keeping substrate temperature and silver deposition to optimized value. The properties of as-deposited films are discussed. Based on the above studies, the optimized p type films have a band gap of 1.64 eV, carrier concentration of 1013 ions/cm3 and Resistivity of order 103 Ω-cm. Chapter 4 presents a systematic study of AgInS2 thin films deposited by ultrasonic spray pyrolysis. AgInS2 films are deposited by varying the substrate temperature and properties of as deposited films are characterized. Structural, morphological, electrical and optical properties of AgInS2 films are explained. From these studies, samples with better properties at particular substrate temperature are optimized. By fixing the substrate temperature, concentration of silver molarity in the precursor solution is varied by keeping other deposition conditions same and the properties of films are discussed. Structural, optical and electrical properties of AgInS2 films are enhanced with the increase in silver concentration. Based on characterization studies, concentration of silver is optimized. Similarly concentration of indium molarity in the precursor solution is varied and the properties of as-deposited films are discussed. Finally, sulfur molarity in the precursor solution is varied and properties of films are discussed. It was observed that increasing sulfur after certain limit does not have any effect on the properties of the films. Based on the above studies, this method resulted in the films with resistivity of 103 Ω-cm and band gap of 1.64 eV. These films showed a carrier concentration of 1013 ions/cm3. Chapter 5 describes the growth of ZnS films using thermal evaporation technique. Influence of thickness on the properties of ZnS films is explained. Samples with good crystallinity, high transmission, and wider gap are selected for device fabrication. This p type layer showed a band gap of 3.52 eV. Solar cells have been fabricated using the AgInS2 films developed by both sputtering and ultrasonic spray pyrolysis techniques. A maximum cell efficiency of 0.92 percent has been achieved for the cell with 0.950 µm thick sputtered AgInS2 layer and thermally evaporated 42 nm thick ZnS layer. In comparison, the ultrasonic spray pyrolysis deposited films gave an efficiency of 0.54 percent. These values are comparable to those mentioned in a couple of reports earlier. Chapter 6 summarizes the conclusions drawn from the present investigations and scope of future work is suggested.

Surface- and tip-enhanced resonant Raman scattering (resonant SERS and TERS) by optical phonons in a monolayer of CdSe quantum dots (QDs) is demonstrated. The SERS enhancement was achieved by employing plasmonically active substrates consisting of gold arrays with varying nanocluster diameters prepared by electron-beam lithography. The magnitude of the SERS enhancement depends on the localized surface plasmon resonance (LSPR) energy, which is determined by the structural parameters. The LSPR positions as a function of nanocluster diameter were experimentally determined from spectroscopic micro-ellipsometry, and compared to numerical simulations showing good qualitative agreement. The monolayer of CdSe QDs was deposited by the Langmuir–Blodgett-based technique on the SERS substrates. By tuning the excitation energy close to the band gap of the CdSe QDs and to the LSPR energy, resonant SERS by longitudinal optical (LO) phonons of CdSe QDs was realized. A SERS enhancement factor of 2 × 10³ was achieved. This allowed the detection of higher order LO modes of CdSe QDs, evidencing the high crystalline quality of QDs. The dependence of LO phonon mode intensity on the size of Au nanoclusters reveals a resonant character, suggesting that the electromagnetic mechanism of the SERS enhancement is dominant. Finally, the resonant TERS spectrum from CdSe QDs was obtained using electrochemically etched gold tips providing an enhancement on the order of 10⁴. This is an important step towards the detection of the phonon spectrum from a single QD. / Dieser Beitrag ist aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

