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.

Investigation of tin-based alternatives for cadmium in optoelectronic thin-films materials

Increasing legislation has steadily been introduced throughout the world to restrict the use of heavy metals, particularly cadmium (Cd) and lead (Pb) in high temperature pigments, ceramics, and optoelectronic material applications. Removal of cadmium from thin-film optical and semiconductor device applications has been hampered by the absence of viable alternatives that exhibit similar properties with stability and durability. We describe a range of tin-based compounds that have been deposited and characterized in terms of their optical and mechanical properties and compare them with existing cadmium-based films that currently find widespread use in the optoelectronic and semiconductor industries. (c) 2008 Optical Society of America.

Comparative study of Barium Fluoride thin films produced by ion-beam sputtering and thermal evaporation

Coatings and filters for spaceflight far-infrared components require a robust, non-absorptive low-index thin film material to contrast with the typically higher refractive index infrared materials. Barium fluoride is one such material for the 10 to 20µm wavelength infrared region, however its optical and mechanical properties vary depending on the process used to deposit it in thin film form. Thin films of dielectric produced by thermal evaporation are well documented as having a lower packing density and refractive index than bulk material. The porous and columnar micro structure of these films causes possible deterioration of their performance in varied environmental conditions, primarily because of the moisture absorption. Dielectric thin films produced by the more novel technique of ion-beam sputtering are denser with no columnar micro structure and have a packing density and refractive index similar to the bulk material. A comparative study of Barium Fluoride (BaF2) thin films made by conventional thermal evaporation and ion-beam sputtering is reported. Films of similar thicknesses are deposited on Cadmium Telluride and Germanium substrates. The optical and mechanical properties of these films are then examined. The refractive index n of the films is obtained from applying the modified Manifacier's evvelope method to the spectral measurements made on a Perkin Elmer 580 spectrophotometer. An estimate is also made of the value of the extinction coefficient k in the infrared wavelength transparent region of the thin film. In order to study the mechanical properties of the BaF2 films, and evaluate their usefulness in spaceflight infrared filters and coatings, the thin film samples are subjected to MIL-F-48616 environmental tests. Comparisons are made of their performance under these tests.

Tschebyshev optical filter design

A method of designing multi-cavity infrared narrowband filters for bandwidth between 10% and 20% is presended: The method is based on a Tschebyshev prototype. The theoretical indices from these are simulated by Herpin equivalent layers, the outer layers may be also simulated by Herrmann's asymetrical tri-layer. The new algorithm of filter design can easily be implemented in any microcomputer.

Digital signal processing of optical monitoring by means of a Kalman filter

A Kalman filter algorithm has been applied to interpret the optical reflectance excursions during vacuum deposition of infrared coatings and multilayer thin-film filters. The application has been described in detail elsewhere and this paper now reports on-line experience for estimating deposition rate and thickness. The estimation proved sufficiently reliable to firstly 'navigate' regular manufacture (as controlled by a skilled operator) and to subsequently reproduce the skill without interpretation or intervention whilst maintaining exemplary product quality. Optical control by means of this Kalman filter application is therefore considered suitable as a basis for the automated manufacture of infrared coatings and multilayer thin-film filters.

Infrared optical coatings for the EarthCARE Multispectral Imager

The Earth Cloud, Aerosol and Radiation Explorer mission (EarthCARE) Multispectral Imager (MSI) is a radiometric instrument designed to provide the imaging of the atmospheric cloud cover and the cloud top surface temperature from a sun-synchronous low Earth orbit. The MSI forms part of a suite of four instruments destined to support the European Space Agency Living Planet mission on-board the EarthCARE satellite payload to be launched in 2016, whose synergy will be used to construct three-dimensional scenes, textures and temperatures of atmospheric clouds and aerosols. The MSI instrument contains seven channels: four solar channels to measure visible and short-wave infrared wavelengths, and three channels to measure infrared thermal emission. In this paper, we describe the optical layout of the infrared instrument channels, thin-film multilayer designs, the coating deposition method and the spectral system throughput for the bandpass interference filters, dichroic beam splitters, lenses and mirror coatings to discriminate wavelengths at 8.8, 10.8, & 12.0 µm. The rationale for the selection of thin-film materials, spectral measurement technique, and environmental testing performance are also presented.

