Implications of TiO2 surface functionalization on polycrystalline mixed halide perovskite films and photovoltaic devices

We exploit TiO2 surface functionalization as a tool to induce the crystallization process of CH3NH3PbI3xClx perovskite thin films resulting in a reduction of the degree of orientation of the (110) crystallographic planes. Notably, the variation of the film crystalline orientational order does not affect the photovoltaic performances of the perovskite-based devices, whose efficiency remains mostly unchanged. Our findings suggest that other factors are more significant in determining the device efficiency, such as the non-homogenous coverage of the TiO2 surface causing charge recombination at the organic/TiO2 interface, defect distribution on the perovskite bulk and at the interfaces, and transport in the organic or TiO2 layer. This observation represents a step towards the comprehension of the perovskite film peculiarities influencing the photovoltaic efficiency for high performance devices.

Multiscale morphology design of hybrid halide perovskites through a polymeric template

Hybrid halide perovskites have emerged as promising active constituents of next generation solution processable optoelectronic devices. During their assembling process, perovskite components undergo very complex dynamic equilibria starting in solution and progressing throughout film formation. Finding a methodology to control and affect these equilibria, responsible for the unique morphological diversity observed in perovskite films, constitutes a fundamental step towards a reproducible material processability. Here we propose the exploitation of polymer matrices as cooperative assembling components of novel perovskite CH3NH3PbI3 : polymer composites, in which the control of the chemical interactions in solution allows a predictable tuning of the final film morphology. We reveal that the nature of the interactions between perovskite precursors and polymer functional groups, probed by Nuclear Magnetic Resonance (NMR) spectroscopy and Dynamic Light Scattering (DLS) techniques, allows the control of aggregates in solution whose characteristics are strictly maintained in the solid film, and permits the formation of nanostructures that are inaccessible to conventional perovskite depositions. These results demonstrate how the fundamental chemistry of perovskite precursors in solution has a paramount influence on controlling and monitoring the final morphology of CH3NH3PbI3 (MAPbI3) thin films, foreseeing the possibility of designing perovskite : polymer composites targeting diverse optoelectronic applications.

Measurements of small ice crystals in arctic cirrus: observations from the Indirect and Semi-Direct Aerosol Campaign (ISDAC)

In-situ observations on the size and shape of particles in arctic cirrus are less common than those in mid-latitude and tropical cirrus with considerable uncertainty about the contributions of small ice crystals (maximum dimension D<50 µm) to the mass and radiative properties that impact radiative forcing. In situ measurements of small ice crystals in arctic cirrus were made during the Indirect and Semi-Direct Aerosol Campaign (ISDAC) in April 2008 during transits of the National Research Council of Canada Convair-580 between Fairbanks and Barrow, Alaska and during Mixed Phase Arctic Cloud Experiment (MPACE) in October 2004 with the University of North Dakota (UND) Citation over Barrow, Alaska. Concentrations of small ice crystals with D < 50 μm from a Cloud and Aerosol Spectrometer (CAS), a Cloud Droplet Probe (CDP), a Forward Scattering Spectrometer Probe (FSSP), and a two-dimensional stereo probe (2DS) were compared as functions of the concentrations of crystals with D > 100 μm measured by a Cloud Imaging Probe (CIP) and two-dimensional stereo probe (2DS) in order to assess whether the shattering of large ice crystals on protruding components of different probes artificially amplified measurements of small ice crystal concentrations. The dependence of the probe comparison on other variables as CIP N>100 (number concentrations greater than diameter D>100 μm),temperature, relative humidity respect to ice (RHice), dominant habit from the Cloud Particle Imager (CPI), aircraft roll, pitch, true air speed and angle of attack was examined to understand potential causes of discrepancies between probe concentrations. Data collected by these probes were also compared against the data collected by a CAS, CDP and CIP during the Tropical Warm Pool-International Cloud Experiment (TWP-ICE) and by a CAS and 2DS during the Tropical Composition, Cloud and Climate Coupling (TC4) missions. During ISDAC, the CAS and FSSP both overestimated measurements of small ice crystals compared to both the CDP and 2DS by 1-2 orders of magnitude. Further, the amount of overestimation increased with the concentrations from the CIP2 (N>100 > 0.1 L-1). There was an unexplained discrepancy in concentrations of small crystals between the CDP and 2DS during ISDAC. In addition, there was a strong dependence on RHice of the average ratios of the N3-50, CAS/N3-50,CDP, N3-50, FSSP096/N3-50,CDP, N3-50, CAS/N3-50,FSSP096, N10-50, CDP/N3-50,2DS, N10-50, FSSP096/N10-50,2DS. Continued studies are needed to understand the discrepancy of these probes.

