Spectroscopic and photoluminescence studies on optically transparent magnetic nanocomposites based on sol–gel glass: Fe3O4

Sol–gel glasses with Fe3O4 nanoparticles having particle sizes laying in the range 10–20 nm were encapsulated in the porous network of silica resulting in nanocomposites having both optical and magnetic properties. Spectroscopic and photoluminescence studies indicated that Fe3O4 nanocrystals are embedded in the silica matrix with no strong Si–O–Fe bonding. The composites exhibited a blue luminescence. The optical absorption edge of the composites red shifted with increasing concentration of Fe3O4 in the silica matrix. There is no obvious shift in the position of the luminescence peak with the concentration of Fe3O4 except that the intensity of the peak is decreased. The unique combinations of magnetic and optical properties are appealing for magneto–optical applications.

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.

Nanocrystalline Ge Flash Memories: Electrical Characterization and Trap Engineering

Conventional floating gate non-volatile memories (NVMs) present critical issues for device scalability beyond the sub-90 nm node, such as gate length and tunnel oxide thickness reduction. Nanocrystalline germanium (nc-Ge) quantum dot flash memories are fully CMOS compatible technology based on discrete isolated charge storage nodules which have the potential of pushing further the scalability of conventional NVMs. Quantum dot memories offer lower operating voltages as compared to conventional floating-gate (FG) Flash memories due to thinner tunnel dielectrics which allow higher tunneling probabilities. The isolated charge nodules suppress charge loss through lateral paths, thereby achieving a superior charge retention time. Despite the considerable amount of efforts devoted to the study of nanocrystal Flash memories, the charge storage mechanism remains obscure. Interfacial defects of the nanocrystals seem to play a role in charge storage in recent studies, although storage in the nanocrystal conduction band by quantum confinement has been reported earlier. In this work, a single transistor memory structure with threshold voltage shift, Vth, exceeding ~1.5 V corresponding to interface charge trapping in nc-Ge, operating at 0.96 MV/cm, is presented. The trapping effect is eliminated when nc-Ge is synthesized in forming gas thus excluding the possibility of quantum confinement and Coulomb blockade effects. Through discharging kinetics, the model of deep level trap charge storage is confirmed. The trap energy level is dependent on the matrix which confines the nc-Ge.

La formación del profesorado basada en la competencia.

Un ejemplo de programa educativo que refleja el cambio educativo actual en Estados Unidos, es el programa conocido por la educación basada en las competencias del profesor (competency-based teacher education). Este concepto educativo es un tipo de estrategia que puede proporcionarnos un procedimiento sistemático para hacer frente a la complejidad educativa, representando algo más que un aislado intento de innovación para modernizar la educación del profesorado. Sus siglas serian CBTE. Quienes estudian el sistema de la educación basada en la competencia del profesor, comprobarán que también se habla en él de la educación basada en la actuación del profesor (perfomance-based teacher education, PBTE). Ambos son términos sinónimos, pero el primero es más ampllio porque no sólo se preocupa de la capacidad del profesor para que actúe de la manera deseada, sino que, a la vez, se interesa por las capacidades que hay que desarrollar y demostrar que corresponden a la complejidad del papel del profesor. La idea de CBTE es que las decisiones en la preparación del profesor han de estar basadas en una competencia demostrada, más que en unas pruebas de preparación o experiencias supuestamente relacionadas con la capacidad. Un creciente número de profesionales de la enseñanza no están dispuestos a aceptar la creencia de que simplemente por el hecho de que alguien sabe. Ello, significa que forzosamente será capaz de aplicar los conocimientos. Ha pasado la época de dar una mayor importancia dentro de los programas de preparación del profesorado a los conocimientos de éste. Los conocimientos y las capacidades son dos temas muy diferentes. La formación del profesorado basada en las competencias es un proceso y no un fin en si mismo. Representa un intento por pasar desde nuestra ambigua condición presente en la preparación del profesor a un programa más claramente delineado y articulado de preparación de profesionales de la enseñanza, tanto de los que están haciendo prácticas como de los ya en servicio. El término de preparación de profesores profesionales, tal como se emplea hoy, no incluye la parte de las artes liberales en este tipo de programa. Pero ¿cuál será el principal criterio para determinar el nivel de competencias que un graduado del programa CBTE ha alcanzado? Hay cinco puntos principales en un largo proceso de evaluación del profesorado, donde se puede admitir la evaluación: el proyecto, la operación, las consecuencias en términos de comportamiento del profesorado, las consecuencias en cuanto a condiciones creadas por el comportamiento del profesorado y las consecuencias en términos del progreso de los estudiantes. Únicamente un programa amplio y continuo de evaluación de datos recogidos desde su creación puede contestar a las preguntas sobre el valor de la educación basada en las capacidades. El problema de quien controla la formación del profesorado es muy fluctuante, y CBTE tendrá mucho que hacer en la redistribución del poder compartido.En realidad, todos los grupos implicados en la educación del profesorado deben participar y encontrar su lugar en el movimiento de las competencias.

