Indoor photovoltaic (IPV) technology has emerged as an effective strategy to sustainably power batteryless Internet of Things (IoT) devices. Though tin perovskite solar cells offer competitive IPV performance, their effectiveness is often compromised by Sn2+ oxidation, particularly when processed with dimethyl sulfoxide (DMSO) solvent. This work explored the IPV performance of DMSO-free tin perovskites FASnI3-x Br x by tuning the halide composition. Notably, X-ray photoelectron spectroscopy confirms no traces of Sn4+, highlighting the critical role of eliminating DMSO. Under 1000 lx indoor illumination, the power conversion efficiency (PCE) increases with Br content, reaching a maximum of 11.1% for FASnI2Br without introducing any reducing agent. Remarkably, after six months of storage, it exhibited an impressive indoor PCE of 11.9%, demonstrating the effectiveness of the DMSO-free processing route for the intrinsic stability of the tin perovskite. These findings provide crucial insights for developing high-performance, lead-free perovskite materials for sustainable energy applications and IoT devices.

Ab initio density-functional calculations show that orthorhombic Pca21 hafnia HfO2 mixed with vanadium at low concentration is a ferroelectric and ferromagnetic insulator. The multiorbital degeneracy of singly-occupied V states in the nominally 4+ ionic state is broken by magnetism, reduced symmetry, and local distortion, causing a single one-electron majority state per V atom to be occupied. A gap of order 1 eV thus survives at all V concentrations, and intrinsic polarization is preserved at the level of 60-70% of the undoped-HfO2 value. Magnetization is found to increase linearly with V content, with values of 30-40 emu/cm3 at concentrations near the end of the stability range (similar to 16% V).

Ab initio density-functional calculations show that orthorhombic Pca21 hafnia HfO2 mixed with vanadium at low concentration is a ferroelectric and ferromagnetic insulator. The multiorbital degeneracy of singly-occupied V states in the nominally 4+ ionic state is broken by magnetism, reduced symmetry, and local distortion, causing a single one-electron majority state per V atom to be occupied. A gap of order 1 eV thus survives at all V concentrations, and intrinsic polarization is preserved, at the level of two-thirds the hafnia value. Ferromagnetic magnetization is found to increase linearly with V content, with values of 30-40 emu/cm3 at concentrations near the end of the stability range.

Tin-based perovskite solar cells offer a less toxic alternative to their lead-based counterparts. Despite their promising optoelectronic properties, their performances still lag behind, with the highest power conversion efficiencies reaching around 15%. This efficiency limitation arises primarily from electronic defects leading to self-p-doping and stereochemical activity of the Sn(II) ion, which distorts the atomic arrangement in the material. In this study, we investigate the effect of strontium doping in tin-based perovskite on the distortion of the material's structure and its optoelectronic properties. Using a combination of Density Functional Theory calculations and experiments, we demonstrate that strontium doping reduces p-doping and structural strain. This approach improves the efficiency from 6.3% in undoped devices to 7.5% in doped devices without relying on dimethyl sulfoxide, a harmful solvent for tin-based perovskites. This method could enable precise control of tin off-centering and self-p-doping, advancing the development of efficient and stable tin perovskite solar cells.

When an organic film is deposited on a metal surface, charge layers are formed at the interface. These are an important feature of the interface electronic structure and play a crucial role as separation layers between electrodes and active layers in organic devices. Here, we report on a study of the interface between diruthenium phthalocyanine, (RuPc)2, and the Ag(001) surface. The molecules form two different commensurable arrangements on the substrate, a low density one for a coverage well below the first monolayer and a high density one up to the completion of the monolayer. The focus of this study is on the interface states evolution with the molecular density on the metal surface and the charge distribution in the thin interfacial layer between molecules and substrate. From this investigation, conducted by low energy electron diffraction, scanning tunneling microscopy/spectroscopy, photoemission spectroscopy, and density functional theory, we have found that, even if individual molecules are characterized by a quite similar surface-to-molecule charge transfer pattern, the two molecular arrangements present different valence band structures and, more interestingly, different modulations of the interface charge. These charge modulations are governed by interfacial states energetically resonant with the molecular states, localized at the position of the molecules as well as by a reaction of the electronic cloud of the metal surface to the molecular adsorption due to a Pauli pushback effect. This complex, spatial charge modulation makes the (RuPc)2/Ag(001) an interesting case of interaction intermediate between physisorption and chemisorption.

Nowadays, a wide number of applications based on magnetic materials rely on the properties arising at the interface between different layers in complex heterostructures engineered at the nanoscale. In ferromagnetic/heavy metal multilayers, such as the [Co/Pt]N and [Co/Pd]N systems, the magnetic proximity effect was demonstrated to be asymmetric, thus inducing a magnetic moment on the Pt (Pd) layer that is typically higher at the top Co/Pt(Pd) interface. In this work, advanced spectroscopic and imaging techniques were combined with theoretical approaches to clarify the origin of this asymmetry both in Co/Pt trilayers and, for the first time, in multilayer systems that are more relevant for practical applications. The different magnetic moment induced at the Co/Pt interfaces was correlated to the microstructural features that are in turn affected by the growth processes that induce a different intermixing during the film deposition, thus influencing the interface magnetic profile.

