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We investigated the impact of quantum confinement on the band gap of chalcogenides 2D nanostructures by means of density functional theory. We studied six different systems: MoS 2 , WS 2 , SnS 2 , GaS, InSe, and HfS 2 and we simulated nanosheets of increasing thickness, ranging from ultrathin films to ∼10-13 nm thick slabs, a size where the properties converge to the bulk. In some cases, the convergence of the band gap with slab thickness is rather slow, and sizeable deviations from the bulk value are still present with few nm-thick sheets. The results of the simulations were compared with the available experimental data, finding a quantitative agreement. The impact of quantum confinement can be rationalized in terms of effective masses of electrons and holes and system's size. These results show the possibility of reliably describing quantum confinement effects on systems for which experimental data are not available., (© 2022 IOP Publishing Ltd.)

We studied the role of iso-valent heteroatoms replacing Ti 4+ cations in the lattice of two titania polymorphs, rutile (r-) and anatase (a-) by means of first principles calculations. The r-TiO 2 (110) and the a-TiO 2 (101) surfaces have been considered and Ti ions in the bulk, sub-surface, and surface sites have been replaced with Si, Ge, Sn, Pb, Zr, Hf, and Ce ions: surface or sub-surface sites are clearly preferred. Since the dopants have the same number of valence electrons as the replaced Ti atom, they can have only two effects: one is steric, related to the different size of the dopant compared to Ti 4+ ; the other is an orbital effect, due to the energy levels associated to the dopant not present on the pristine surface. Both these effects can modify locally the geometric and electronic structure of the surface, in particular by introducing new states in the band gap. To check the effect of the dopants on the surface reactivity we studied as an example the decomposition of HCOOH which can follow four different paths with desorption of (a) H 2, (b) CO, (c) H 2 O, or (d) CO 2 . The results show the very different behavior of the two titania polymorphs considered, rutile and anatase: rutile is more reactive and more easily reduced than anatase. For specular reasons, the presence of the dopants has in general more pronounced effects on anatase, as they can deeply modify the surface reactivity and the HCOOH decomposition path., (© 2021 IOP Publishing Ltd.)

Semiconductor heterojunctions are widely applied in solid-state device applications, including semiconductor lasers, solar cells, and transistors. In photocatalysis they are of interest due to their capability to hinder charge carriers' recombination. A key role in the performance of heterojunctions is that of the alignment of the band edges of the two units composing the junction. In this work, we compare the performances of three widely applied approaches for the simulation of semiconductors heterostructures, based on density functional theory calculations with hybrid functionals. We benchmark the band offsets of ten semiconductors heterostructures for which experimental values are available: AlP/GaP, AlP/Si, AlAs/GaAs, AlAs/Ge, GaAs/Ge, GaP/Si, ZnSe/Ge, ZnSe/AlAs, ZnSe/GaAs, and TiO 2 /SrTiO 3 . The methods considered are (i) the alternating slabs junction (ASJ), (ii) the surface terminated junction (STJ), and (iii) the independent units (IU) approach. Moreover, two different ways to determine a common reference have been considered, (i) the plane averaged electrostatic potential, and (ii) the energy of the core levels. Advantages, drawbacks and overall performances of each method are discussed. The results suggest that the accuracy in the estimation of the band offsets is ∼0.2 eV when the ASJ method is applied. The STJ approach provides a similar accuracy, while the neglection of any interface effect, as in the IU method, provides only a qualitative estimate of the band offset and can result in significant deviations from the experiment., (© 2021 IOP Publishing Ltd.)

