Preparation and Study of Optical Properties of CdS, CdS-TiO2 and CdS-Au Nanocomposites for Photonic Applications

Nanophotonics can be regarded as a fusion of nanotechnology and photonics and it is an emerging field providing researchers opportunities in fundamental science and new technologies. In recent times many new methodsand techniques have been developed to prepare materials at nanoscale dimensions. Most of these materials exhibit unique and interesting optical properties and behavior. Many of these have been found to be very useful to develop new devices and systems such as tracers in biological systems, optical limiters, light emitters and energy harvesters. This thesis presents a summary of the work done by the author in the field by choosing a few semiconductor systems to prepare nanomaterials and nanocomposites. Results of the study of linear and nonlinear optical properties of materials thus synthesized are also presented in the various chapters of this thesis. CdS is the material chosen here and the methods and the studies of the detailed investigation are presented in this thesis related to the optical properties of CdS nanoparticles and its composites. Preparation and characterization methods and experimental techniques adopted for the investigations were illustrated in chapter 2 of this thesis. Chapter 3 discusses the preparation of CdS, TiO2 and Au nanoparticles. We observed that the fluorescence behaviour of the CdS nanoparticles, prepared by precipitation technique, depends on excitation wavelength. It was found that the peak emission wavelength can be shifted by as much as 147nm by varyingthe excitation wavelengths and the reason for this phenomenon is the selective excitation of the surface states in the nanoparticles. This provided certain amount of tunability for the emission which results from surface states.TiO2 nanoparticle colloids were prepared by hydrothermal method. The optical absorption study showed a blue shift of absorption edge, indicating quantum confinement effect. The large spectral range investigated allows observing simultaneously direct and indirect band gap optical recombination. The emission studies carried out show four peaks, which are found to be generated from excitonic as well as surface state transitions. It was found that the emission wavelengths of these colloidal nanoparticles and annealed nanoparticles showed two category of surface state emission in addition to the excitonic emission. Au nanoparticles prepared by Turkevich method showed nanoparticles of size below 5nm using plasmonic absorption calculation. It was also found that there was almost no variation in size as the concentration of precursor was changed from 0.2mM to 0.4mM.We have observed SHG from CdS nanostructured thin film prepared onglass substrate by chemical bath deposition technique. The results point out that studied sample has in-plane isotropy. The relative values of tensor components of the second-order susceptibility were determined to be 1, zzz 0.14, xxz and 0.07. zxx These values suggest that the nanocrystals are oriented along the normal direction. However, the origin of such orientation remains unknown at present. Thus CdS is a promising nonlinear optical material for photonic applications, particularly for integrated photonic devices. CdS Au nanocomposite particles were prepared by mixing CdS nanoparticles with Au colloidal nanoparticles. Optical absorption study of these nanoparticles in PVA solution suggests that absorption tail was red shifted compared to CdS nanoparticles. TEM and EDS analysis suggested that the amount of Au nanoparticles present on CdS nanoparticles is very small. Fluorescence emission is unaffected indicating the presence of low level of Au nanoparticles. CdS:Au PVA and CdS PVA nanocomposite films were fabricated and optically characterized. The results showed a red-shift for CdS:Au PVA film for absorption tail compared to CdS PVA film. Nonlinear optical analysis showed a huge nonlinear optical absorption for CdS:Au PVA nanocomposite and CdS:PVA films. Also an enhancement in nonlinear optical absorption is found for CdS:Au PVA thin film compared to the CdS PVA thin film. This enhancement is due to the combined effect of plasmonic as well as excitonic contribution at high input intensity. Samples of CdS doped with TiO2 were also prepared and the linear optical absorption spectra of these nanocompositeparticles clearly indicated the influence of TiO2 nanoparticles. TEM and EDS studies have confirmed the presence of TiO2 on CdS nanoparticles. Fluorescence studies showed that there is an increase in emission peak around 532nm for CdS nanoparticles. Nonlinear optical analysis of CdS:TiO2 PVA nanocomposite films indicated a large nonlinear optical absorption compared to that of CdS:PVA nanocomposite film. The values of nonlinear optical absorption suggests that these nanocomposite particles can be employed for optical limiting applications. CdSe-CdS and CdSe-ZnS core-shell QDs with varying shell size were characterized using UV–VIS spectroscopy. Optical absorption and TEM analysis of these QDs suggested a particle size around 5 nm. It is clearly shown that the surface coating influences the optical properties of QDs in terms of their size. Fluorescence studies reveal the presence of trap states in CdSe-CdS and CdSe- ZnS QDs. Trap states showed an increase as a shell for CdS is introduced and increasing the shell size of CdS beyond a certain value leads to a decrease in the trap state emission. There is no sizeable nonlinear optical absorption observed. In the case of CdSe- ZnS QDs, the trap state emission gets enhanced with the increase in ZnS shell thickness. The enhancement of emission from trap states transition due to the increase in thickness of ZnS shell gives a clear indication of distortion occurring in the spherical symmetry of CdSe quantum dots. Consequently the nonlinear optical absorption of CdSe-ZnS QDs gets increased and the optical limiting threshold is decreased as the shell thickness is increased in respect of CdSe QDs. In comparison with CdSe-CdS QDs, CdSe-ZnS QDs possess much better optical properties and thereby CdSe-ZnS is a strong candidate for nonlinear as well as linear optical applications.

