Epitaxial growth of visible to infra-red transparent conducting In2O3 nanodot dispersions and reversible charge storage as a Li-ion battery anode

Unique bimodal distributions of single crystal epitaxially grown In2O3 nanodots on silicon are shown to have excellent IR transparency greater than 87% at IR wavelengths up to 4 μm without sacrificing transparency in the visible region. These broadband antireflective nanodot dispersions are grown using a two-step metal deposition and oxidation by molecular beam epitaxy, and backscattered diffraction confirms a dominant (111) surface orientation. We detail the growth of a bimodal size distribution that facilitates good surface coverage (80%) while allowing a significant reduction in In2O3 refractive index. This unique dispersion offers excellent surface coverage and three-dimensional volumetric expansion compared to a thin film, and a step reduction in refractive index compared to bulk active materials or randomly porous composites, to more closely match the refractive index of an electrolyte, improving transparency. The (111) surface orientation of the nanodots, when fully ripened, allows minimum lattice mismatch strain between the In2O3 and the Si surface. This helps to circumvent potential interfacial weakening caused by volume contraction due to electrochemical reduction to lithium, or expansion during lithiation. Cycling under potentiodynamic conditions shows that the transparent anode of nanodots reversibly alloys lithium with good Coulombic efficiency, buffered by co-insertion into the silicon substrate. These properties could potentially lead to further development of similarly controlled dispersions of a range of other active materials to give transparent battery electrodes or materials capable of non-destructive in situ spectroscopic characterization during charging and discharging.

Loading effect in copper(II) oxide cluster-surface-modified titanium(IV) oxide on visible- and UV-light activities

Cu(acac)2 is chemisorbed on TiO2 particles [P-25 (anatase/rutile = 4/1 w/w), Degussa] via coordination by surface Ti–OH groups without elimination of the acac ligand. Post-heating of the Cu(acac)2-adsorbed TiO2 at 773 K yields molecular scale copper(II) oxide clusters on the surface (CuO/TiO2). The copper loading amount (Γ/Cu ions nm–2) is controlled in a wide range by the Cu(acac)2 concentration and the chemisorption–calcination cycle number. Valence band (VB) X-ray photoelectron and photoluminescence spectroscopy indicated that the VB maximum of TiO2 rises up with increasing Γ, while vacant midgap levels are generated. The surface modification gives rise to visible-light activity and concomitant significant increase in UV-light activity for the degradation of 2-naphthol and p-cresol. Prolonging irradiation time leads to the decomposition to CO2, which increases in proportion to irradiation time. The photocatalytic activity strongly depends on the loading, Γ, with an optimum value of Γ for the photocatalytic activity. Electrochemical measurements suggest that the surface CuO clusters promote the reduction of adsorbed O2. First principles density functional theory simulations clearly show that, at Γ < 1, unoccupied Cu 3d levels are generated in the midgap region, and at Γ > 1, the VB maximum rises and the unoccupied Cu 3d levels move to the conduction band minimum of TiO2. These results suggest that visible-light excitation of CuO/TiO2 causes the bulk-to-surface interfacial electron transfer at low coverage and the surface-to-bulk interfacial electron transfer at high coverage. We conclude that the surface CuO clusters enhance the separation of photogenerated charge carriers by the interfacial electron transfer and the subsequent reduction of adsorbed O2 to achieve the compatibility of high levels of visible and UV-light activities.

(Table 1) Luminescence datings from Varchushka and Pyoza rivers, Russia

The Pyoza River area in the Arkhangelsk district exposes sedimentary sequences suitable for study of the interaction between consecutive Valdaian ice sheets in Northern Russia. Lithostratigraphic investigations combined with luminescence dating have revealed new evidence on the Late Pleistocene history of the area. Overlying glacigenic deposits of the Moscowian (Saalian) glaciation marine deposits previously confined to three separate transgression phases have all been connected to the Mikulinian (Eemian) interglacial. Early Valdaian (E. Weichselian) proglacial, lacustrine and fluvial deposits indicate glaciation to the east or north and consequently glacier damming and meltwater run-off in the Pyoza area around 90-110 ka BP. Interstadial conditions with forest-steppe tundra vegetation and lacustrine and fluvial deposition prevailed at the end of the Early Valdaian around 75-95 ka BP. A terrestrial-based glaciation from easterly uplands reached the Pyoza area at the Early to Middle Valdaian transition around 65-75 ka BP and deposited glaciofluvial strata and subglacial till (Yolkino Till). During deglaciation, laterally extensive glaciolacustrine sediments were deposited in ice-dammed lakes in the early Middle Valdaian around 55-75 ka BP. The Barents-Kara Sea ice sheet deposited the Viryuga Till on the lower Pyoza from northerly directions. The ice sheet formed the Pyoza marginal moraines, which can be correlated with the Markhida moraines further east, and proglacial lacustrine deposition persisted in the area during the first part of the Middle Valdaian. Glacio-isostatic uplift caused erosion followed by pedogenesis and the formation of a deflation horizon in the Middle Valdaian. Widely dispersed periglacial river plains were formed during the Late Valdaian around 10-20 ka BP. Thus, the evidence of a terrestrial-based ice sheet from easterly uplands in the Pyoza area suggests that local piedmont glaciers situated in highlands such as the Timan Ridge or the Urals could have developed into larger, regionally confined ice sheets. Two phases of ice damming and development of proglacial lakes occurred during the Early and Middle Valdaian. The region did not experience glaciation during the Late Valdaian.

