Polímeros de coordenação à base de cobalto(II) e N,N'-bis(4-piridil)-1,4,5,8-naftaleno diimida como ligante e suas propriedade estruturais, espectroscópicas e fotoelétricas

Polímeros de coordenação têm atraído a atenção de pesquisadores na última década por conta de sua incrível versatilidade e virtualmente infinito número de possibilidades de combinação de ligantes orgânicos e centros metálicos. Estes compostos normalmente herdam as características magnéticas, eletrônicas e espectroscópicas de seus componentes base. Entretanto, apesar do crescente número de trabalhos na área, ainda são raros os polímeros de coordenação que apresentem condutividade elétrica. Para este fim, utilizou-se a N,N\'-bis(4-piridil)-1,4,5,8-naftaleno diimida, ou NDI-py, que pertence a uma classe de compostos rígidos, planares, quimicamente e termicamente estáveis e que já foram extensamente estudados por suas propriedades fotoeletroquímicas e semicondução do tipo n. O primeiro polímero de coordenação sintetizado, MOF-CoNDI-py-1, indicou ser um polímero linear, de estrutura 1D. O segundo, MOF-CoNDI-py-2, que conta com ácido tereftálico como ligante suporte, é um sólido cristalino com cela unitária monoclínica pertencente ao grupo espacial C2/c, determinado por difração de raios-X de monocristal. A rede apresenta um arranjo trinuclear de íons Co(II) alto spin com coordenados em uma geometria de octaedro distorcido, enquanto os ligantes NDI-py se encontram em um arranjo paralelo na estrutura, em distâncias apropriadas para transferência eletrônica. Com o auxílio de cálculo teóricos a nível de DFT, foi realizado um estudo aprofundado dos espectros eletrônicos e vibracionais, com atribuição das transições observadas, tanto para o MOF-CoNDI-py-2 quanto para o ligante NDI-py livre. A rede de coordenação absorve em toda a região do espectro eletrônico analisada, de 200 nm a 2500 nm, além de apresentar luminescência com característica do ligante. Dispositivos eletrônicos fabricados com um cristal do MOF-CoNDI-py-2 revelaram condutividades da ordem de 7,9 10-3 S cm -1, a maior já observada para um MOF. Além de elevada, a condutividade elétrica dos cristais demonstrou-se altamente anisotrópica, sendo significativamente menos condutor em algumas direções. Os perfis de corrente versus voltagem foram analisados em termos de mecanismos de condutividade, sendo melhores descritos por um mecanismo limitado pelo eletrodo to tipo Space-Charge Limited Current, concordando com a proposta de condutividade através dos planos de NDI-py na rede. A condutividade dos cristais também é fortemente dependente de luz, apresentando fotocondução quando irradiado por um laser vermelho, de 632 nm, enquanto apresenta um comportamento fotorresistivo frente a uma fonte de luz branca. Estes resultados, combinados, trazem um MOF em uma estrutura incomum e com elevada condutividade elétrica, modulada por luz, em medidas diretas de corrente. Não existem exemplos conhecidos de MOFs na literatura com estas características.

Investigation of photorefractive subharmonics in the absence of wavemixing

Using a new optical configuration free from the influence of photorefractive optical nonlinearity, we investigate the main characteristics of the spatial subharmonic K/2 excited in a Bi12SiO20 crystal by a light-intensity pattern with wave vector K and frequency O. It is shown that in a large region of intensity and applied electric field the optimum value O of the frequency corresponds to the conditions of parametric excitation of the weakly damped eigenmodes of the medium: the space-charge waves. The threshold and above-threshold characteristics of the subharmonic regime are in good agreement with the theory.

Longitudinal parametric oscillation in photorefractive sillenites: comparison between theory and experiment

By using an alternative setup for photorefractive parametric oscillation in which wave mixing between the recording beams is avoided it has become possible to make more detailed comparisons with the space-charge wave theory. In the present paper we compare the experimental features of longitudinal parametric oscillation observed in a crystal of Bi12SiO20 with the theoretical predictions.

Resonant two-wave mixing in photorefractive materials with the aid of dc and ac fields

A recently predicted resonant effect for the enhancement of two-wave mixing in photorefractive materials is investigated. The resonance occurs when the frequency of the applied ac field agrees with the eigenfrequency of the excited space-charge wave. Experimentally a clear resonance is found, as predicted by the theory, for high dc electric fields, but the resonance is smeared out for lower fields. A modified theory, taking into account the second temporal harmonic of the space-charge wave, shows good agreement with the experimental results.

Excitation of higher spatial harmonics by a moving light pattern in sillenites

We investigate numerically the dependence of higher harmonics of the space-charge field on the detuning frequency between the pump waves, which form a running interference pattern. Bistability and hysteresis of harmonics are predicted for a contrast of the interference pattern m =(0.25-0.3). For contrasts m˜1 and small detuning frequencies we show the existence of a narrow resonance, connected with the nonlinear excitation of a slowly decreasing sequence of spatial harmonics. For experiments we use a BSO crystal in the optical configuration which avoids nonlinear optical distortions. The experimental data show good qualitative agreement with theory.