Na busca de um melhor entendimento das propriedades eletrônicas e magnéticas dos isolantes topológicos nos deparamos com uma das suas caraterísticas mais marcantes, a existência de estados de superfície metálicos com textura helicoidal de spin os quais são protegidos de impurezas não magnéticas. Na superfície estes canais de spin possuem um potencial enorme para aplicações em dispositivos spintrônicos. Muito há para se fazer e o tratamento via cálculos de primeiros princípios por simulações permite um caráter preditivo que corrobora na elucidação de fenômenos físicos via análises experimentais. Nesse trabalho analisamos as propriedades eletrônicas de isolantes topológicos tais como: (Bi,Sb)$_2$(Te,Se)$_3$, Germaneno e Germaneno funcionalizado. Cálculos baseados em DFT evidenciam a importância das separações entre as camadas de Van der Waals nos materiais Bi$_2$Se$_3$ e Bi$_2$Te$_3$. Mostramos que devido a falhas de empilhamento, pequenas oscilações no eixo de QLs (\\textit{Quintuple Layers}) podem gerar um desacoplamento dos cones de Dirac, além de criar estados metálicos na fase \\textit{bulk} de Bi$_2$Te$_3$. Em se tratando do Bi$_2$Se$_3$ um estudo sistemático dos efeitos de impurezas de metais de transição foi realizado. Observamos que há quebra de degenerescência do cone de Dirac se houver magnetização em quaisquer dos eixos. Além disso se a magnetização permanecer no plano, além de uma pequena quebra de degenerescência, há um deslocamento do mesmo para outro ponto da rede recíproca. No entanto, se a magnetização apontar para fora do plano a quebra ocorre no próprio ponto $\\Gamma$, porém de maneira mais intensa. Importante enfatizar que além de mapear os sítios com suas orientações magnéticas de menor energia observamos que a quebra da degenerescência está diretamente relacionada com a geometria local da impureza. Isso proporciona imagens de STM distintas para cada sítio possível, permitindo que um experimental localize cada situação no laboratório. Estudamos ainda a transição topológica na liga (Bi$_x$Sb$_{1-x}$)$_2$Se$_3$, onde identificamos um isolante trivial e topológico para $x=0$ e $x=1$. Apesar de óbvia a existência de tal transição, detalhes importantes ainda não estão esclarecidos. Concluímos que a dopagem com impurezas não magnéticas proporciona uma boa técnica para manipulação e engenharia de cone nesta família de materiais, de forma que dependendo da faixa de dopagem podemos eliminar a condutividade que advém do \\textit{bulk}. Finalmente estudamos superfícies de Germaneno e Germaneno funcionalizado com halogênios. Usando uma funcionalização assimétrica e com a avalição do invariante topológico $Z_2$ notamos que o material Ge-I-H é um isolante topológico podendo ser aplicado na elaboração de dispositivos baseados em spin. / In the search of a better understanding of the electronic and magnetic properties of topological insulators we are faced with one of its most striking features, the existence of metallic surface states with helical spin texture which are protected from non-magnetic impurities. On the surface these spin channels allows a huge potential for applications in spintronic devices. There is much to do and treating calculations via \\textit{Ab initio} simulations allows us a predictive character that corroborates the elucidation of physical phenomena through experimental analysis. In this work we analyze the electronic properties of topological insulators such as: (Bi, Sb)$_2$(Te, Se)$_3$, Germanene and functionalized Germanene. Calculations based on DFT show the importance of the separation from interlayers of Van der Waals in materials like Bi$_2$Se$_3$ and Bi$_2$Te$_3$. We show that due to stacking faults, small oscillations in the QLs axis (\\textit{Quintuple Layers}) can generate a decoupling of the Dirac cones and create metal states in the bulk phase Bi$_2$Te$_3$. Regarding the Bi$_2$Se$_3$ a systematic study of the effects of transition metal impurities was performed. We observed that there is a degeneracy lift of the Dirac cone if there is any magnetization on any axis. If the magnetization remains in plane, we observe a small shift to another reciprocal lattice point. However, if the magnetization is pointing out of the plane a lifting in energy occurs at the very $ \\Gamma $ point, but in a more intense way. It is important to emphasize that in addition to mapping the sites with their magnetic orientations of lower energy we saw that the lifting in energy is directly related to the local geometry of the impurity. This provides distinct STM images for each possible site, allowing an experimental to locate each situation in the laboratory. We also studied the topological transition in the alloy (Bi$_x$Sb$_{1-x}$)$_ 2$Se$_3$, where we identify a trivial and topological insulator for $x = 0$ and $x = 1$. Despite the obvious existence of such a transition, important details remain unclear. We conclude that doping with non-magnetic impurities provides a good technique for handling and cone engineering this family of materials so that depending on the range of doping we can eliminate conductivity channels coming from the bulk. Finally we studied a Germanene and functionalized Germanene with halogens. Using an asymmetrical functionalization and with the topological invariant $Z_2$ we noted that the Ge-I-H system is a topological insulator that could be applied in the development of spin-based devices.