Lipid-Based Liquid Crystals As Carriers for Antimicrobial Peptides: Phase Behavior and Antimicrobial Effect

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Lightweight metal halide and hydride fast Li ion conductors

This work was motivated by the extensive research on lithium solid state materials, which have attracted increasing interest for potential applications in hydrogen storage and/or lithium ion batteries due to their extraordinary properties. In this thesis, LiBH4-derived materials, LiInBr4 and complex phases based on lithium ammonia borane with potential use as solid state electrolytes were successfully synthesised and characterised.

Diketonylpyridinium cations as a support of new ionic liquid crystals and ion-conductive materials: analysis of counter-ion effects

Ionic liquid crystals (ILCs) allow the combination of the high ionic conductivity of ionic liquids (ILs) with the supramolecular organization of liquid crystals (LCs). ILCs salts were obtained by the assembly of long-chained diketonylpyridinium cations of the type [HOO^(R(n)pyH)] + and BF_(4)^(-) , ReO_(4)^(-), NO_(3)^(-), CF_(3)SO_(3)^(-), CuCl_(4)^(2-) counter-ions. We have studied the thermal behavior of five series of compounds by differential scanning calorimetry (DSC) and hot stage polarized light optical microscopy (POM). All materials show thermotropic mesomorphism as well as crystalline polymorphism. X-ray diffraction of the [HOO^(R(12)pyH)][ReO_(4)] crystal reveals a layered structure with alternating polar and apolar sublayers. The mesophases also exhibit a lamellar arrangement detected by variable temperature powder X-ray diffraction. The CuCl_(4)^(2-) salts exhibit the best LC properties followed by the ReO_(4)^(-) ones due to low melting temperature and wide range of existence. The conductivity was probed for the mesophases in one species each from the ReO_(4)^(-) , and CuCl_(4)^(2-) families, and for the solid phase in one of the non-mesomorphic Cl^(-) salts. The highest ionic conductivity was found for the smectic mesophase of the ReO_(4)^(-) containing salt, whereas the solid phases of all salts were dominated by electronic contributions. The ionic conductivity may be favored by the mesophase lamellar structure.

Swelling properties of alkali-metal doped polymeric anion-exchange membranes in alcohol media for application in fuel cells

Swelling properties of four commercial anion-exchange membranes with different structure have been analyzed in several hydro-organic media. With this target, the liquid uptake and the surface expansion of the membranes in contact with different pure liquids, water and alcohols (methanol, ethanol and 1-propanol), and with water alcohol mixtures with different concentrations have been experimentally determined in presence and in absence of an alkaline medium (LiOH, NaOH and KOH of different concentrations). The alkali-metal doping effect on the membrane water uptake has also been investigated, analyzing the influence of the hydroxide concentration and the presence of an alcohol in the doping solution. The results show that the membrane structure plays an essential role in the influence that alcohol nature and alkaline media has on the selective properties of the membrane. The heterogeneous membranes, with lower density, show higher liquid uptakes and dimensional changes than the homogeneous membranes, regardless of the doping conditions. (C) 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Mechanical behaviour at high temperature of alkali-activated aluminosilicates (geopolymers)