Radiation flux from the upper and lower hemispheres in the visible spectral range

This paper describes measurements from shortwave radiation radiosonde ascents done at the Atlantische Expedition 1969. Using the results from a total of 67 ascents mean components of the shortwave radiation budget of the atmospheric layer between the ocean surface and the top of the ascent are discussed. The influence of clouds on the radiation balance is shown by dividing the ascents in classes of cloudiness and cloud altitude. Thereby the albedo of the ocean surface is increasing with increasing amount of cloudiness. Similar the albedo of the troposphere increases involving an increased heating rate of the atmospheric layer.

2.2 eV luminescence in GaN

The yellow Luminescence in GaN centered at 2.2 eV has been studied in various epitaxial layers grown by MOVPE on sapphire and by the sandwich sublimation method on 6H-SiC substrates. The photoluminescence and optically detected magnetic resonance results can be consistently explained by a recombination model involving shallow donors and deep donors.

The influence of photon excitation and proton irradiation on the luminescence properties of yttria stabilized zirconia doped with praseodymium ions

Lanthanide doped zirconia based materials are promising phosphors for lighting applications. Transparent yttria stabilized zirconia fibres, in situ doped with Pr3+ ions, were grown by the laser floating zone method. The single crystalline doped fibres were found to be homogeneous in composition and provide an intense red luminescence at room temperature. The stability of this luminescence due to transitions between the 1D2 → 3H4 multiplets of the Pr3+ ions (intra-4f2 configuration) was studied by photo- and iono-luminescence. The evolution of the red integrated photoluminescence intensity with temperature indicates that the overall luminescence decreases to ca. 40% of the initial intensity at 14 K when heated to room temperature (RT). RT analysis of the iono-luminescence dependence on irradiation fluence reveals a decrease of the intensity (to slightly more than ∼60% of the initial intensity after 25 min of proton irradiation exposure). Nevertheless the luminescence intensity saturates at non-zero values for higher irradiation fluences revealing good potential for the use of this material in radiation environments.

Towards NIR emission: 2-(1H-tetrazol-1-yl)pyridine as versatile ligand for the synthesis of two new families of cationic and neutral Ir(III) complexes.

In the last decades, cyclometalated Ir(III) complexes have drawn a large interest for their unique properties: they are excellent triplet state emitters, thus the emission is phosphorescent in nature; typically high quantum yields and good stability make them good candidates for luminescent materials. Moreover, through an opportune choice of the ligands, it is possible to tune the emission along the whole visible spectra. Thanks to these interesting features, Ir(III) complexes have found different applications in several areas of applied science, from OLEDs to bioimaging. In particular, regarding the second application, a remarkable red-shift in the emission is required, in order to minimize the problem of the tissue penetration and the possible damages for the organisms. With the aim of synthesizing a new family of NIR emitting Ir(III) complexes, we envisaged the possibility to use for the first time 2-(1H-tetrazol-1-yl)pyridine as bidentate ligand able to provide the required red-shift of the emission of the final complexes. Exploiting the versatility of the ligand, I prepared two different families of heteroleptic Ir(III) complexes. In detail, in the first case the 2-(1H-tetrazol-1-yl)pyridine was used as bis-chelating N^N ligand, leading to cationic complexes, while in the second case it was used as cyclometalating C^N ligand, giving neutral complexes. The structures of the prepared molecules have been characterised by NMR spectroscopy and mass spectrometry. Moreover, the neutral complexes’ emissive properties have been measured: emission spectra have been recorded in solution at both room temperature and 77K, as well as in PMMA matrix. DFT calculation has then been performed and the obtained results have been compared to experimental ones.

Error correcting codes for visible light communication systems

Over the past few years, the number of wireless networks users has been increasing. Until now, Radio-Frequency (RF) used to be the dominant technology. However, the electromagnetic spectrum in these region is being saturated, demanding for alternative wireless technologies. Recently, with the growing market of LED lighting, the Visible Light Communications has been drawing attentions from the research community. First, it is an eficient device for illumination. Second, because of its easy modulation and high bandwidth. Finally, it can combine illumination and communication in the same device, in other words, it allows to implement highly eficient wireless communication systems. One of the most important aspects in a communication system is its reliability when working in noisy channels. In these scenarios, the received data can be afected by errors. In order to proper system working, it is usually employed a Channel Encoder in the system. Its function is to code the data to be transmitted in order to increase system performance. It commonly uses ECC, which appends redundant information to the original data. At the receiver side, the redundant information is used to recover the erroneous data. This dissertation presents the implementation steps of a Channel Encoder for VLC. It was consider several techniques such as Reed-Solomon and Convolutional codes, Block and Convolutional Interleaving, CRC and Puncturing. A detailed analysis of each technique characteristics was made in order to choose the most appropriate ones. Simulink models were created in order to simulate how diferent codes behave in diferent scenarios. Later, the models were implemented in a FPGA and simulations were performed. Hardware co-simulations were also implemented to faster simulation results. At the end, diferent techniques were combined to create a complete Channel Encoder capable of detect and correct random and burst errors, due to the usage of a RS(255,213) code with a Block Interleaver. Furthermore, after the decoding process, the proposed system can identify uncorrectable errors in the decoded data due to the CRC-32 algorithm.