High quality ammonium oxofluorotitanate discoid crystal is successfully grown on glass with an aqueous solution of ammonium hexafluorotitanate and boric acid at the molar ratio of 0.6. The concentration of hydrofluoric acid is less on the glass substrate surface and enhances the ammonium oxofluorotitanate nucleation growth. The growth rate is much higher than that grown on dioctadecyldimethylammonium. From the examinations of X-ray diffraction and high-resolution transmission electron microscopy, the crystal shows high crystalline quality and uniformity. Each titanium oxide octahedral is linked with fluorine and nitrogen atoms. Therefore, ammonium oxofluorotitanate has high potential to be thermally decomposed into high crystalline fluorine and nitrogen co-doped titanium oxide. A simple process for the preparation of nanocrystalline anatase phase titanium oxide converted from ammonium oxofluorotitanate by thermal treatment was developed. The nanocrystalline anatase phase titanium oxide shows a large bandgap reduction due to the co-doping of high concentrations of fluorine and nitrogen. Due to the excellent nanocrystalline quality and the co-doping of higher concentrations of fluorine and nitrogen at the thermal treatment temperature of 800 OC, it is 1.3 times the photocatalytic activities of P-25 due to the visble region usage of Hg lamp light source. The 11.2 times the visible photocatalytic activities of P-25 using blue light-emitting diode as the light source is obtained from thermal treatment temperature of 600 OC. There is one to one correspondence between carrier lifetime and photocatalytic activity. As a result, a highly reactive and visible-light-driven photocatalysis is achieved. The heterostructure of zinc selenide/titanium oxide and zinc sulfide/titanium oxide were prepared by metal-organic chemical vapor deposition on the above-prepared titanium oxide. The energy bandgap of zinc sulfide is much larger than that of titanium oxide and can act as a window for titanium oxide. It would not hinder titanium oxide absorption and preserve the role of fluorine and nitrogen co-doping. The energy bandgap of zinc selenide is near the maximum intensity of solar spectrum and acts as a sensitizer of titanium oxide. The lifetime of electron and hole pairs of heterostructure are about 240 and 207 nsec, which are longer than 65 nsec of titanium oxide prepared at 800 oC thermal treatment. Their photocatalytic activities are further improved to 2.0 and 1.5 times higher than that of commercial P-25. The photocatalysis of titanium oxide is very sensitive to the surface states. Titanium oxide surface defects can act as trapping sites for photo-induced holes and facilitate the separation of photo-induced carriers. Zinc selenide and zinc sulfide can passivate the surface well. It may say that titanium oxide surface defects removal has a negative impact. The density, height, diameter, PL wavelength and intensity of zinc selenide self-assembled quantum dots grown on zinc sulfide/gallium arsenide with the zinc sulfide thickness from 15 to 160 nm are studied. For a fixed 30 sec zinc selenide self-assembled quantum dots growth, it cannot be formed with the zinc sulfide thickness below 15 nm due to the close lattice match between zinc sulfide and gallium arsenide. The zinc sulfide/gallium arsenide is fully lattice relaxed with the zinc sulfide thickness higher than 130 nm examined by X-ray diffraction. The higher quality and density of zinc selenide self-assembled quantum dots can be obtained on zinc sulfide/gallium arsenide with the zinc sulfide thickness far beyond its critical thickness. The maximum zinc selenide self-assembled quantum dots density of 4.9 x 109 cm-2 with the strongest photoluminescence intensity is obtained at the zinc sulfide/gallium arsenide thickness of 130 nm. Clusters are formed on the surface of zinc selenide/gallium arsenide. The selenium segregation is the main mechanism for the formation of clusters. The dislocations will enhance the selenium segregation. Higher zinc selenide cluster corresponds to higher density of dislocations. The non-spherical cluster is formed from the mergence of the two clusters. High quality zinc oxide rods and zinc hydroxide slices are successfully grown on gallium arsenide with the aqueous solution of zinc nitrate and hexamethylenetetramine. The growth can be controlled by the appropriate nitric acid concentration incorporation in the solution. After thermal annealing, the zinc oxide slices transformed from zinc hydroxide slices can contribute much higher photocatalytic activity to 1.2 times to P-25.