Investigation of photorefractive subharmonics in the absence of wavemixing

Using a new optical configuration free from the influence of photorefractive optical nonlinearity, we investigate the main characteristics of the spatial subharmonic K/2 excited in a Bi12SiO20 crystal by a light-intensity pattern with wave vector K and frequency O. It is shown that in a large region of intensity and applied electric field the optimum value O of the frequency corresponds to the conditions of parametric excitation of the weakly damped eigenmodes of the medium: the space-charge waves. The threshold and above-threshold characteristics of the subharmonic regime are in good agreement with the theory.

Low frequency peculiarities of the photorefractive response in sillenites

We investigate experimentally and theoretically the dependence of the amplitude of the spatial fundamental grating, created by a pair of coherent light beams while using the running grating technique [M.P. Petrov, S.I. Stepanov and A.V. Khomenko, Photorefractive Crystals in Coherent Optical Systems, Springer Series in Optical Sciences (Springer, 1991); P. Refregier, L. Solymar, H. Rajbenbach and J.P. Huignard, J. Appl. Phys. 58 (1985) 45], as a function of detuning frequency and beam ratio ß in photorefractive Bi12SiO20. It is shown that for ß > 0.05, in addition to the main peak in the frequency dependence of the amplitude, there is an additional peak of lower frequency which, as a rule, dominates the main peak. The position of the main peak depends on ß. The experimental results are in good agreement with the theoretical analysis and the general ideas about excitation and nonlinear interaction of weakly damped space-charge waves.

Low frequency peculiarities of the photorefractive response in sillenites

We investigate experimentally and theoretically the dependence of the amplitude of the spatial fundamental grating, created by a pair of coherent light beams while using the running grating technique [M.P. Petrov, S.I. Stepanov and A.V. Khomenko, Photorefractive Crystals in Coherent Optical Systems, Springer Series in Optical Sciences (Springer, 1991); P. Refregier, L. Solymar, H. Rajbenbach and J.P. Huignard, J. Appl. Phys. 58 (1985) 45], as a function of detuning frequency and beam ratio ß in photorefractive Bi12SiO20. It is shown that for ß > 0.05, in addition to the main peak in the frequency dependence of the amplitude, there is an additional peak of lower frequency which, as a rule, dominates the main peak. The position of the main peak depends on ß. The experimental results are in good agreement with the theoretical analysis and the general ideas about excitation and nonlinear interaction of weakly damped space-charge waves.

Excitation of higher spatial harmonics by a moving light pattern in sillenites

We investigate numerically the dependence of higher harmonics of the space-charge field on the detuning frequency between the pump waves, which form a running interference pattern. Bistability and hysteresis of harmonics are predicted for a contrast of the interference pattern m =(0.25-0.3). For contrasts m˜1 and small detuning frequencies we show the existence of a narrow resonance, connected with the nonlinear excitation of a slowly decreasing sequence of spatial harmonics. For experiments we use a BSO crystal in the optical configuration which avoids nonlinear optical distortions. The experimental data show good qualitative agreement with theory.

Longitudinal parametric oscillation in photorefractive sillenites: comparison between theory and experiment

By using an alternative setup for photorefractive parametric oscillation in which wave mixing between the recording beams is avoided it has become possible to make more detailed comparisons with the space-charge wave theory. In the present paper we compare the experimental features of longitudinal parametric oscillation observed in a crystal of Bi12SiO20 with the theoretical predictions.

Resonant two-wave mixing in photorefractive materials with the aid of dc and ac fields

A recently predicted resonant effect for the enhancement of two-wave mixing in photorefractive materials is investigated. The resonance occurs when the frequency of the applied ac field agrees with the eigenfrequency of the excited space-charge wave. Experimentally a clear resonance is found, as predicted by the theory, for high dc electric fields, but the resonance is smeared out for lower fields. A modified theory, taking into account the second temporal harmonic of the space-charge wave, shows good agreement with the experimental results.

Ferroelectric-like behaviour of melanin:humidity effect on current-voltage characteristics

The influence of low vacuum on quasistatic current-voltage (I–V) dependences and the impact of wet air pulse on dynamic bipolar I-V-loops and unipolar I-V-curves of fungal melanin thin layers have been studied for the first time. The threshold hysteresis voltages of I–V dependences are near to the standard electrode potentials of anodic water decomposition. Short wet air pulse impact leads to sharp increase of the current and appearance of “hump”-like and “knee”-like features of I-V-loops and I-V-curves, respectively. By treatment of I-V-loop allowing for I-V-curve shape the maxima of displacement current are revealed. The peculiarities of I-V-characteristics were modelled by series-parallel RC-circuit with Zener diodes as nonlinear elements. As a reason of appearance of temporal polar media with reversible ferroelectric-like polarization and ionic space charge transfer is considered the water-assisted dissociation of some ionic groups of melanin monomers that significantly influences electrophysical parameters of melanin nanostructures.