Thermo- Optic and Nonlinear-Optical studies on CdSe Quantum Dots for Photonic Applications

In general, linear- optic, thermo- optic and nonlinear- optical studies on CdSe QDs based nano uids and their special applications in solar cells and random lasers have been studied in this thesis. Photo acous- tic and thermal lens studies are the two characterization methods used for thermo- optic studies whereas Z- scan method is used for nonlinear- optical charecterization. In all these cases we have selected CdSe QDs based nano uid as potential photonic material and studied the e ect of metal NPs on its properties. Linear optical studies on these materials have been done using vari- ous characterization methods and photo induced studies is one of them. Thermal lens studies on these materials give information about heat transport properties of these materials and their suitability for applica- tions such as coolant and insulators. Photo acoustic studies shows the e ect of light on the absorption energy levels of the materials. We have also observed that these materials can be used as optical limiters in the eld of nonlinear optics. Special applications of these materials have been studied in the eld of solar cell such as QDSSCs, where CdSe QDs act as the sensitizing materials for light harvesting. Random lasers have many applications in the eld of laser technology, in which CdSe QDs act as scattering media for the gain.

Systematic Storytelling: Interactivity, Agency and Non-linear Narratives

In this lecture we go over the fundamentals of interactive game narratives. Defining what we mean by narrative, and placing games in context with other ergodic literature. We look at non-linear structures, agency, and the narrative paradox. Concluding with a set of mechanisms that games designers use to manage agency in their narrative games.

Non-commutative symbolic coding

We give a non-commutative generalization of classical symbolic coding in the presence of a synchronizing word. This is done by a scattering theoretical approach. Classically, the existence of a synchronizing word turns out to be equivalent to asymptotic completeness of the corresponding Markov process. A criterion for asymptotic completeness in general is provided by the regularity of an associated extended transition operator. Commutative and non-commutative examples are analysed.

Stability criteria for the contextual emergence of macrostates in neural networks

More than thirty years ago, Amari and colleagues proposed a statistical framework for identifying structurally stable macrostates of neural networks from observations of their microstates. We compare their stochastic stability criterion with a deterministic stability criterion based on the ergodic theory of dynamical systems, recently proposed for the scheme of contextual emergence and applied to particular inter-level relations in neuroscience. Stochastic and deterministic stability criteria for macrostates rely on macro-level contexts, which make them sensitive to differences between different macro-levels.