In this work we investigate TiO 2 and BiVO 4 nanostructures by means of density functional theory (DFT) calculations, to provide an estimate of the band alignment in TiO 2 /BiVO 4 interfaces, highly active in photo-electrochemistry and photocatalytic water splitting. Calculations were carried out with both DFT range separated and self-consistent dielectric dependent hybrid functionals (HSE06 and PBE0 DD ). The impact of systems' size has been investigated. The converged electronic levels of TiO 2 and BiVO 4 surfaces have been used to predict the band alignment in TiO 2 /BiVO 4 heterostructures. Results indicated that when TiO 2 (101) surface is matched with BiVO 4 (110), a type-II alignment is obtained, where the band edges of BiVO 4 are higher in energy that those of TiO 2 . This picture is favorable for charge-carriers separation upon photoexcitation, where electrons move toward TiO 2 and holes toward BiVO 4 . On the contrary, if TiO 2 (101) is interfaced to BiVO 4 (010) the offset between the band edges is negligible, thus reducing the driving force toward separation of charge carriers. These results rationalize the dependence on the facet's exposure of the observed photocatalytic performances of TiO 2 /BiVO 4 composites, where the TiO 2 (101)/BiVO 4 (110) interface outperforms the TiO 2 (101)/BiVO 4 (010) one.

The valence and conduction band (CB) alignments and the nature of the WO 3 /BiVO 4 heterojunction have been analysed in detail based on hybrid functionals density functional theory calculations. The WO 3 /BiVO 4 junction is widely studied in photocatalysis for its capability to reduce electron-hole recombination and to improve efficiency. This is assumed to be due to a favourable band alignment of the junction's components, which generates a flow of negative charge carriers towards WO 3 , and positive ones towards BiVO 4 . This conclusion is often based on the properties of the two isolated, non-interacting units. Here, we propose an explicit interface model where the (0 0 1) surface of WO 3 is put in contact with the (0 1 0) surface of BiVO 4 rotated by about 45°, which leads to a small strain and a favourable cation-anion matching. The interface displays a moderate charge transfer and a small interface dipole. This leads to only moderate effects on the band alignment, which remains qualitatively similar to that obtained from the two independent oxides. We also considered in detail the role of the amount of exact exchange used in the description of the heterojunction, and in particular of the BiVO 4 component, for which rather different hybrid functional approaches have been proposed in the literature.

CuWO 4 is a semiconducting oxide with interesting applications in photocatalysis. In this paper we present an accurate study of the electronic properties of stoichiometric and oxygen deficient CuWO 4 based on a dielectric dependent hybrid density functional. In CuWO 4 the Cu ions (Cu 2+ ) are in a 3d 9 configuration, so that the material must be classified as a magnetic insulator. Various magnetic configurations of CuWO 4 have been considered, the most stable configuration being anti-ferromagnetic. The band structure, described in terms of density of states (DOS), exhibit the presence of a wide band dominated by W 5d states, separated by about 5 eV from the top of the valence band (VB), consisting of O 2p states partly mixed with Cu 3d states. The empty component of the Cu 3d orbitals forms a narrow band 3.6 eV above the VB maximum. The electronic structure emerging from the DOS curves and the Kohn-Sham energies is hard to reconcile with an experimental band gap of 2.1-2.3 eV. This gap can be rationalized within the Mott-Hubbard model of magnetic insulators, and has been computed from the total energies of the system with one electron removed from the O 2p band and one electron added to the Cu 3d states. Computing the charge transition levels for CuWO 4 , we come to a theoretical band gap of 2.1 eV, in excellent agreement with the experimental observations. We also studied the nature of the oxygen vacancy in CuWO 4 with particular attention to the electron redistribution following the oxygen removal. The excess electrons, in fact, can occupy the localized 3d states of Cu or the localized 5d states of W. The resulting solution depends on various factors, including the concentration of oxygen vacancies.

Understanding the electronic structure of metal oxide semiconductors is crucial to their numerous technological applications, such as photoelectrochemical water splitting and solar cells. The needed experimental and theoretical knowledge goes beyond that of pristine bulk crystals, and must include the effects of surfaces and interfaces, as well as those due to the presence of intrinsic defects (e.g. oxygen vacancies), or dopants for band engineering. In this review, we present an account of the recent efforts in predicting and understanding the optoelectronic properties of oxides using ab initio theoretical methods. In particular, we discuss the performance of recently developed dielectric-dependent hybrid functionals, providing a comparison against the results of many-body GW calculations, including G 0 W 0 as well as more refined approaches, such as quasiparticle self-consistent GW. We summarize results in the recent literature for the band gap, the band level alignment at surfaces, and optical transition energies in defective oxides, including wide gap oxide semiconductors and transition metal oxides. Correlated transition metal oxides are also discussed. For each method, we describe successes and drawbacks, emphasizing the challenges faced by the development of improved theoretical approaches. The theoretical section is preceded by a critical overview of the main experimental techniques needed to characterize the optoelectronic properties of semiconductors, including absorption and reflection spectroscopy, photoemission, and scanning tunneling spectroscopy (STS).