The electronic energy levels of cyclo(glycine-phenylalanine), cyclo(tryptophan-tyrosine) and cyclo(tryptophan-tryptophan) dipeptides are investigated with a joint experimental and theoretical approach. Experimentally, valence photoelectron spectra in the gas phase are measured using VUV radiation. Theoretically, we first obtain low-energy conformers through an automated conformer-rotamer ensemble sampling scheme based on tight-binding simulations. Then, different first principles computational schemes are considered to simulate the spectra: Hartree-Fock (HF), density functional theory (DFT) within the B3LYP approximation, the quasi-particle GW correction, and the quantum-chemistry CCSD method. Theory allows assignment of the main features of the spectra. A discussion on the role of electronic correlation is provided, by comparing computationally cheaper DFT scheme (and GW) results with the accurate CCSD method.

We report on a systematic study of bis-ruthenium phthalocyanine, (RuPc)(2), layers deposited on Au(111), Ag(111), and graphite. By scanning tunneling microscopy and density functional theory calculations, a detailed picture of the molecular orbitals rearrangement due to the contact with the substrate is drawn, which reveals a significant substrate impact on the molecule charge and spin patterns. On the metal substrates a reduction of the Ru-Ru dimer magnetic moment is observed due to the filling of a spin-down singly unoccupied molecular orbital. However, the higher work function of Au(111) induces a charge backdonation, which results in an unexpected spin polarization of the molecule ligand. On the other hand, the contact with graphite leaves the electronic and magnetic properties of (RuPc)(2) largely unaffected. The self-assembling process of the molecules on the different substrates has also been thoroughly investigated and interpreted in the light of molecular orbital rearrangements. On the low interacting graphite substrate, the process is mainly driven by molecule-molecule interactions leading to a square structure. Conversely, on Ag(111) and Au(111), the stronger molecule-substrate interaction produces a more complex scenario characterized by a manifold of structures.

The electronic structure of ε-Ga2O3 thin films has been investigated by ab initio calculations and photoemission spectroscopy with UV, soft, and hard X-rays to probe the surface and bulk properties. The latter measurements reveal a peculiar satellite structure in the Ga 2p core level spectrum, absent at the surface, and a core-level broadening that can be attributed to photoelectron recoil. The photoemission experiments indicate that the energy separation between the valence band and the Fermi level is about 4.4 eV, a valence band maximum at the Γ point and an effective mass of the highest lying bands of – 4.2 free electron masses. The value of the bandgap compares well with that obtained by optical experiments and with that obtained by calculations performed using a hybrid density-functional, which also reproduce well the dispersion and density of states.

Lowering of the Fermi level and hindering of negative oxygen species adsorption are induced in ZnO by cobalt substitution (5%).

We have investigated the formation and the properties of ultrathin films of ruthenium phthalocyanine (RuPc)2 vacuum deposited on graphite by scanning tunneling microscopy and synchrotron photoemission spectroscopy measurements, interpreted in close conjunction with ab initio simulations. Thanks to its unique dimeric structure connected by a direct Ru-Ru bond, (RuPc)2 can be found in two stable rotameric forms separated by a low-energy barrier. Such isomerism leads to a peculiar organization of the molecules in flat, horizontal layers on the graphite surface, characterized by a chessboard-like alternation of the two rotamers. Moreover, the molecules are vertically connected to form π-stacked columnar pillars of akin rotamers, compatible with the high conductivity measured in (RuPc)2 powders. Such features yield an unprecedented supramolecular assembly of phthalocyanine films, which could open interesting perspectives toward the realization of new architectures of organic electronic devices.

We have correlated the surface conductivity of hydrogen-terminated diamond to the electronic structure in the Fermi region. Significant density of electronic states (DOS) in proximity of the Fermi edge has been measured by photoelectron spectroscopy (PES) on surfaces exposed to air, corresponding to a p-type electric conductive regime, while upon annealing a depletion of the DOS has been achieved, resembling the diamond insulating state. The surface and subsurface electronic structure has been determined, exploiting the different probing depths of PES applied in a photon energy range between 7 and 31 eV. Ab initio density functional calculations including surface charge depletion and band-bending effects favorably compare with electronic states measured by angular-resolved photoelectron spectroscopy. Such states are organized in the energy-momentum space in a twofold structure: one, bulk-derived, band disperses in the Gamma-X direction with an average hole effective mass of (0.43 +/- 0.02)m(0), where m(0) is the bare electron mass; a second flatter band, with an effective mass of (2.2 +/- 0.9)m(0), proves that a hole gas confined in the topmost layers is responsible for the conductivity of the (2 x 1) hydrogen-terminated diamond (100) surface.