Symmetry breaking, mixing, instability, and low frequency variability in a minimal Lorenz-like system

Starting from the classical Saltzman two-dimensional convection equations, we derive via a severe spectral truncation a minimal 10 ODE system which includes the thermal effect of viscous dissipation. Neglecting this process leads to a dynamical system which includes a decoupled generalized Lorenz system. The consideration of this process breaks an important symmetry and couples the dynamics of fast and slow variables, with the ensuing modifications to the structural properties of the attractor and of the spectral features. When the relevant nondimensional number (Eckert number Ec) is different from zero, an additional time scale of O(Ec−1) is introduced in the system, as shown with standard multiscale analysis and made clear by several numerical evidences. Moreover, the system is ergodic and hyperbolic, the slow variables feature long-term memory with 1/f3/2 power spectra, and the fast variables feature amplitude modulation. Increasing the strength of the thermal-viscous feedback has a stabilizing effect, as both the metric entropy and the Kaplan-Yorke attractor dimension decrease monotonically with Ec. The analyzed system features very rich dynamics: it overcomes some of the limitations of the Lorenz system and might have prototypical value in relevant processes in complex systems dynamics, such as the interaction between slow and fast variables, the presence of long-term memory, and the associated extreme value statistics. This analysis shows how neglecting the coupling of slow and fast variables only on the basis of scale analysis can be catastrophic. In fact, this leads to spurious invariances that affect essential dynamical properties (ergodicity, hyperbolicity) and that cause the model losing ability in describing intrinsically multiscale processes.

Time complexity analysis of the stochastic diffusion search

The Stochastic Diffusion Search algorithm -an integral part of Stochastic Search Networks is investigated. Stochastic Diffusion Search is an alternative solution for invariant pattern recognition and focus of attention. It has been shown that the algorithm can be modelled as an ergodic, finite state Markov Chain under some non-restrictive assumptions. Sub-linear time complexity for some settings of parameters has been formulated and proved. Some properties of the algorithm are then characterised and numerical examples illustrating some features of the algorithm are presented.

(Non-)ergodicity of a degenerate diffusion modeling the fiber lay down process

We analyze the large time behavior of a stochastic model for the lay down of fibers on a moving conveyor belt in the production process of nonwovens. It is shown that under weak conditions this degenerate diffusion process has a unique invariant distribution and is even geometrically ergodic. This generalizes results from previous works [M. Grothaus and A. Klar, SIAM J. Math. Anal., 40 (2008), pp. 968–983; J. Dolbeault et al., arXiv:1201.2156] concerning the case of a stationary conveyor belt, in which the situation of a moving conveyor belt has been left open.

Design of delay-tolerant linear dispersion codes

In cooperative communication networks, owing to the nodes' arbitrary geographical locations and individual oscillators, the system is fundamentally asynchronous. This will damage some of the key properties of the space-time codes and can lead to substantial performance degradation. In this paper, we study the design of linear dispersion codes (LDCs) for such asynchronous cooperative communication networks. Firstly, the concept of conventional LDCs is extended to the delay-tolerant version and new design criteria are discussed. Then we propose a new design method to yield delay-tolerant LDCs that reach the optimal Jensen's upper bound on ergodic capacity as well as minimum average pairwise error probability. The proposed design employs stochastic gradient algorithm to approach a local optimum. Moreover, it is improved by using simulated annealing type optimization to increase the likelihood of the global optimum. The proposed method allows for flexible number of nodes, receive antennas, modulated symbols and flexible length of codewords. Simulation results confirm the performance of the newly-proposed delay-tolerant LDCs.

