Designing intrinsically photostable low band gap polymers:a smart tool combining EPR spectroscopy and DFT calculations

A rapid and efficient method to identify the weak points of the complex chemical structure of low band gap (LBG) polymers, designed for efficient solar cells, when submitted to light exposure is reported. This tool combines Electron Paramagnetic Resonance (EPR) using the 'spin trapping method' coupled with density functional theory modelling (DFT). First, the nature of the short life-time radicals formed during the early-stages of photo-degradation processes are determined by a spin-trapping technique. Two kinds of short life-time radical (R and R′O) are formed after 'short-duration' illumination in an inert atmosphere and in ambient air, respectively. Second, simulation allows the identification of the chemical structures of these radicals revealing the most probable photochemical process, namely homolytical scission between the Si atom of the conjugated skeleton and its pendent side-chains. Finally, DFT calculations confirm the homolytical cleavage observed by EPR, as well as the presence of a group that is highly susceptible to photooxidative attack. Therefore, the synergetic coupling of a spin trapping method with DFT calculations is shown to be a rapid and efficient method for providing unprecedented information on photochemical mechanisms. This approach will allow the design of LBG polymers without the need to trial the material within actual solar cell devices, an often long and costly screening procedure.

Modifying the band gap and optical properties of Germanium nanowires by surface termination

Semiconductor nanowires, based on silicon (Si) or germanium (Ge) are leading candidates for many ICT applications, including next generation transistors, optoelectronics, gas and biosensing and photovoltaics. Key to these applications is the possibility to tune the band gap by changing the diameter of the nanowire. Ge nanowires of different diameter have been studied with H termination, but, using ideas from chemistry, changing the surface terminating group can be used to modulate the band gap. In this paper we apply the generalised gradient approximation of density functional theory (GGA-DFT) and hybrid DFT to study the effect of diameter and surface termination using –H, –NH2 and –OH groups on the band gap of (001), (110) and (111) oriented germanium nanowires. We show that the surface terminating group allows both the magnitude and the nature of the band gap to be changed. We further show that the absorption edge shifts to longer wavelength with the –NH2 and –OH terminations compared to the –H termination and we trace the origin of this effect to valence band modifications upon modifying the nanowire with –NH2 or –OH. These results show that it is possible to tune the band gap of small diameter Ge nanowires over a range of ca. 1.1 eV by simple surface chemistry.

The Key Factors In Fabrication Of High-Quality Ordered Macroporous Copper Film

The template-directed fabrication of highly-ordered porous film is of significant importance in implementation of the photonic band gap structure. The paper reports a simple and effective method to improve the electrodeposition of metal porous film by utilizing highly-ordered polystyrene spheres (PSs) template. By surface-modification method, the hydrophobic property of the PSs template surfaces was changed into hydrophilic one. It was demonstrated that the surface modi. cation process enhanced the permeability of the electrolyte solution in the nanometer-sized voids of the colloidal template. The homogeneously deposited copper film with the highly-ordered voids in size of less than 500 nm was successfully obtained. In addition, it was found that large defects, such as microcracks in the template, strongly influenced the macroporous films quality. An obvious preferential growth in the cracked area was observed. (C) 2008 Elsevier B. V. All rights reserved.

Photonics and lasing in liquid crystal materials

Owing to fundamental reasons of symmetry, liquid crystals are soft materials. This softness allows long length-scales, large susceptibilities and the existence of modulated phases, which respond readily to external fields. Liquid crystals with such phases are tunable, self-assembled, photonic band gap materials; they offer exciting opportunities both in basic science and in technology. Since the density of photon states is suppressed in the stop band and is enhanced at the band edges, these materials may be used as switchable filters or as mirrorless lasers. Disordered periodic liquid crystal structures can show random lasing. We highlight recent advances in this rapidly growing area, and discuss future prospects in emerging liquid crystal materials. Liquid crystal elastomers and orientationally ordered nanoparticle assemblies are of particular interest. © 2006 The Royal Society.