Investigation of cadmium alternatives in thin-film coatings - art. no. 62860C

The health risks associated with the inhalation or ingestion of cadmium are well documented([1,2]). During the past 18 years, EU legislation has steadily been introduced to restrict its use, leaving a requirement for the development of replacement materials. This paper looks at possible alternatives to various cadmium II-VI dielectric compounds used in the deposition of optical thin-films for various opto-electronic devices. Application areas of particular interest are for infrared multilayer interference filter fabrication and solar cell industries, where cadmium-based coatings currently find widespread use. The results of single and multilayer designs comprising CdTe, CdS, CdSe and PbTe deposited onto group IV and II-VI materials as interference filters for the mid-IR region are presented. Thin films of SnN, SnO2, SnS and SnSe are fabricated by plasma assisted CVD, reactive RF sputtering and thermal evaporation. Examination of these films using FTIR spectroscopy, SEM, EDX analysis and optical characterisation methods provide details of material dispersion, absorption, composition, refractive index, energy band gap and layer thicknesses. The optimisation of deposition parameters in order to synthesise coatings with similar optical and semiconductor properties as those containing cadmium has been investigated. Results of environmental, durability and stability trials are also presented.

An ultra-wide passband (5-30µm) filter for FTIR studies of Photosystem II

This paper reports on the design and manufacture of an ultra-wide (5-30µm) infrared edge filter for use in FTIR studies of the low frequency vibrational modes of metallo-proteins. We present details of the spectral design and manufacture of such a filter which meets the demanding bandwidth and transparency requirements of the application, and spectra that present the new data possible with such a filter. A design model of the filter and the materials used in its construction has been developed capable of accurately predicting spectral performance at both 300K and at the reduced operating temperature at 200K. This design model is based on the optical and semiconductor properties of a multilayer filter containing PbTe (IV-VI) layer material in combination with the dielectric dispersion of ZnSe (II-VI) deposited on a CdTe (II-VI) substrate together with the use of BaF2 (II-VII) as an antireflection layer. Comparisons between the computed spectral performance of the model and spectral measurements from manufactured coatings over a wavelength range of 4-30µm and temperature range 300-200K are presented. Finally we present the results of the FTIR measurements of Photosystem II showing the improvement in signal to noise ratio of the measurement due to using the filter, together with a light induced FTIR difference spectrum of Photosystem II.

Novel material combinations for enhanced infrared filter performance

The introduction of non-toxic fluride compounds as direct replacements for Thorium Fluoride (ThF4) has renewed interest in the use of low index fluoride compounds in high performance infrared filters. This paper reports the results of an investigation into the effects of combining these low index materials, particularly Barium Fluoride (BaF2), with the high index material Lead Telluride (PbTe) in bandpass and edge filters. Infrared filter designs using conventional and the new material ombination are compared, and infrared filters using these material combinations have been manufactured and have been shown to suffer problems with residual stress. A possible solution to this problem utilising Zinc Sulphide (ZnS) layers with compensating compressive stress is discussed.

Preliminary results from the infrared multilayer filters and materials exposed to the space environment on the NASA LDEF mission

With continually increasing demands for improvements to atmospheric and planetary remote-sensing instrumentation, for both high optical system performance and extended operational lifetimes, an investigation to access the effects of prolonged exposure of the space environment to a series of infrared interference filters and optical materials was promoted on the NASA LDEF mission. The NASA Long Duration Exposure Facility (LDEF) was launchd by the Space Shuttle to transport various science and technology experiments both to and from space, providing investigators with the opportunity to study the effects of the space environment on materials and systems used in space-flight applications. Preliminary results to be discussed consist of transmission measurements obtained and processed from an infrared spectrophotometer both before (1983) and after (1990) exposure compared with unexposed control specimens, together with results of detailed microscopic and general visual examinations performed on the experiment. The principle lead telluride (PbTe) and Zinc Sulphide (ZnS) based multilayer filters selected for this preliminary investigation consist of : an 8-12µm low pass edge filter, a 10.6µm 2.5% half bandwidth (HBW) double half-wave narrow bandpass filter, and a 10% HBW triple half-wave wide bandpass filter at 15µm. Optical substrates of MgF2 and KRS-5 (T1BrI) will also be discussed.