Na busca de um melhor entendimento das propriedades eletrônicas e magnéticas dos isolantes topológicos nos deparamos com uma das suas caraterísticas mais marcantes, a existência de estados de superfície metálicos com textura helicoidal de spin os quais são protegidos de impurezas não magnéticas. Na superfície estes canais de spin possuem um potencial enorme para aplicações em dispositivos spintrônicos. Muito há para se fazer e o tratamento via cálculos de primeiros princípios por simulações permite um caráter preditivo que corrobora na elucidação de fenômenos físicos via análises experimentais. Nesse trabalho analisamos as propriedades eletrônicas de isolantes topológicos tais como: (Bi,Sb)$_2$(Te,Se)$_3$, Germaneno e Germaneno funcionalizado. Cálculos baseados em DFT evidenciam a importância das separações entre as camadas de Van der Waals nos materiais Bi$_2$Se$_3$ e Bi$_2$Te$_3$. Mostramos que devido a falhas de empilhamento, pequenas oscilações no eixo de QLs (\\textit{Quintuple Layers}) podem gerar um desacoplamento dos cones de Dirac, além de criar estados metálicos na fase \\textit{bulk} de Bi$_2$Te$_3$. Em se tratando do Bi$_2$Se$_3$ um estudo sistemático dos efeitos de impurezas de metais de transição foi realizado. Observamos que há quebra de degenerescência do cone de Dirac se houver magnetização em quaisquer dos eixos. Além disso se a magnetização permanecer no plano, além de uma pequena quebra de degenerescência, há um deslocamento do mesmo para outro ponto da rede recíproca. No entanto, se a magnetização apontar para fora do plano a quebra ocorre no próprio ponto $\\Gamma$, porém de maneira mais intensa. Importante enfatizar que além de mapear os sítios com suas orientações magnéticas de menor energia observamos que a quebra da degenerescência está diretamente relacionada com a geometria local da impureza. Isso proporciona imagens de STM distintas para cada sítio possível, permitindo que um experimental localize cada situação no laboratório. Estudamos ainda a transição topológica na liga (Bi$_x$Sb$_{1-x}$)$_2$Se$_3$, onde identificamos um isolante trivial e topológico para $x=0$ e $x=1$. Apesar de óbvia a existência de tal transição, detalhes importantes ainda não estão esclarecidos. Concluímos que a dopagem com impurezas não magnéticas proporciona uma boa técnica para manipulação e engenharia de cone nesta família de materiais, de forma que dependendo da faixa de dopagem podemos eliminar a condutividade que advém do \\textit{bulk}. Finalmente estudamos superfícies de Germaneno e Germaneno funcionalizado com halogênios. Usando uma funcionalização assimétrica e com a avalição do invariante topológico $Z_2$ notamos que o material Ge-I-H é um isolante topológico podendo ser aplicado na elaboração de dispositivos baseados em spin. / In the search of a better understanding of the electronic and magnetic properties of topological insulators we are faced with one of its most striking features, the existence of metallic surface states with helical spin texture which are protected from non-magnetic impurities. On the surface these spin channels allows a huge potential for applications in spintronic devices. There is much to do and treating calculations via \\textit{Ab initio} simulations allows us a predictive character that corroborates the elucidation of physical phenomena through experimental analysis. In this work we analyze the electronic properties of topological insulators such as: (Bi, Sb)$_2$(Te, Se)$_3$, Germanene and functionalized Germanene. Calculations based on DFT show the importance of the separation from interlayers of Van der Waals in materials like Bi$_2$Se$_3$ and Bi$_2$Te$_3$. We show that due to stacking faults, small oscillations in the QLs axis (\\textit{Quintuple Layers}) can generate a decoupling of the Dirac cones and create metal states in the bulk phase Bi$_2$Te$_3$. Regarding the Bi$_2$Se$_3$ a systematic study of the effects of transition metal impurities was performed. We observed that there is a degeneracy lift of the Dirac cone if there is any magnetization on any axis. If the magnetization remains in plane, we observe a small shift to another reciprocal lattice point. However, if the magnetization is pointing out of the plane a lifting in energy occurs at the very $ \\Gamma $ point, but in a more intense way. It is important to emphasize that in addition to mapping the sites with their magnetic orientations of lower energy we saw that the lifting in energy is directly related to the local geometry of the impurity. This provides distinct STM images for each possible site, allowing an experimental to locate each situation in the laboratory. We also studied the topological transition in the alloy (Bi$_x$Sb$_{1-x}$)$_ 2$Se$_3$, where we identify a trivial and topological insulator for $x = 0$ and $x = 1$. Despite the obvious existence of such a transition, important details remain unclear. We conclude that doping with non-magnetic impurities provides a good technique for handling and cone engineering this family of materials so that depending on the range of doping we can eliminate conductivity channels coming from the bulk. Finally we studied a Germanene and functionalized Germanene with halogens. Using an asymmetrical functionalization and with the topological invariant $Z_2$ we noted that the Ge-I-H system is a topological insulator that could be applied in the development of spin-based devices.