Density of photon states in dye-doped chiral nematic liquid crystal cells in the presence of losses and gain

We calculate the density of photon states (DOS) of the normal modes in dye-doped chiral nematic liquid crystal (LC) cells in the presence of various loss mechanisms. Losses and gain are incorporated into the transmission characteristics through the introduction of a small imaginary part in the dielectric constant perpendicular and along the director, for which we assume no frequency dispersion. Theoretical results are presented on the DOS in the region of the photonic band gap for a range of values of the loss coefficient and different values of the optical anisotropy. The obtained values of the DOS at the photonic band gap edges predict a reversal of the dominant modes in the structure. Our results are found to be in good agreement with the experimentally obtained excitation thresholds in chiral nematic LC lasers. The behavior of the DOS is also discussed for amplifying LC cells providing additional insight to the lasing mechanism of these structures. © 2012 American Physical Society.

Density of photon states in dye-doped chiral nematic liquid crystal cells in the presence of losses and gain.

We calculate the density of photon states (DOS) of the normal modes in dye-doped chiral nematic liquid crystal (LC) cells in the presence of various loss mechanisms. Losses and gain are incorporated into the transmission characteristics through the introduction of a small imaginary part in the dielectric constant perpendicular and along the director, for which we assume no frequency dispersion. Theoretical results are presented on the DOS in the region of the photonic band gap for a range of values of the loss coefficient and different values of the optical anisotropy. The obtained values of the DOS at the photonic band gap edges predict a reversal of the dominant modes in the structure. Our results are found to be in good agreement with the experimentally obtained excitation thresholds in chiral nematic LC lasers. The behavior of the DOS is also discussed for amplifying LC cells providing additional insight to the lasing mechanism of these structures.

High speed optical communication systems: From modulation formats to radically new fibres

High volumes of data traffic along with bandwidth hungry applications, such as cloud computing and video on demand, is driving the core optical communication links closer and closer to their maximum capacity. The research community has clearly identifying the coming approach of the nonlinear Shannon limit for standard single mode fibre [1,2]. It is in this context that the work on modulation formats, contained in Chapter 3 of this thesis, was undertaken. The work investigates the proposed energy-efficient four-dimensional modulation formats. The work begins by studying a new visualisation technique for four dimensional modulation formats, akin to constellation diagrams. The work then carries out one of the first implementations of one such modulation format, polarisation-switched quadrature phase-shift keying (PS-QPSK). This thesis also studies two potential next-generation fibres, few-mode and hollow-core photonic band-gap fibre. Chapter 4 studies ways to experimentally quantify the nonlinearities in few-mode fibre and assess the potential benefits and limitations of such fibres. It carries out detailed experiments to measure the effects of stimulated Brillouin scattering, self-phase modulation and four-wave mixing and compares the results to numerical models, along with capacity limit calculations. Chapter 5 investigates hollow-core photonic band-gap fibre, where such fibres are predicted to have a low-loss minima at a wavelength of 2μm. To benefit from this potential low loss window requires the development of telecoms grade subsystems and components. The chapter will outline some of the development and characterisation of these components. The world's first wavelength division multiplexed (WDM) subsystem directly implemented at 2μm is presented along with WDM transmission over hollow-core photonic band-gap fibre at 2μm. References: [1]P. P. Mitra, J. B. Stark, Nature, 411, 1027-1030, 2001 [2] A. D. Ellis et al., JLT, 28, 423-433, 2010.

Langmuir-Blodgett assembly of colloidal crystals combined with controlled infiltration of conducting metal oxides