Investigation of ultra wideband multi-channel dichroic beamsplitters from 0.3 to 52µm

The development of a set of multi-channel dichroics which includes a 6 channel dichroic operating over the wavelength region from 0.3 to 52µm is described. In order to achieve the optimum performance, the optical constants of PbTe, Ge and CdTe coatings in the strongly absorptive region have been determined by use of a new iterative method using normal incidence reflectance measurement of the multilayer together with initial values of energy gap Eg and infinite refractive index n for the semiconductor model. The design and manufacture of the dichroics is discussed and the final results are presented.

Performance model for cooled IR filters

A low-temperature model is described for infrared multilayer filters containing PbTe (or other semiconductor) and ZnSe (or other II/VI). The model is based on dielectric dispersion with semiconductor carrier dispersion added. It predicts an improved performance on cooling such as would be useful to avoid erroneous signals from optics in spaceflight radiometers. Agreement with measurement is obtained over the initial temperature range 70-400K and wavelength range 2.5-20µm.

Measurement of infrared multilayer filters at temperatures down to 4 deg K

Measurement is reported at 4 deg K (and blocked transmission below 10-5) of PbTe/ZnS thin-film filters deposited on Ge substrates. The reduced carrier-absorption which is obtained by cooling these PbTe films is found to accord with simple theory. Advantage for various high-performance multilayers by cooling is significant at the longer wavelengths, and has been verified.

Far infrared filters for the GALILEO-Jupiter and other missions

Extrapolation of PbTe/II-VI multilayer interference-filter technique from 20 to beyond 40µm is described and PbTe transparency reviewed; improvements below 20µm are reported. A composite filter cutting on steeply at 40µm is described that uses absorptive films of ZnS and As2S3, thin Quartz, and supplementary multilayer interference. Absorptive filters are described containing the II-VI compounds since these are found transparent at wavelengths shorter and longer than their reststrahl.

Cooled filters 16-42µm for FIR astronomy

The design and manufacture of dielectric-film interference filters for cooled FIR stronmy is described. The bands are 16.5-21.5µm, 17.5-19.5µm, 19.5-21.5µm and 27µm cut on. The films are PbTe/CdSe and the substrates are CdTe (some 1/2 mm thick), without absorption in the region: KRS-6 films are used for antireflection.

High-strength, healable, supramolecular polymer nanocomposites

A supramolecular polymer blend, formed via π-π interactions between a π-electron rich pyrenyl endcapped oligomer and a chain-folding oligomer containing pairs of π-electron poor naphthalene-diimide (NDI) units, has been reinforced with cellulose nanocrystals (CNCs) to afford a healable nanocomposite material. Nanocomposites with varying weight percentage of CNCs (from 1.25 to 20.0 wt.%) within the healable supramolecular polymeric matrix have been prepared via solvent casting followed by compression molding, and their mechanical properties and healing behavior have been evaluated. It is found that homogeneously dispersed films can be formed with CNCs at less than 10 wt.%. Above 10 wt.% CNC heterogeneous nanocomposites were obtained. All the nanocomposites formed could be re-healed upon exposure to elevated temperatures although, for the homogeneous films, it was found that the healing rate was reduced with increasing CNC content. The best combination of healing efficiency and mechanical properties was obtained with the 7.5 wt.% CNC nanocomposite which exhibited a tensile modulus enhanced by as much as a factor of 20 over the matrix material alone and could be fully re-healed at 85 °C within 30 minutes. Thus it is demonstrated that supramolecular nanocomposites can afford greatly enhanced mechanical properties relative to the unreinforced polymer, while still allowing efficient thermal healing.

Shape-controlled continuous synthesis of metal nanostructures

A segmented flow-based microreactor is used for the continuous production of faceted nanocrystals. Flow segmentation is proposed as a versatile tool to manipulate the reduction kinetics and control the growth of faceted nanostructures; tuning the size and shape. Switching the gas from oxygen to carbon monoxide permits the adjustment in nanostructure growth from 1D (nanorods) to 2D (nanosheets). CO is a key factor in the formation of Pd nanosheets and Pt nanocubes; operating as a second phase, a reductant, and a capping agent. This combination confines the growth to specific structures. In addition, the segmented flow microfluidic reactor inherently has the ability to operate in a reproducible manner at elevated temperatures and pressures whilst confining potentially toxic reactants, such as CO, in nanoliter slugs. This continuous system successfully synthesised Pd nanorods with an aspect ratio of 6; thin palladium nanosheets with a thickness of 1.5 nm; and Pt nanocubes with a 5.6 nm edge length, all in a synthesis time as low as 150 s.