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In this work, ab initio Density Functional Theory calculations are performed to investigate the evolution of the electronic and optical properties of 2D Tellurium—called Tellurene—for three different allotropic forms (α -, β - and γ -phase), as a function of the number of layers. We estimate the exciton binding energies and radii of the studied systems, using a 2D analytical model. Our results point out that these quantities are strongly dependent on the allotropic form, as well as on the number of layers. Remarkably, we show that the adopted method is suitable for reliably predicting, also in the case of Tellurene, the exciton binding energy, without the need of computationally demanding calculations, possibly suggesting interesting insights into the features of the system. Finally, we inspect the nature of the mechanisms ruling the interaction of neighbouring Tellurium atoms helical chains (characteristic of the bulk and α -phase crystal structures). We show that the interaction between helical chains is strong and cannot be explained by solely considering the van der Waals interaction. [ABSTRACT FROM AUTHOR]

We combine density functional theory and many body perturbation theory to investigate the electronic properties of Si(100) and Ge(100) surfaces terminated with halogen atoms (–I, –Br, –Cl, –F) and other chemical functionalizations (–H, –OH, –CH3) addressing the absolute values of their work function, electronic affinity and ionization potential. Our results point out that electronic properties of functionalized surfaces strongly depend on the chemisorbed species and much less on the surface crystal orientation. The presence of halogens at the surface always leads to an increment of the work function, ionization potential and electronic affinity with respect to fully hydrogenated surfaces. On the contrary, the presence of polar –OH and –CH3 groups at the surface leads to a reduction of the aforementioned quantities with respect to the H-terminated system. Starting from the work functions calculated for the Si and Ge passivated surfaces, we apply a simple model to estimate the properties of functionalized SiGe surfaces. The possibility of modulating the work function by changing the chemisorbed species and composition is predicted. The effects induced by different terminations on the band energy line-up profile of SiGe surfaces are then analyzed. Interestingly, our calculations predict a type-II band offset for the H-terminated systems and a type-I band offset for the other cases. [ABSTRACT FROM AUTHOR]

Silicon nanocrystals and nanowires have been extensively studied because of their novel properties and their applications in electronic, optoelectronic, photovoltaic, thermoelectric and biological devices. Here we discuss results from ab initio calculations for undoped and doped Si nanocrystals and nanowires, showing how theory can aid and improve comprehension of the structural, electronic and optical properties of these systems. [ABSTRACT FROM AUTHOR]

The properties of n- and p-doped silicon nanocrystals obtained through ab initio calculations are reviewed here. The aim is the understanding of the effects induced by substitutional doping on the structural, electronic and optical properties of free-standing and matrix-embedded Si nanocrystals. The preferential positioning of the dopants and their effects on the structural properties with respect to the undoped case, as a function of the nanocrystals diameter and termination, are identified through total-energy considerations. The localization of the acceptor and donor related levels in the band gap of the Si nanocrystals, together with the impurity activation energy, are discussed as a function of the nanocrystals size. The dopant induced differences in the optical properties with respect to the undoped case are presented. Finally, the case of B and P co-doped nanocrystals is discussed showing that if carriers are perfectly compensated, the Si nanocrystals undergo a minor structural distortion around the impurities inducing a significant decrease of the impurities formation energies with respect to the single doped case. Due to co-doping, additional peaks are introduced in the absorption spectra, giving rise to a size-dependent red shift of the absorption spectra. [ABSTRACT FROM AUTHOR]

Si nanocrystals have been extensively studied because of their novel properties and their potential applications in electronic, optoelectronic, photovoltaic, thermoelectric and biological devices. These new properties are achieved through the combination of the quantum confinement of carriers and the strong influence of surface chemistry. As in the case of bulk Si the tuning of the electronic, optical and transport properties is related to the possibility of doping, in a controlled way, the nanocrystals. This is a big challenge since several studies have revealed that doping in Si nanocrystals differs from the one of the bulk. Theory and experiments have underlined that doping and codoping are influenced by a large number of parameters such as size, shape, passivation and chemical environment of the silicon nanocrystals. However, the connection between these parameters and dopant localization as well as the occurrence of self-purification effects are still not clear. In this review we summarize the latest progress in this fascinating research field considering free-standing and matrix-embedded Si nanocrystals both from the theoretical and experimental point of view, with special attention given to the results obtained by ab-initio calculations and to size-, surface- and interface-induced effects. [ABSTRACT FROM AUTHOR]