The objective of this study is analysing the characteristics of five different solar cell technologies regarding their efficiency, fill factor, cost and environmental impacts and comparing their improvement records over years considering their efficiency. The five solar cell technologies of interest are amorphous silicon, monocrystalline silicon, polycrystalline silicon, cupper indium gallium selenide thin film and cadmium telluride thin film. The structure and manufacturing process of each of cell technologies were discussed. The study was conducted by the aid of available scientific reports regarding the electrical characteristics of different solar cell technologies. The extracted information regarding efficiency rate and fill factor was analysed using graphs and significant findings are discussed. The five technologies are also compared regarding their cost and ease of fabrication and their impacts on environment and recycling challenges. The result of this study is suggesting the most promising technology that may be the optimal option for further investment and research.

Over the last few decades, a vast research is going on, to study the optical properties of the nano particles i.e., metal and semiconductors thoroughly. Till date most of the optical studies are based on single particle measurement of a quantum dot (QD) or a chromophore under the influence of an external plasmonic field stimulus. In this the-sis, we tried to address the energy transfer at non local level on a layer of compact, monolayer QD assemblies over micro meter range. The energy transfer occurs in the presence of external field of metal particles or nanorods leads to the enhancement or quenching the emission from a layer of QDs. Chapter 1 is introduction to the basic theoretical aspects of excitons in semiconductor (QDs) and its optical properties under strong confinement regime. The discussion is followed with the optical properties of gold nanoparticles and rods, describing size and shape dependent variation of absorption properties, based on Mie and Mie-Gans theory. Theoretical background of collective effects in QD assemblies based on exciton-plasmonic interactions at single particle level as well as polarization based plasmo-nenhanced fluorescence has been subjected. Experimental techniques are explained in chapter 2 which contains the details of the synthesis of polymer capped nanoparticles with the respective characterization. A discussion on the synthesis methods for cadmium selenide QDs, gold nano particles and the rods with different polymer cap-ping legends and the related capping exchange methods. The thin film preparation of QD monolayers as well as hybrid nano assemblies using several techniques, i.e., Langmuir-Blodgett (LB), dip coat methods are provided. Further the details of surface morphology of the prepared thin films has been studied by different microscopic techniques i.e., atomic force microscopy (AFM), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The details of the PL emission measurements of these hybrid arrays using confocal, Raman and polarization based near field scanning optical microscope (NSOM) modes followed with the life time measurements. In third chapter, the substantial strong coupling and collective emission regime is engineered in the QD monolayer films embedded with tiny gold nano particles keeping the QD density same. Tuning the photoluminescence (PL) of semiconducting QD assemblies using small Au NPs in different ratio, different packing density and extent of spectral overlap between QD photoluminescence and the metal nanoparticle absorbance has been discussed. We provided possible experimental and theoretical evidence for the plasmon-mediated emergence of collective emission and enhanced quantum efficiency in these QD films with the consolidation of multiple emitters and multiple NPs. The quantum efficiency of these hybrid assemblies is further explored with different material as well as the size effect of metal nano particles. Chapter 4 comprises the experiment results of the self-assembled compact and partially aligned gold nano rod (GNR) arrays on QD monolayer films. We experimentally demonstrated the quantum efficiency of these QD hybrid assemblies is gaining max-imum when the longitudinal surface plasmon resonance (LSPR) absorption maxima of GNR arrays is resonant with the QD monolayer PL maxima and is always non-existent for the off resonant case. Further, we reported the variability in the size and morphology of these GNR domains leads to the maximum achieved enhancement as well as anisotropy value in comparison with isolated rods and the explored conditions to further enhance the efficiency in these QD hybrid assemblies.