Colloidal photonic crystals (PhCs) possess a periodic dielectric structure which gives rise to a photonic band gap (PBG) and offer great potential in the ability to modify or control light at visible wavelengths. Although the refractive index contrast between the void or infill and the matrix material is paramount for photonics applications, integration into real optoelectronics devices will require a range of added functionalities such as conductivity. As such, colloidal PhCs can be used as templates to direct infiltration of other functional materials using a range of deposition strategies. The work in this thesis seeks to address two challenges; first to develop a reproducible strategy based on Langmuir-Blodgett (LB) deposition to assemble high quality colloidal PhCs based on silica with precise film thickness as most other assembly methods suffer from a lack of reproducibility thickness control. The second is to investigate the use of LBdeposited colloidal PhCs as templates for infiltration with conducting metal oxide materials using vapor phase deposition techniques. Part of this work describes the synthesis and assembly of colloidal silica spheres with different surface chemical functionalities at the air-water interface in preparation for LB deposition. Modification of surface funtionality conferred varying levels of hydrophobicity upon the particles. The behaviour of silica monolayer films at the air-water interface was characterised by Brewster Angle Microscopy and surface pressure isotherms with a view to optimising the parameters for LB deposition of multilayer colloidal PhC films. Optical characterisation of LB-fabricated colloidal PhCs indicated high quality photonic behaviour, exhibiting a pseudo PBG with a sharp Bragg diffraction peak in the visible region and reflectance intensities greater than 60%. Finally the atomic layer deposition (ALD) of nominally undoped ZnO and aluminium “doped” ZnO (Al-doped ZnO) inside the pores of a colloidal PhC assembled by the LB technique was carried out. ALD growth in this study was performed using trimethyl aluminium (TMA) and water as precursors for the alumina and diethyl zinc (DEZn) and water for the ZnO. The ZnO:Al films were grown in a laminate mode, where DEZn pulses were substituted for TMA pulses in the sequences with a Zn:Al ratio 19:1. The ALD growth of ZnO and ZnO:Al in colloidal PhCs was shown to be highly conformal, tuneable and reproducible whilst maintaining excellent photonic character. Furthermore, at high levels of infiltration the opal composite films demonstrated significant conductivity.

A Novel Method for Switching and Tuning of PBG Structures

Photonic band-gap (PBG) structures are utilized in microwave components as filters to suppress unwanted signals. In this work, rectangular perforations were created in the ground plane of a microstrip line to construct a PBG structure. A gold-coated alumina substrate was utilized to switch or tune the bandstop characteristics of this structure. It was demonstrated that the bandstop characteristics were switched off from - 35 to - 1 dB at 16 GHz. Tuning of the bandstop edge with a shift of 1.5 GHz was also shown

Dispositivos planares integrados utilizando método dinâmico com metamateriais e PBG

This work presents a theoretical, numerical and computation analysis of parameters of a rectangular microstrip antenna with metamaterial substrate, fin line as a coupler and also integrated devices like integrated filter antenna. It is applied theory to full-wave of Transverse Transmission Line - TTL method, to characterize the magnitude of the substrate and obtain the general equations of the electromagnetic fields. About the metamaterial, they are characterized by permittivity and permeability tensor, reaching to the general equations for the electromagnetic fields of the antenna. It is presented a study about main representation of PBG(Photonic Band Gap) material and its applied for a specific configuration. A few parameters are simulated some structures in order to reduce the physical dimensions and increase the bandwidth. The results are presented through graphs. The theoretical and computational analysis of this work have shown accurate and relatively concise. Conclusions are drawn and suggestions for future work

Desenvolvimento de um ressoador retangular de fenda com múltiplas camadas de substrato e com utilização de material PBG para sistema de comunicação sem fio