Thin films prepared from tungstate glass matrix

Vitreous samples containing high concentrations of WO3 (above 40% M) have been used as a target to prepare thin films. Such films were deposited using the electron beam evaporation method onto soda-lime glass substrates. These films were characterized by X-ray diffraction (XRD), perfilometry, X-ray energy dispersion spectroscopy (EDS), M-Lines and UV-vis absorption spectroscopy. In this work, experimental parameters were established to obtain stable thin films showing a chemical composition close to the glass precursor composition and with a high concentration of WO3. These amorphous thin films of about 4 mu m in thickness exhibit a deep blue coloration but they can be bleached by thermal treatment near the glass transition temperature. Such bleached films show several guided modes in the visible region and have a high refractive index. Controlled crystallization was realized and thus it was possible to obtain WO3 microcrystals in the amorphous phase. (C) 2007 Elsevier B.V. All rights reserved.

Electrodeposition and characterization of thin selenium films modified with lead ad-atoms

The deposition and characterization of Se films doped with Pb underpotentially deposited (UPD) ad-atoms was studied in this work. The employed experimental techniques were cyclic voltammetry, chronoamperometry, electrochemical impedance spectroscopy, UV-vis spectroscopy and atomic force microscopy. The initial deposition of Se film by chronoamperometry yielded a thin film composed of approximately 700 layers. The Pb UPD on Se was achieved by chronoamperometry in a potential value previously determined in voltammetric experiments. This deposition yielded a deposition charge of approximately 7.5% of the total one. The film resistance altered from 320 Omega cm(2) for Se to 65 Omega cm(2) for the Se/Pb one. Flat band potential values and number of acceptors and donors were also calculated for both films and the values obtained were + 0.95 and -0.51 V for Se and Se/Pb, respectively. The Se coating presented 1.2 x 10(17) cm(3) acceptors while the Se/Pb one presented 3.2 x 10(17) cm(3) donors. The band gap values for both films were 2.4 eV and 1.9 eV, correspondingly. (C) 2008 Elsevier B.V. All rights reserved.

Visible emission from Er-doped SnO2 thin films deposited by sol-gel

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Study on the orientation degree of Pb1-xLaxTiO3 thin films by the rocking curve technique and its morphological aspects

Thin films of perovskite-type materials such as PbTiO3, BaTiO3, (Pb,La)TiO3, (Pb, La)(ZrTi)O-3, KNbO3, and Pb(Mg,Nb)03 have been attracting great interest for applications like non-volatile memories, ultrasonic sensors and optical devices. Thin film should be epitaxially grown or at least highly textured since the properties of this anisotropic material depend on the crystallographic orientation. For optical devices, in particular, an epitaxial thin film without defects are essential to reduce optical propagation losses. Pb1-xLaxTiO3 (PLT) where x=0, 13 and 27% thin films were prepared by a chemical method (polymeric precursors method), and deposited by the spin coating technique onto substrates of SrTiO3 (STO) and LaAlO3 (LAO). The films were then beat treated at 500 degrees C in a controlled atmosphere of 0,. The orientation degree of the thin films was obtained from rocking curve technique, by means of X-ray difftaction analysis. A microstructural study revealed that the films were crack-free, homogeneous and have low roughness. (c) 2006 Elsevier B.V. All rights reserved.

Investigation of phase transition in ferroelectric Pb0.70Sr0.30TiO3 thin films

We have carried out dielectric and Raman spectroscopy studies at the 298-623 K temperature range in polycrystalline Pb0.70Sr0.30TiO3 thin films grown by a soft chemical method. The diffuse phase-transition behavior of the thin films was observed by means of the dielectric constant versus temperature curves, which show a broad peak. Such behavior was confirmed later by Raman spectroscopy measurements up to 823 K, indicating that a diffuselike phase transition takes place at around 548-573 K. The damping factor of the E(1TO) soft mode was calculated using the damped simple harmonic oscillator model. on the other hand, Raman modes persist above the tetragonal to cubic phase transition temperature although all optical modes should be Raman inactive. The origin of these modes was interpreted in terms of a breakdown of the microscopic local cubic symmetry by chemical disorder. The lack of a well-defined transition temperature and the presence of broad bands at some temperature interval above the ferroelectric-paraelectric phase-transition temperature suggested a diffuse nature of the phase transition. This result corroborates the dielectric constant versus temperature data, which showed a broad ferroelectric phase transition in this thin film. (C) 2004 American Institute of Physics.

