Emanuele Smecca

Atomistic origins of CH3NH3PbI3 degradation to PbI2 in vacuum

We study the mechanisms of CH3NH3PbI3 degradation and its transformation to PbI2 by means of X-ray diffraction and the density functional theory. The experimental analysis shows that the material can degrade in both air and vacuum conditions, with humidity and temperature-annealing strongly accelerating such process. Based on ab initio calculations, we argue that even in the absence of humidity, a decomposition of the perovskite structure can take place through the statistical formation of molecular defects with a non-ionic character, whose volatility at surfaces should break the thermodynamic defect equilibria. We finally discuss the strategies that can limit such phenomenon and subsequently prolong the lifetime of the material.

Similar Structural Dynamics for the Degradation of CH3 NH3 PbI3 in Air and in Vacuum.

We investigate the degradation path of MAPbI3 (MA=methylammonium) films over flat TiO2 substrates at room temperature by means of X-ray diffraction, spectroscopic ellipsometry, X-ray photoelectron spectroscopy, and high-resolution transmission electron microscopy. The degradation dynamics is found to be similar in air and under vacuum conditions, which leads to the conclusion that the occurrence of intrinsic thermodynamic mechanisms is not necessarily linked to humidity. The process has an early stage, which drives the starting tetragonal lattice in the direction of a cubic atomic arrangement. This early stage is followed by a phase change towards PbI2 . We describe how this degradation product is structurally coupled with the original MAPbI3 lattice through the orientation of its constituent PbI6 octahedra. Our results suggest a slight octahedral rearrangement after volatilization of HI+CH3 NH2 or MAI, with a relatively low energy cost. Our experiments also clarify why reducing the interfaces and internal defects in the perovskite lattice enhances the stability of the material.

Spontaneous bidirectional ordering of CH3NH3(+) in lead iodide perovskites at room temperature: The origins of the tetragonal phase.

CH3NH3PbI3 is a hybrid organic-inorganic material with a perovskite structure and a temperature-dependent polymorphism whose origins are still unclear. Here we perform ab initio molecular dynamics simulations in order to investigate the structural properties and atom dynamics of CH3NH3PbI3 at room temperature. Starting from different initial configurations, we find that a single-crystalline system undergoes a spontaneous ordering process which brings the ions to alternately point towards the center of two out of the six faces of the cubic framework, i.e. towards the 〈100〉 and 〈010〉 directions. This bidirectional ordering gives rise to a preferential distortion of the inorganic lattice on the a-b plane, shaping the observed tetragonal symmetry of the system. The process requires tens of picoseconds for CH3NH3PbI3 supercells with just eight ions.

Multi-Scale-Porosity TiO2 scaffolds grown by innovative sputtering methods for high throughput hybrid photovoltaics.

We propose an up-scalable, reliable, contamination-free, rod-like TiO2 material grown by a new method based on sputtering deposition concepts which offers a multi-scale porosity, namely: an intra-rods nano-porosity (1–5 nm) arising from the Thornton’s conditions and an extra-rods meso-porosity (10–50 nm) originating from the spatial separation of the Titanium and Oxygen sources combined with a grazing Ti flux. The procedure is simple, since it does not require any template layer to trigger the nano-structuring, and versatile, since porosity and layer thickness can be easily tuned; it is empowered by the lack of contaminations/solvents and by the structural stability of the material (at least) up to 500 °C. Our material gains porosity, stability and infiltration capability superior if compared to conventionally sputtered TiO2 layers. Its competition level with chemically synthesized reference counterparts is doubly demonstrated: in Dye Sensitized Solar Cells, by the infiltration and chemisorption of N-719 dye (∼1 × 1020 molecules/cm3); and in Perovskite Solar Cells, by the capillary infiltration of solution processed CH3NH3PbI3 which allowed reaching efficiency of 11.7%. Based on the demonstrated attitude of the material to be functionalized, its surface activity could be differently tailored on other molecules or gas species or liquids to enlarge the range of application in different fields.

AlN texturing and piezoelectricity on flexible substrates for sensor applications

We show that AlN-based piezocapacitors with relatively high piezoelectric coefficient (d33) values (3–4 pC/N) can be fabricated on polyimide (PI) substrates at 160 °C or even at room temperature by sputtering processes. With respect to PI, a reduction of the piezoelectric performances was observed on polyethylene naphthalate (PEN). With the same approach, a d33 value as high as 8 pC/N was achieved on rigid substrates (SiO2/Si). In all cases, a thin Al buffer layer was deposited, immediately before AlN, without breaking the vacuum in the deposition chamber, in order to preserve the interface from contaminations that would obstruct the optimal atomic stratification with the desired [0001] growth axis. The piezoelectric behavior was thus correlated to the degree of texturing of the AlN layer through the evaluation of the XRD texturing coefficients and to the morphology by means of AFM analyses. We show that a high level of roughness introduced by the PEN substrate, coupled with the effect of the substrate fl...