A number of studies have investigated the properties of monomeric and double-decker phthalocyanines (Pcs) adsorbed on metal surfaces, in view of applications in spintronics devices. In a combined experimental and theoretical study, we consider here a different member of the Pcs family, the (RuPc)2 dimer, whose structure is characterized by two paired up magnetic centers embedded in a double-decker architecture. For (RuPc)2 on Ag(111), we show that this architecture works as a preserving cage by shielding the Ru-Ru pair from a direct interaction with the surface atoms. In fact, while noticeable surface-to-molecule charge transfer occurs with the ensuing quenching of the molecular magnetic moment, such phenomena occur here in the absence of a direct Ru-Ag coupling or structural rearrangement, at variance with other Pcs and thanks to the above shielding effect. These unique properties of the (RuPc)2 architecture are expected to permit an easy control of the surface-to-molecule charge-transfer process as well as of the molecular magnetic properties, thus making the (RuPc)2 dimer a significant paradigm for innovative "cage" structures as well as a promising candidate for applications in spintronics nano or single-molecule devices.

Impressive changes in the transport and ferromagnetic properties of Co-doped ZnO thin films have been obtained by postgrowth hydrogen irradiation at temperatures of 400 °C. Hydrogen incorporation increases the saturation magnetization by one order of magnitude (up to ∼1.50 μB/Co) and increases the carrier density and mobility by about a factor of two. In addition to the magnetic characterization, the transport and structural properties of hydrogenated ZnO:Co have been investigated by Hall effect, local probe conductivity measurements, micro-Raman, and X-ray absorption spectroscopy. Particular care has been given to the detection of Co oxides and metal Co nanophases, whose influence on the increase in the transport and ferromagnetic properties can be excluded on the ground of the achieved results. The enhancement in ferromagnetism is directly related to the dose of H introduced in the samples. On the contrary, despite the shallow donor character of H atoms, the increase in carrier density n is not related to the H dose. These apparently contradictory effects of H are fully accounted for by a mechanism based on a theoretical model involving Co-VO (Co-O vacancy) pairs.

The investigation of the electrical properties of Co-doped ZnO thin films provides two unexpected results: a decrease of the electrical conductivity and the contemporary occurrence of a reduction of conductivity and of an enhancement of ferromagnetic order. The former result is surprising since Zn atoms are replaced with iso-valent Co atoms. The latter finding questions previously suggested beneficial effects of n-type doping on the ZnO: Co magnetic behavior. While morphological and structural characterization permits us to exclude an influence of the morphology and of the presence of Co metal or Co-oxide phases on present experimental findings, with the aid of first-principles electronic structure calculations, we propose a qualitative picture which can explain in a coherent way both the changes in conductivity and ferromagnetic behavior ensuing from the Co doping and the above-mentioned, beneficial effects of n-type doping.

Based on hybrid density-functional calculations, we propose that ferromagnetism in the prototypical bixbyite sesquioxide In2O3 doped with Cr is due to Cr-oxygen vacancy complexes, while isolated Cr cannot support carrier-mediated magnetic coupling. Our proposal is consistent with experimental facts such as the onset of ferromagnetism in O-lean conditions only, the low or vanishing net moment in unintentionally doped material, and its increase upon intentional doping.

We used a synergic Co-edge X-ray absorption spectroscopy (XAS) and density functional theory calculations approach to perform a study of defects which could account for the room temperature ferromagnetism of ZnCoO, an oxide of great potential interest in semiconductor spintronics. Our results suggest that a key role is played by specific defect complexes in which O vacancies are located close to the Co atoms. Extended defects such as Co clusters have a marginal function, although we observe their formation at the epilayer surface under certain growth conditions. We also show preliminary results of the study of hydrogen-induced defects in ZnCoO epilayers deliberately hydrogen irradiated via a Kaufman source. Hydrogen was in fact predicted to mediate a ferromagnetic spin-spin interaction between neighboring magnetic impurities.

Nonplanar titanyl phthalocyanine (TiOPc) molecules, characterized by a central, highly dipolar Ti-O group, can offer further degrees of freedom in tailoring the properties of hybrid organic inorganic structures. Here, we combine scanning tunneling microscopy and low-energy electron diffraction measurements with ab initio density functional theory calculations to investigate the interaction of TiOPc molecules with the Ag(100) surface. Isolated molecules are adsorbed with the macrocycle parallel to the surface in two different configurations: with the 0 atom pointing outward (UP configuration) or with the 0 atom pointing toward the surface (DOWN configuration). A different interaction of UP and DOWN molecules with the surface can account for their different orientation on the surface as well as for the observation of marked chiral effects only for UP molecules. Self-assembled domains of randomly mixed UP and DOWN molecules form at the monolayer coverage, driven by a subtle interplay between the molecule surface interaction, the intermolecular dipolar attraction, and the side interaction between adjacent molecules. Chiral patterns of isolated molecules, observed by STM, are transferred to these domains. Remarkably, theoretical calculations disclose an interfacial nature of such chiral properties. Finally, a metallic behavior observed for the monolayer disappears for TiOPc molecules in a second layer, which are electronically decoupled from the substrate.