In recent years, there has been an increasing interest on renewable energy sources as substitute to fossil fuels. Among various processes of energy generation, electrochemical methods such as storage and conversion systems, electrolysis of water (production of H2 and O2), fuel cells, batteries, supercapacitors and solar cells have received great attention. The core of these energy technologies is a series of electrochemical processes, which directly depend on the nature of ‘electro catalyst’. The design and preparation of an electro catalyst is based on new concepts such as controlled surface roughness, atomic topographic profiles, defined catalytic sites, atomic rearrangements, and phase transitions during electrochemical reactions. Good electro catalysts should possess low over potential, high exchange current density, high stability, low cost and high abundance. The most fundamental reactions in the area of electrochemistry are hydrogen evolution (HER) and oxygen reduction (ORR) reactions. They are important in different energy systems such as fuel cells and batteries. Platinum has been a favoured electro catalyst due to its high activity, favourable density of states at Fermi level and chemical inertness. The low abundance, however, limits its large scale applications. Alternate materials with high catalytic activities are always required. In this particular direction, metal chalcogenides such as sulphides and selenides have attracted attention in recent years. The present thesis describes the synthesis of different phases of palladium and nickel chalcogenides and their applicability in various electrochemical reactions, both in aqueous and organic media. First part includes the synthesis of highly crystalline palladium selenide phases namely Pd17Se15, Pd7Se4 and Pd4Se by employing facile single source molecular precursor method. Pure palladium selenide phases are prepared by thrombolysis of highly processable intermediate complexes formed from metal and selenium precursors. Continuous films of different dimensions on various substrates (glass, ITO, FTO etc.) could be prepared (figure 1). This is one of the requirements for processing any new material. Thickness of the films could be altered by changing the volume of precursor complex coated on the substrate. All the phases are found to be metallic in nature with resistivity values in the range of 30 to 180 µΩ.cm. Figure 1. (a) Scanning electron micrograph and (b) photographic image of Pd17Se15 prepared on different substrates glass (1), Si (2), fluorine doped tin oxide (FTO) (3) and DSSC solar cell fabricated using FTO coated Pd17Se15 as the counter electrode (4). Other components of DSSC are given in the experimental section. All the palladium selenides phases are shown to be catalytically active towards electrochemical reactions such as HER and ORR. It is observed that the activities of the phases depend on the stoichiometric ratio of palladium to selenium. Higher the palladium content in the phase, higher is the catalytic activity observed. Therefore, the activities of the chalcogenides can be easily tuned by varying the ratio of metal to chalcogen. Tafel slopes of 50–60 mV/decade are observed for all three phases towards HER indicating that Volmer- Heyrovsky mechanism is operative. The exchange current densities are in the range of 2.3 x 10-4 A cm-2 to 6.6 x 10-6 A cm-2 (figure 2a). Figure 2. (a) Linear sweep voltammograms of Pd17Se15, Pd7Se4 and Pd4Se in 0.5 M H2SO4 (HER) and (b) 0.1 M KOH (ORR) at a scan rate of 2 mVs-1. These phases are found to be highly robust and stable under different pH conditions. Stability of the phases is confirmed by characterizing the catalysts post-HER process, using various techniques such as XPS, XRD and SEM. High activities observed for Pd4Se is explained based on electrochemically active surface area values determined from under potential deposition studies and also based on DFT calculations. Computational studies reveal the presence of different charge distribution on palladium in all the three phases which is likely to be another reason for varied activities. Palladium