Low temperature sputtered TiO2 nano sheaths on electrospun PES fibers as high porosity photoactive material

We propose a low temperature approach based on combining an electrospinning methodology and reactive sputtering processes to realise a porous mesh of polyethersulfone (PES) fibers (∼700 nm in diameter) wrapped by TiO2 nano-sheaths, active under UV illumination. The mesh has a porosity as high as ∼91% in volume and was prepared at T ≤ 160 °C. The effectiveness of the TiO2/PES mesh under UV was proved by Methylene Blue (MB) dissociation experiments and related to the TiO2 coverage properties, namely its thickness (∼15 nm), its nano-structuring (grains diameter 8–10 nm) and lattice structure (anatase) that improve the photo-activity action. The combination of electro-spinning plus sputtering processes lays the basis for high porosity and low cost, high throughput, high yield and flexible purifying filter technologies.

Metal-Organic Chemical Vapor Deposition (MOCVD) Synthesis of Heteroepitaxial Pr0.7Ca0.3MnO3 Films: Effects of Processing Conditions on Structural/Morphological and Functional Properties

Calcium-doped praseodymium manganite films (Pr0.7Ca0.3MnO3, PCMO) were prepared by metal-organic chemical vapor deposition (MOCVD) on SrTiO3 (001) and SrTiO3 (110) single-crystal substrates. Structural characterization through X-ray diffraction (XRD) measurements and transmission electron microscopy (TEM) analyses confirmed the formation of epitaxial PCMO phase films. Energy dispersive X-ray (EDX) and X-ray photoelectron spectroscopy (XPS) characterization was used to confirm lateral and vertical composition and the purity of the deposited films. Magnetic measurements, obtained in zero-field-cooling (ZFC) and field-cooling (FC) modes, provided evidence of the presence of a ferromagnetic (FM) transition temperature, which was correlated to the transport properties of the film. The functional properties of the deposited films, combined with the structural and chemical characterization collected data, indicate that the MOCVD approach represents a suitable route for the growth of pure, good quality PCMO for the fabrication of novel spintronic devices.

Stability and Degradation in Hybrid Perovskites: Is the Glass Half-Empty or Half-Full?

Methylammonium lead iodide (CH3NH3PbI3) is an extensively used perovskite material with a remarkable potential for solar energy conversion. Despite its high photovoltaic efficiency, the material suffers from fast degradation when aging in atmospheric conditions and/or under sunlight. Here we review the principal degradation mechanisms of CH3NH3PbI3, focusing on the thermodynamic, environmental and polymorphic parameters that impact the stability of the material. A critical analysis of the available data indicates that degradation under ambient conditions is a defect-generation process that is highly localized on surfaces and interfaces, while it is further enhanced above the tetragonal-cubic transition at ∼54 °C. Within this context, we discuss the conservative role of N2 and propose strategies for the emergence of industrially viable hybrid photovoltaics.

Metal/P-GaN Contacts on AlGaN/GaN Heterostructures for Normally-Off HEMTs

In this paper, the electrical properties of different metal/p-GaN contacts (Ti/Al, TiN/Ti/Al and Ni/Au) have been investigated to get a deeper understanding of the behavior of p-GaN/AlGaN/GaN heterostructures for normally-off HEMTs. In particular, the study of the temperature dependent current-voltage characteristics allowed to identify the dominant carrier transport mechanism at the metal/p-GaN interface (Thermionic Field Emission). From the fit of the experimental current-voltage data it was possible to determine the Schottky barrier height values for the three systems, 2.08 eV (Ti/Al), 1.57 eV (TiN/Ti/Al) and 1.89 eV (Ni/Au). Hence, choosing the highest barrier height contact (Ti/Al) as gate electrode on a p-GaN/AlGaN/GaN heterostructure, optimized based on simulations, allowed to obtain devices with a normally-off behavior and a positive Vth of +1.3 V.

A Comparison Among Low Temperature Piezoelectric Flexible Sensors Based on Polysilicon TFTs for Advanced Tactile Sensing on Plastic

In this work, we present a comparison among four different piezoelectric materials (PVDF-TrFE, Piezopaint, AlN and ZnO), all deposited at low temperature (from RT up to 160 °C) on flexible substrate such as thin Polyimide, in order to investigate their possible implementation as flexible tactile sensors. Flexible capacitive sensors were tested by using a mini-shaker, investigating the sensors behavior in force and frequency with the intent of mimicking the human sense of touch. We optimized the piezoelectric properties of the materials by using specific texturing buffer layers or maximizing the poling procedure to increase the dipole alignment. Finally, by using a multi-foil approach, the different sensors have been integrated with polysilicon thin film transistor fabricated on flexible substrates and the specific device sensitivity was evaluated.