Multiscale Analysis for Field-Effect Penetration through Two-Dimensional Materials

Gate-tunable two-dimensional (2D) materials-based quantum capacitors (QCs) and van der Waals heterostructures involve tuning transport or optoelectronic characteristics by the field effect. Recent studies have attributed the observed gate-tunable characteristics to the change of the Fermi level in the first 2D layer adjacent to the dielectrics, whereas the penetration of the field effect through the one-molecule-thick material is often ignored or oversimplified. Here, we present a multiscale theoretical approach that combines first-principles electronic structure calculations and the Poisson–Boltzmann equation methods to model penetration of the field effect through graphene in a metal–oxide–graphene–semiconductor (MOGS) QC, including quantifying the degree of “transparency” for graphene two-dimensional electron gas (2DEG) to an electric displacement field. We find that the space charge density in the semiconductor layer can be modulated by gating in a nonlinear manner, forming an accumulation or inversion layer at the semiconductor/graphene interface. The degree of transparency is determined by the combined effect of graphene quantum capacitance and the semiconductor capacitance, which allows us to predict the ranking for a variety of monolayer 2D materials according to their transparency to an electric displacement field as follows: graphene > silicene > germanene > WS2 > WTe2 > WSe2 > MoS2 > phosphorene > MoSe2 > MoTe2, when the majority carrier is electron. Our findings reveal a general picture of operation modes and design rules for the 2D-materials-based QCs.

Endoscopic optical coherence tomography : design and application

This thesis presents an investigation on endoscopic optical coherence tomography (OCT). As a noninvasive imaging modality, OCT emerges as an increasingly important diagnostic tool for many clinical applications. Despite of many of its merits, such as high resolution and depth resolvability, a major limitation is the relatively shallow penetration depth in tissue (about 2∼3 mm). This is mainly due to tissue scattering and absorption. To overcome this limitation, people have been developing many different endoscopic OCT systems. By utilizing a minimally invasive endoscope, the OCT probing beam can be brought to the close vicinity of the tissue of interest and bypass the scattering of intervening tissues so that it can collect the reflected light signal from desired depth and provide a clear image representing the physiological structure of the region, which can not be disclosed by traditional OCT. In this thesis, three endoscope designs have been studied. While they rely on vastly different principles, they all converge to solve this long-standing problem.

A hand-held endoscope with manual scanning is first explored. When a user is holding a hand- held endoscope to examine samples, the movement of the device provides a natural scanning. We proposed and implemented an optical tracking system to estimate and record the trajectory of the device. By registering the OCT axial scan with the spatial information obtained from the tracking system, one can use this system to simply ‘paint’ a desired volume and get any arbitrary scanning pattern by manually waving the endoscope over the region of interest. The accuracy of the tracking system was measured to be about 10 microns, which is comparable to the lateral resolution of most OCT system. Targeted phantom sample and biological samples were manually scanned and the reconstructed images verified the method.

Next, we investigated a mechanical way to steer the beam in an OCT endoscope, which is termed as Paired-angle-rotation scanning (PARS). This concept was proposed by my colleague and we further developed this technology by enhancing the longevity of the device, reducing the diameter of the probe, and shrinking down the form factor of the hand-piece. Several families of probes have been designed and fabricated with various optical performances. They have been applied to different applications, including the collector channel examination for glaucoma stent implantation, and vitreous remnant detection during live animal vitrectomy.

Lastly a novel non-moving scanning method has been devised. This approach is based on the EO effect of a KTN crystal. With Ohmic contact of the electrodes, the KTN crystal can exhibit a special mode of EO effect, termed as space-charge-controlled electro-optic effect, where the carrier electron will be injected into the material via the Ohmic contact. By applying a high voltage across the material, a linear phase profile can be built under this mode, which in turn deflects the light beam passing through. We constructed a relay telescope to adapt the KTN deflector into a bench top OCT scanning system. One of major technical challenges for this system is the strong chromatic dispersion of KTN crystal within the wavelength band of OCT system. We investigated its impact on the acquired OCT images and proposed a new approach to estimate and compensate the actual dispersion. Comparing with traditional methods, the new method is more computational efficient and accurate. Some biological samples were scanned by this KTN based system. The acquired images justified the feasibility of the usage of this system into a endoscopy setting. My research above all aims to provide solutions to implement an OCT endoscope. As technology evolves from manual, to mechanical, and to electrical approaches, different solutions are presented. Since all have their own advantages and disadvantages, one has to determine the actual requirements and select the best fit for a specific application.