Non-ergodicity of inviscid two-dimensional flow on a beta-plane and on the surface of a rotating sphere

It is shown that, for a sufficiently large value of β, two-dimensional flow on a doubly-periodic beta-plane cannot be ergodic (phase-space filling) on the phase-space surface of constant energy and enstrophy. A corresponding result holds for flow on the surface of a rotating sphere, for a sufficiently rapid rotation rate Ω. This implies that the higher-order, non-quadratic invariants are exerting a significant influence on the statistical evolution of the flow. The proof relies on the existence of a finite-amplitude Liapunov stability theorem for zonally symmetric basic states with a non-vanishing absolute-vorticity gradient. When the domain size is much larger than the size of a typical eddy, then a sufficient condition for non-ergodicity is that the wave steepness ε < 1, where ε = 2[surd radical]2Z/βU in the planar case and $\epsilon = 2^{\frac{1}{4}} a^{\frac{5}{2}}Z^{\frac{7}{4}}/\Omega U^{\frac{5}{2}}$ in the spherical case, and where Z is the enstrophy, U the r.m.s. velocity, and a the radius of the sphere. This result may help to explain why numerical simulations of unforced beta-plane turbulence (in which ε decreases in time) seem to evolve into a non-ergodic regime at large scales.

Mobile-to-mobile MIMO transmit-receive diversity systems: analysis and performance in three-dimensional double-correlated channels

Mobile-to-mobile (M-to-M) communications are expected to play a crucial role in future wireless systems and networks. In this paper, we consider M-to-M multiple-input multiple-output (MIMO) maximal ratio combining system and assess its performance in spatially correlated channels. The analysis assumes double-correlated Rayleigh-and-Lognormal fading channels and is performed in terms of average symbol error probability, outage probability, and ergodic capacity. To obtain the receive and transmit spatial correlation functions needed for the performance analysis, we used a three-dimensional (3D) M-to-M MIMO channel model, which takes into account the effects of fast fading and shadowing. The expressions for the considered metrics are derived as a function of the average signal-to-noise ratio per receive antenna in closed-form and are further approximated using the recursive adaptive Simpson quadrature method. Numerical results are provided to show the effects of system parameters, such as distance between antenna elements, maximum elevation angle of scatterers, orientation angle of antenna array in the x–y plane, angle between the x–y plane and the antenna array orientation, and degree of scattering in the x–y plane, on the system performance. Copyright © 2011 John Wiley & Sons, Ltd.

Analysis and compensation of I/Q imbalance in MIMO transmit-receive diversity systems

In wireless communication systems, all in-phase and quadrature-phase (I/Q) signal processing receivers face the problem of I/Q imbalance. In this paper, we investigate the effect of I/Q imbalance on the performance of multiple-input multiple-output (MIMO) maximal ratio combining (MRC) systems that perform the combining at the radio frequency (RF) level, thereby requiring only one RF chain. In order to perform the MIMO MRC, we propose a channel estimation algorithm that accounts for the I/Q imbalance. Moreover, a compensation algorithm for the I/Q imbalance in MIMO MRC systems is proposed, which first employs the least-squares (LS) rule to estimate the coefficients of the channel gain matrix, beamforming and combining weight vectors, and parameters of I/Q imbalance jointly, and then makes use of the received signal together with its conjugation to detect the transmitted signal. The performance of the MIMO MRC system under study is evaluated in terms of average symbol error probability (SEP), outage probability and ergodic capacity, which are derived considering transmission over Rayleigh fading channels. Numerical results are provided and show that the proposed compensation algorithm can efficiently mitigate the effect of I/Q imbalance.

Performance analysis of MIMO MRC in 3D mobile-to-mobile double-correlated channels

In this paper, we consider multiple-input multiple- output (MIMO) maximal ratio combining (MRC) systems and assess the system performance in terms of average symbol error probability (SEP), outage probability and ergodic capacity in double-correlated Rayleigh-and-Lognormal fading channels. In order to derive the receive and transmit correlation functions needed for the performance analysis, a three-dimensional (3D) MIMO mobile-to-mobile (M-to-M) channel model, which takes into account the effects of fast fading and shadowing is used. Numerical results are provided to show the effects of system parameters, such as maximum elevation angle of scatterers, orientation angle of antenna array in the x-y plane, angle between x-y plane and the antenna array orientation, and degree of scattering in the x-y plane, on the system performance.