Recently, a well-ordered silicatene/silicon-carbide hybrid thin-film supported on Ru(0 0 0 1) has been reported (2015 Surf. Sci. 632 9-13). The thin-film consist of a monolayer of corner sharing (SiO4)-tetrahedra on top of a (Si2C3) monolayer supported on the Ru(0 0 0 1) surface. This silicatene/silicon-carbide hybrid system may exhibit interesting properties for nano-technological applications and represents another example of a 2D material. We explore the physical and chemical properties of the silicatene/silicon-carbide thin-film using DFT and compare the vibrational spectra with existing experimental data. The characteristics of the silicatene/silicon-carbide hybrid system are compared with those of the bilayer-silicatene (pure SiO2 film). We found large differences in the adsorption modes of the two thin-films on the Ru(0 0 0 1) support. Whereas the bilayer-silicatene physisorbs on the Ru(0 0 0 1) surface, the silicatene/silicon-carbide layer binds via chemisorption. The chemical properties of the two thin-films were probed by adsorption of H atoms at various positions, as well as by Al-doping and the formation of hydroxyl groups (Al-OH). These results show that despite the similar structure of the top layer and the identical metal support (Ru), the mixed silicatene/silicon-carbide system behaves quite differently from the pure silica two-layer counterpart.

Transition metal atoms incorporated into insulating materials (oxides in particular) can deeply modify their adsorption properties. In particular, charge transfer to adsorbed species can be induced by the presence of substitutional dopants, which introduce new electronic states in the band gap of the host crystal. Here we show, by means of density functional theory calculations, that Nb represents an excellent dopant to turn the rather inactive CaO(100) surface into an electron-rich support. The charge transfer ability of the doped material is shown by comparing the adsorption properties of the electronegative Au atoms on pure and Nb-doped CaO. While in the first case the CaO-Au bonding is relatively weak and the Au atom is essentially neutral, in the Nb-doped system a much stronger adhesion is found due to a net charge transfer from the Nb dopant and to the formation of a gold anion. This mechanism occurs also for Nb in high oxidation states. Nb is thus an excellent modifier of the calcium oxide properties.

We report the chemistry and photophysics of atomic gold and silver particles in inorganic glasses. By synchrotron irradiation of gold-doped soda-lime silicate glasses we could create and identify unambiguously the gold dimer as a stable and bright luminescing particle embedded in the glassy matrix. The gold dimer spectra coincide perfectly with rare gas matrix spectra of Au(2). The glass matrix is, however, stable for years, and is hence perfectly suited for various applications. If the irradiated gold-doped sample is annealed at 550 degrees C a bright green luminescence can be recognized. Intense 337 nm excitation induces a decrease of the green luminescence and the reappearance of the 753 nm Au(2) emission, indicating a strong interrelationship between both luminescence centers. Time-dependent density functional theory (TD-DFT) calculations indicate that the green luminescence can be assigned to noble metal dimers bound to silanolate centers. These complexes are recognized as the first stages in the further cluster growth process, which has been investigated with small-angle x-ray scattering (SAXS). In silver-doped glasses, Ag(0) atoms can be identified with electron paramagnetic resonance (EPR) spectroscopy after synchrotron activation. Annealing at 300 degrees C decreases the concentration of Ag(1), but induces an intense white light emission with 337 nm excitation. The white luminescence can be decomposed into bands that are attributed to small silver clusters such as Ag(2), Ag(3) and Ag(4), and an additional band matching the green emission of gold-doped glasses.