In the globalized world modern telecommunications have assumed key role within the company, causing a large increase in demand for the wireless technology of communication, which has been happening in recent years have greatly increased the number of applications using this technology. Due to this demand, new materials are developed to enable new control mechanisms and propagation of electromagnetic waves. The research to develop new technologies for wireless communication presents a multidisciplinary study that covers from the new geometries for passive antennas, active up to the development of materials for devices that improve the performance at the frequency range of operation. Recently, planar antennas have attracted interest due to their characteristics and advantages when compared with other types of antennas. In the area of mobile communications the need for antennas of this type has become increasingly used, due to intensive development, which needs to operate in multifrequency antennas and broadband. The microstrip antennas have narrow bandwidth due to the dielectric losses generated by irradiation. Another limitation is the degradation of the radiation pattern due to the generation of surface waves in the substrate. Some techniques have been developed to minimize this limitation of bandwidth, such as the study of type materials PBG - Photonic Band Gap, to form the dielectric material. This work has as main objective the development project of a slot resonator with multiple layers and use the type PBG substrate, which carried out the optimization from the numerical analysis and then designed the device initially proposed for the band electromagnetic spectrum between 3-9 GHz, which basically includes the band S to X. Was used as the dielectric material RT/Duroid 5870 and RT/Duroid 6010.LM where both are laminated ceramic-filled PTFE dielectric constants 2.33 and 10.2, respectively. Through an experimental investigation was conducted an analysis of the simulated versus measured by observing the behavior of the radiation characteristics from the height variation of the dielectric multilayer substrates. We also used the LTT method resonators structures rectangular slot with multiple layers of material photonic PBG in order to obtain the resonance frequency and the entire theory involving the electromagnetic parameters of the structure under consideration. xviii The analysis developed in this work was performed using the method LTT - Transverse Transmission Line, in the field of Fourier transform that uses a component propagating in the y direction (transverse to the real direction of propagation z), thus treating the general equations of the fields electric and magnetic and function. The PBG theory is applied to obtain the relative permittivity of the polarizations for the sep photonic composite substrates material. The results are obtained with the commercial software Ansoft HFSS, used for accurate analysis of the electromagnetic behavior of the planar device under study through the Finite Element Method (FEM). Numerical computational results are presented in graphical form in two and three dimensions, playing in the parameters of return loss, frequency of radiation and radiation diagram, radiation efficiency and surface current for the device under study, and have as substrates, photonic materials and had been simulated in an appropriate computational tool. With respect to the planar device design study are presented in the simulated and measured results that show good agreement with measurements made. These results are mainly in the identification of resonance modes and determining the characteristics of the designed device, such as resonant frequency, return loss and radiation pattern

Materiais supercondutores HTS para arranjos de antenas e aplicação de PBG para micro-ondas

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior

Fibra de crital fotônico: fundamentação e aplicações

The main purpose of this dissertation, consists of the study and analysis of the PBG (Photonic Band Gap )..tecnology incorporated in optical fiber structures. So, we'l1 present a complete PBG structure theory, and folowing this, we'l1 present also a chapter for convencional optical fiber, due to the need to construct the base theory of them, and latter a more complete work about photonic crystal fiber. Finaly, we'l1 show the results of the signals , dispersion, and obtained curves under the right dimensions according to the required signals, for convencional optical and photonic crystal fiber. Knowing that PBG crystals with low losses act as perfect mirrors for forbidden frequences and knowing that the persence of structures of PBG as substrates, brings some desirable characteristics such as spontaneous emition supression and superficial waves. We' 11 show according to these characteristics its applications in telecomunication. Therefore, the enphasis of this work is to show that the optical fibers are the only practible thing to integrate the enormous quantity of data and video at intemet' s market, developing, manipulating, changing, and multiplexing the optical fibers chanels in an area where we expect that the photonic crystals has an important hole, since the photonic crystals can be projected and made to avoid losses in the bands of certain wavelength which permits the increase in efficiency ofthe optical components projected with crystals. A sequence of this work would be the utilisation of the PBG structures in the new system of optical network without fiber developed by Bell laboratories of the lucent tecnology, last year using light rays for transmiting information through the air. The new system of optical networks without fiber will permit sending the data of 15 cd-rooms in less then one second, what represents 65 times more information than those transmitted through the actual radio frequences

Ressoador retangular defenda com quatro camadas fotônicas

Recently, planar antennas have attracted interest due to its characteristics as well as the advantages they offer compared to other types of antennas. In the area of mobile communications the need for such antennas has become increasingly intense due to development, which requires antennas that operate in multifrequency and broadband. The microstrip antennas have narrow bandwidth due to losses in the dielectric caused by irradiation. Another limitation is the radiation pattern degradation due to generation of surface waves in the substrate. Some techniques are being developed to minimize this bandwidth limitation, as is the case in the study of type materials PBG - Photonic Band Gap, to compose the dielectric material. The analysis developed in this work were performed with use of the method LTT - Transverse Transmission Line, in the field of Fourier transform that uses a component propagating in the y direction (transerve real direction of propagation z), thus treating the general equations of the fields electric and magnetic fields as a functions of y E and Hy . This work has as main objective the method LTT structures resonator line slot with four layers of material photonic PBG, for obtaining the complex resonant frequency and efficiency of this structure. PBG theory is applied to obtain the relative permittivity for the substrate biases sep compounds photonic material. Numerical-computational results in graph form in two dimensions for all the analysis are presented for the proposed structures that have photonic materials, as substrates