Electroluminescence of zinc oxide thin-films prepared via polymeric precursor and via sol-gel methods

Zinc oxide (ZnO) is an electroluminescent (EL) material that can emit light in different regions of electromagnetic spectrum when electrically excited. Since ZnO is chemically stable, inexpensive and environmentally friendly material, its EL property can be useful to construct solid-state lamps for illumination or as UV emitter. We present here two wet chemical methods to prepare ZnO thin-films: the Pechini method and the sol-gel method, with both methods resulting in crystalline and transparent films with transmittance > 85% at 550 nm. These films were used to make thin-film electroluminescent devices (TFELD) using two different insulator layers: lithium fluoride (LiF) or silica (SiO2). All the devices exhibit at least two wide emission bands in the visible range centered at 420 nm and at 380 nm attributed to the electronic defects in the ZnO optical band gap. Besides these two bands, the device using SiO2 and ZnO film obtained via sol-gel exhibits an additional band in the UV range centered at 350 nm which can be attributed to excitonic emission. These emission bands of ZnO can transfer their energy when a proper dopant is present. For the devices produced the voltage-current characteristics were measured in a specific range of applied voltage. (C) 2007 Elsevier B.V. All rights reserved.

Conditions giving rise to intense visible room temperature photoluminescence in SrWO4 thin films: the role of disorder

The nature of intense visible photoluminescence at room temperature of SrWO4 (SWO) non-crystalline thin films is discussed in the light of experimental results and theoretical calculations. The SWO thin films were synthesized by the polymeric precursors method. Their structural properties have been obtained by X-ray diffraction data and the corresponding photoluminescence (PL) spectra have been measured. The UV-vis optical spectra measurements suggest the creation of localized states in the disordered structure. The photoluminescence measurements reveal that the PL changes with the degree of disorder in the SWO thin film. To understand the origin of visible PL at room temperature in disordered SWO, we performed quantum-mechanical calculations on crystalline and disordered SWO periodic models. Their electronic structures are analyzed in terms of DOS, hand dispersion and charge densities. We used DFT method with the hybrid non-local B3LYP approximation. The polarization induced by the symmetry break and the existence of localized levels favors the creation of trapped holes and electrons, giving origin to the room temperature photoluminescence phenomenon in the SWO thin films. (c) 2004 Elsevier B.V. All rights reserved.

Electrical conduction mechanism and phase transition studies using dielectric properties and Raman spectroscopy in ferroelectric Pb0.76Ca0.24TiO3 thin films

We have studied the phase transition behavior of Pb0.76Ca0.24TiO3 thin films using Raman scattering and dielectric measurement techniques. We also have studied the leakage current conduction mechanism as a function of temperature for these thin films on platinized silicon substrates. A Pb0.76Ca0.24TiO3 thin film was prepared using a soft chemical process, called the polymeric precursor method. The results showed that the dependence of the dielectric constant upon the frequency does not reveal any relaxor behavior. However, a diffuse character-type phase transition was observed upon transformation from a cubic paraelectric phase to a tetragonal ferroelectric phase. The temperature dependency of Raman scattering spectra was investigated through the ferroelectric phase transition. The soft mode showed a marked dependence on temperature and its disappearance at about 598 K. on the other hand, Raman modes persist above the tetragonal to cubic phase transition temperature, although all optical modes should be Raman inactive above the phase transition temperature. The origin of these modes must be interpreted in terms of a local breakdown of cubic symmetry by some kind of disorder. The lack of a well-defined transition temperature suggested a diffuse-type phase transition. This result corroborate the dielectric constant versus temperature data, which showed a broad ferroelectric phase transition in the thin film. The leakage current density of the PCT24 thin film was studied at elevated temperatures, and the data were well fitted by the Schottky emission model. The Schottky barrier height of the PCT24 thin film was estimated to be 1.49 eV. (C) 2003 American Institute of Physics.

Theoretical and experimental study of the relation between photoluminescence and structural disorder in barium and strontium titanate thin films

Thin films of barium and strontium titanate (BST), synthesized by the polymeric precursor solution and spin coated on [Pt (140nm)/Ti (10 nM)/SiO2(1000 nm)/Si] substrates were found to be photoluminescent at room temperature when heat treated below 973 K, i.e. before their crystallization. First principles quantum mechanical techniques, based on density functional theory (DFT) were employed to study the electronic structure of two periodic models: one is standing for the crystalline BST thin film and the other one for the structurally disordered thin film. The aim is to compare the photoluminescence (PL) spectra of the crystalline and disordered thin films with their UV-vis spectra and with their computed electronic structures. The calculations show that new localized states are created inside the band gap of the crystalline model, as predicted by the UV-vis spectra. The study of the charge repartition in the structure before and after deformation of the periodic model shows that a charge gradient appears among the titanate clusters. This charge gradient, together with the new localized levels, gives favorable conditions for the trapping of holes and electrons in the structure, and thus to a radiative recombination process. Our models are not only consistent with the experimental data, they also allow to explain the relations between structural disorder and photoluminescence at room temperature. (c) 2005 Elsevier Ltd. All rights reserved.