selenides are also explored as catalysts towards ORR in alkaline medium. Kinetic parameters and reaction mechanism are determined using RDE studies. All the three phases are found to be active and Pd4Se shows the highest activity, following a direct 4 electron reduction pathway (figure 2b). Other two phases follow 2 electron pathway terminating at hydrogen peroxide stage. Catalytic activity of Pd17Se15 is further improved by Nano structuring of the material and by synthesizing the material on active supports such as rGO, acetylene black and today carbon. ORR plays an important role in metal-air batteries. The palladium chalcogenides are used as electrodes in metal-air batteries. Specific energy density observed in the case of Mg-air primary batteries is higher for Pd4Se than the other two phases (figure 3a). Figure 3. (a) Discharge curves of Mg-O2 battery with different phases of palladium selenides as cathodes. Constant current density of 0.5 mA cm-2 is used for discharge. (b) Characteristic J–V curves of DSSCs with Pd17Se15, Pd7Se4 and Pt as counter electrodes. Versatility of these phases is further studied towards redox reaction in non-aqueous medium (I3-/I-). This reaction plays a crucial role in the regeneration of the dye in dye-sensitized solar cells (DSSC). Palladium selenide phases prepared on FTO plates are employed as counter electrodes in DSSC. The solar light conversion efficiencies are found to be 7.45 and 6.8% for Pd17Se15 and Pd7Se4 respectively and are comparable to that of platinum (figure 3b). The reason for high activities may be attributed to high electronic conductivity and low work function of the phases. The following chapter deals with the synthesis of palladium sulphide phases (Pd4S and Pd16S7) using both hydrothermal and single source precursor methods. Electro catalytic activities of the phases are shown towards HER and ORR and Pd4S exhibits better catalytic activities than that of Pd16S7 phase. Direct electrochemistry of cytochrome c is achieved on Pd4S with ∆E of ~64 mV (figure 4a). Electrochemical oxidation of ethanol, ethylene glycol (EG) and glycerol are also studied on the Pd4S phase and the activity is found to follow the order, glycerol > ethylene glycol > ethanol (figure 4b). Figure 4. (a) Cyclic voltammograms of Pd4S in (1) 0.1 M phosphate buffer solution (pH 7.0) and (2) in presence of 0.2 mM cytochrome c at a scan rate of 50 mVs-1 and (b) Voltammograms of Pd4S in presence of different alcohols (ethanol, EG and glycerol) in 1 M KOH solution at sweep rate of 50 mVs-1. Concentration of alcohols used is 0.1 M. The effect of dimensionality on the electro catalytic activity of nickel selenide phases forms part of the next chapter. Nickel selenide (NiSe) nanostructures possessing different morphologies of wires, spheres and hexagons are synthesized by varying the selenium precursors namely, selenourea, selenium dioxide (SeO2) and potassium selenocyanate (KSeCN), respectively using hydrothermal method. The different selenium precursors result in morphologies that are probably dictated by the by-products as well as relative rates of amorphous selenium formation and dissolution. The three different morphologies are used as catalysts for HER, ORR and glucose oxidation reactions. The wire morphology is found to be better than that of spheres and hexagons for all the reactions. Among the reactions studied, NiSe is found to be good for HER and glucose oxidation while ORR seems to terminate at the peroxide stage. In alkaline medium, nickel forms hydroxides and oxy-hydroxides and these oxyhydroxides are catalytically active towards the oxidation of glucose. Therefore, nickel selenides are employed as highly selective non-enzymatic glucose sensors and detection limit of 5 µM is observed. Electrical measurements on a single nanowire and a hexagon morphology of NiSe are carried out on devices fabricated by focused ion beam (FIB) technique (figure 5). The semiconducting nature of NiSe is revealed in the I-v measurements. The band gap of the material is found to be 1.9 eV and hence the single nanowire and hexagon are shown to act as visible light