This study was designed to determine the effect of temperature on the mechanical strength (in both in vivo and post-exposure trials) of two alkaline cements (without OPC): (a) 100% fly ash (FA) and (b) 85% FA + 15% bauxite, the activated alkaline solution used was 85% 10-M NaOH + 15% sodium silicate. A Type I 42.5 R Portland cement was used as a control. Two series of trials were conducted: (i) in vivo trials in which bending and compressive strength, fracture toughness and modulus of elasticity were determined at different temperatures; and (ii) post-firing trials, assessing residual bending and compres-sive strength after a 1-h exposure to high temperatures and subsequent cooling. The findings showed that from 25 to 600 C, irrespective of the type of test (in vivo or post-firing), compressive mechanical strength rose, with the specimens exhibiting elastic behaviour and consequently brittle failure. At tem-peratures of over 600 C, behaviour differed depending on the type of test: (i) in the in vivo trials the high temperature induced pseudo-plastic strain and a decline in mechanical strength that did not necessarily entail specimen failure; (ii) in the post-firing trials, compressive strength rose.

Single-Polarization Double Refraction in Plasmonic Crystals: Considerations on Energy Flow

We examined the optical properties of nanolayered metal-dielectric lattices. At subwavelength regimes, the periodic array of metallic nanofilms demonstrates nonlocality-induced double refraction, conventional positive and as well as negative. In particular, we report on energy-flow considerations concerning both refractive behaviors concurrently. Numerical simulations provide transmittance of individual beams in Ag-TiO2 metamaterials under different configurations. In regimes of the effective-medium theory predicting elliptic dispersion, negative refraction may be stronger than the expected positive refraction.

Dynamics of Granular Crystals with Elastic-Plastic Contacts

We study the behavior of granular crystals subjected to impact loading that creates plastic deformation at the contacts between constituent particles. Granular crystals are highly periodic arrangements of spherical particles, arranged into densely packed structures resembling crystals. This special class of granular materials has been shown to have unique dynamics with suggested applications in impact protection. However, previous work has focused on very low amplitude impacts where every contact point can be described using the Hertzian contact law, valid only for purely elastic deformation. In this thesis, we extend previous investigation of the dynamics of granular crystals to significantly higher impact energies more suitable for the majority of applications. Additionally, we demonstrate new properties specific to elastic-plastic granular crystals and discuss their potential applications as well. We first develop a new contact law to describe the interaction between particles for large amplitude compression of elastic-plastic spherical particles including a formulation for strain-rate dependent plasticity. We numerically and experimentally demonstrate the applicability of this contact law to a variety of materials typically used in granular crystals. We then extend our investigation to one-dimensional chains of elastic-plastic particles, including chains of alternating dissimilar materials. We show that, using the new elastic-plastic contact law, we can predict the speed at which impact waves with plastic dissipation propagate based on the material properties of the constituent particles. Finally, we experimentally and numerically investigate the dynamics of two-dimensional and three-dimensional granular crystals with elastic-plastic contacts. We first show that the predicted wave speeds for 1D granular crystals can be extended to 2D and 3D materials. We then investigate the behavior of waves propagating across oblique interfaces of dissimilar particles. We show that the character of the refracted wave can be predicted using an analog to Snell's law for elastic-plastic granular crystals and ultimately show how it can be used to design impact guiding "lenses" for mitigation applications.

Temporal solitonic crystals and non-Hermitian informational lattices

Clusters of temporal optical solitons—stable self-localized light pulses preserving their form during propagation—exhibit properties characteristic of that encountered in crystals. Here, we introduce the concept of temporal solitonic information crystals formed by the lattices of optical pulses with variable phases. The proposed general idea offers new approaches to optical coherent transmission technology and can be generalized to dispersion-managed and dissipative solitons as well as scaled to a variety of physical platforms from fiber optics to silicon chips. We discuss the key properties of such dynamic temporal crystals that mathematically correspond to non-Hermitian lattices and examine the types of collective mode instabilities determining the lifetime of the soliton train. This transfer of techniques and concepts from solid state physics to information theory promises a new outlook on information storage and transmission.