Carrier multiplication is a non-radiative recombination mechanism that leads to the generation of two or more electron-hole pairs after absorption of a single photon. By reducing the occurrence of dissipative effects, this process can be exploited to increase solar cell performance. In this work, we introduce two different theoretical fully ab initio tools that can be adopted to study carrier multiplication in nanocrystals. The tools are described in detail and compared. Subsequently, we calculate carrier multiplication lifetimes in H- and OH-terminated silicon nanocrystals, pointed out the role played by the passivation on the carrier multiplication processes. [ABSTRACT FROM AUTHOR]

First-principles calculations of work function tuning induced by different chemical terminations on Si(100) surface are presented and discussed. We find that the presence of halogen atoms (I, Br, Cl, and F) leads to an increase of the work function if compared to the fully hydrogenated surface. This is a quite general effect and is directly linked to the chemisorbed atoms electronegativity as well as to the charge redistribution at the interface. All these results are examined with respect to previous theoretical works and experimental data obtained for the (100) as well as other Si surface orientations. Based on this analysis, we argue that the changes in the electronic properties caused by variations of the interfacial chemistry strongly depend on the chemisorbed species and much less on the surface crystal orientation. [ABSTRACT FROM AUTHOR]

We present density functional theory calculations of carrier multiplication properties in a system of strongly coupled silicon nanocrystals. Our results suggest that nanocrystal—nanocrystal interaction can lead to a reduction of the carrier multiplication energy threshold without altering the carrier multiplication efficiency at high energies, in agreement with experiments. The time evolution of the number of electron—hole pairs generated in a system of strongly interacting nanocrystals upon absorption of high-energy photons is analyzed by solving a system of coupled rate equations, where exciton recycling mechanisms are implemented. We reconsider the role played by Auger recombination which is here accounted also as an active, nondetrimental process. [ABSTRACT FROM AUTHOR]

The conversion of solar radiation into electric current with high efficiency is one of the most important topics of modern scientific research, as it holds great potential as a source of clean and renewable energy. Exploitation of interaction between nanocrystals seems to be a promising route to the establishment of third-generation photovoltaics. Here, we adopt a fully ab initio scheme to estimate the role of nanoparticle interplay in the carrier multiplication dynamics of interacting silicon nanocrystals. Energy and charge transfer-based carrier multiplication events are studied as a function of nanocrystal separation, demonstrating the benefits induced by the wavefunction sharing regime. We prove the relevance of these recombinative mechanisms for photovoltaic applications in the case of silicon nanocrystals arranged in dense arrays, quantifying at an atomic scale which conditions maximize the outcome. [ABSTRACT FROM AUTHOR]

A detailed description, at the atomistic scale, of the dynamics of excess electrons and holes is fundamental in order to improve the performance of many optoelectronic devices. Among all recombination processes, nonradiative decay paths play a fundamental role in most semiconductor devices, such as optoelectronic devices and solar cells, limiting their efficiency. In this work, a precise ab initio analysis of the direct Auger recombination processes in both n- and p-type Si and GaAs crystals is presented. Our simulations of minority carrier Auger lifetimes rely on an accurate electronic band structure, calculated using density functional theory with the inclusion of quasiparticle corrections. The results obtained are in good agreement with experimental data for both n-Si and p-GaAs, proving the importance of the direct Auger recombination mechanism in such systems. On the contrary, we show that different nonradiative recombination paths are necessary to explain the experimental results for both p-Si and n-GaAs. [ABSTRACT FROM AUTHOR]