photodetector. Figure 5. SEM images of (a) single NiSe nanowire and (b) single NiSe hexagon with Pt contacts fabricated by FIB technique. Figure 6. Cyclic voltammograms of NiSe nanowires in 0.5 M aqueous NaOH in the (i) absence and (ii) the presence of 0.5 mM glucose, at a scan rate of 20 mVs-1 and (b) Galvanostatic discharge performance of Ni3Se2 with different morphologies (A, B and C represent Ni3Se2 prepared from SeO2, selenourea and KSeCN respectively). The next chapter includes the synthesis of different morphologies of Ni3Se2 using three different selenium precursors (SeO2, KSeCN and selenourea) and the study of their activities towards electrochemical reactions such as HER and glucose oxidation (figure 6a). Electrical measurements demonstrated the metallic behaviour of the material. These are also shown to be efficient electrode materials in energy storage devices such as supercapacitors with high specific capacitance of 2200 F/g (figure 6b). The studies are summarized in the last chapter with scope for further work. The appendixes show preliminary studies on electrooxidation of glycerol and propanol on Pd supported on TiN, synthesis of other selenides of Ni, Cu, Ag and Ti, and electro synthesis of metal-organic frameworks. (For figures pl refer the abstract pdf file)

A straightforward, rapid method to create colloidally stable and brightly luminescent core/shell CdSe-based nanoplatelets (NPLs) with fluorescence quantum yields (QYs) up to 50% is demonstrated. A layer-by-layer deposition technique based on a two-phase mixture ‒ consisting of a nonpolar phase which includes the NPLs, and a saturated ionic polar phase ‒ to separate the reagents and hinder the nucleation of the shell material is used. The deposition of the first sulfur layer leads to a significant red-shift (by more than 100 nm) of the optical absorption and emission of the NPLs. Hence, by varying either the sulfur precursor content or the reaction time one can precisely and continuously tune the absorption and emission maxima from 520 to 630 nm. This evolution of the absorption onset during the shell growth is explained quantitatively using density-functional theory and atomistic statistical simulations. The emission can be further enhanced by exposure of the NPL solution to ambient sunlight. Finally, it is demonstrated that the core/shell NPLs can be transferred from the organic solution to aqueous media with no reduction of their QY that opens the door to a broad range of practical applications.

Surface- and tip-enhanced resonant Raman scattering (resonant SERS and TERS) by optical phonons in a monolayer of CdSe quantum dots (QDs) is demonstrated. The SERS enhancement was achieved by employing plasmonically active substrates consisting of gold arrays with varying nanocluster diameters prepared by electron-beam lithography. The magnitude of the SERS enhancement depends on the localized surface plasmon resonance (LSPR) energy, which is determined by the structural parameters. The LSPR positions as a function of nanocluster diameter were experimentally determined from spectroscopic micro-ellipsometry, and compared to numerical simulations showing good qualitative agreement. The monolayer of CdSe QDs was deposited by the Langmuir–Blodgett-based technique on the SERS substrates. By tuning the excitation energy close to the band gap of the CdSe QDs and to the LSPR energy, resonant SERS by longitudinal optical (LO) phonons of CdSe QDs was realized. A SERS enhancement factor of 2 × 10³ was achieved. This allowed the detection of higher order LO modes of CdSe QDs, evidencing the high crystalline quality of QDs. The dependence of LO phonon mode intensity on the size of Au nanoclusters reveals a resonant character, suggesting that the electromagnetic mechanism of the SERS enhancement is dominant. Finally, the resonant TERS spectrum from CdSe QDs was obtained using electrochemically etched gold tips providing an enhancement on the order of 10⁴. This is an important step towards the detection of the phonon spectrum from a single QD. / Dieser Beitrag ist aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.