Abstract: Within a first-principles framework we show the dependence of the optical properties of silicon nanocrystallites embedded in a silica matrix on the crystalline vs. amorphous order of the system. Moreover we calculate how many-body effects modify the electronic and optical properties of the embedded silicon nanodots. A discussion about the different roles played by dimensionality, interface properties, disorder and excitonic effects on the electronic and optical properties of the confined nanostructures is presented. [Copyright &y& Elsevier]

Abstract: Motivated by the pioneering work of McFarland and Tang on multilayer photovoltaic devices, we discuss here structural and electronic properties of the Au/TiO2(110) interface for a coverage of 1 monolayer (1 ML) of gold, both for a stoichiometric and a reduced (Ti-rich) rutile surface. A detailed analysis of the Schottky barrier height for such systems is presented and the effects generated on this barrier by the presence of an oxygen vacancy (localized on the rutile support) are discussed. [Copyright &y& Elsevier]

We discuss results of ab initio calculations for Si, Ge, and Si/Ge nanowires and nanocrystals showing that theory can improve the comprehension of the properties of these systems. First, we consider doped and undoped freestanding hydrogenated nanowires and we explore their properties as a function of the size, geometry, and composition. Secondly, we focus the discussion on the electronic properties of matrix embedded Si, Ge, and Si/Ge nanocrystals by pointing out the role played by composition, quantum confinement, and strain. The discussed results show that, for Si/Ge nanowires, the interface between Si and Ge region plays an important role determining, in some case, the formation of a type II band offset, which is essential for photovoltaic applications. Moreover, for Si/Ge core–shell nanowires, it is shown that: i) selective doping results in the formation of hole or electron accumulation, with interesting consequences for the use of these materials in thermoelectrics and ii) through compensated doping, it is possible to tune the optical properties of these systems. For the embedded nanocrystals, the outcomes suggest that Ge nanocrystals can be suitable as optical absorption centers and that Si/Ge nanocrystals, owing to the localization of the band edge states, are interesting for photovoltaic cells. In this work, Marri et al. discuss first‐principles calculations concerning the microscopic properties of Si, Ge, and Si/Ge nanowires (NWs) and nanocrystals (NCs). These systems are very interesting for their possible technological applications. The authors prove that electronic, optical, and transport properties of NWs can be tuned by changing composition and geometry. Moreover, the authors deeply analyze the role played by quantum confinement and by strain in Si, Ge, and Si/Ge NCs. The novelty and importance of these results may support further experimental investigation for the design of advanced Si‐ and Ge‐based nanodevices. [ABSTRACT FROM AUTHOR]

One of the most important goals in the field of renewable energy is the development of original solar cell schemes employing new materials to overcome the performance limitations of traditional solar cell devices. Among such innovative materials, nanostructures have emerged as an important class of materials that can be used to realize efficient photovoltaic devices. When these systems are implemented into solar cells, new effects can be exploited to maximize the harvest of solar radiation and to minimize the loss factors. In this context, carrier multiplication seems one promising way to minimize the effects induced by thermalization loss processes thereby significantly increasing the solar cell power conversion. In this work we analyze and quantify different types of carrier multiplication decay dynamics by analyzing systems of isolated and coupled silicon nanocrystals. The effects on carrier multiplication dynamics by energy and charge transfer processes are also discussed.

Effective and safe systemic treatment for advanced hepatocellular carcinoma (HCC) with severe underlying cirrhosis is not yet available. Sorafenib, an oral multikinase inhibitor, has proved to be effective in the treatment of patients affected by HCC with Child-Pugh class A liver function. For patients with cirrhosis-associated HCC having Child-Pugh class B and C liver function, no systemic treatments of documented efficacy and safety exist. We report a case of metastatic HCC associated with Child-Pugh class B cirrhosis that was treated with low, "metronomic" doses of capecitabine (1000 mg/day continuously). This treatment was effective and well tolerated and the response was maintained for 18 months. Metronomic capecitabine may represent a possible alternative in the treatment of those patients with advanced cirrhosis-associated HCC who cannot be treated with sorafenib.