Alessandra Alberti

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.

Temperature dependence of the specific resistance in Ti∕Al∕Ni∕Au contacts on n-type GaN

The temperature dependence of the specific resistance ρc in annealed Ti∕Al∕Ni∕Au contacts on n-type GaN was monitored, obtaining information on the current transport mechanisms. After annealing at 600°C, the contacts exhibited a rectifying behavior and became Ohmic only after high temperature processes (>700°C), with ρc in the low 10−5Ωcm2 range. The results demonstrated that the current transport is ruled by two different mechanisms: thermoionic field emission occurs in the contacts annealed at 600°C, whereas field emission dominates after higher temperature annealing. The significant physical parameters related to the current transport, i.e., the Schottky barrier height and the carrier concentration under the contact, could be determined. In particular, a reduction of the Schottky barrier from 1.21eV after annealing at 600°Cto0.81eV at 800°C was determined, accompanied by a strong increase of the carrier concentration, i.e., from 2×1018cm−3 in the as-prepared sample to 4.6×1019cm−3 in the annealed conta...

Nanoscale carrier transport in Ti∕Al∕Ni∕Au Ohmic contacts on AlGaN epilayers grown on Si(111)

In this letter, a correlation between nanostructure and current flow in Ti∕Al∕Ni∕Au Ohmic contacts on AlGaN films grown on Si(111) is reported. A cross correlation between conductive-atomic force microscopy and structural analyses (x-ray diffraction, transmission electron microscopy) demonstrates that the structure and the electrical properties of the different phases formed inside the reacted layer upon annealing are crucial for the nanoscale current transport. The experimental measurement of the resistivity of the main phases formed upon annealing (AlNi, AlAu4, and Al2Au) indicated that the low resistivity Al2Au phase provides preferential conductive paths for the current flow through the contact.

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.

Flexible pH sensors based on polysilicon thin film transistors and ZnO nanowalls

A fully flexible pH sensor using nanoporous ZnO on extended gate thin film transistor (EGTFT) fabricated on polymeric substrate is demonstrated. The sensor adopts the Low Temperature Polycrystalline Silicon (LTPS) TFT technology for the active device, since it allows excellent electrical characteristics and good stability and opens the way towards the possibility of exploiting CMOS architectures in the future. The nanoporous ZnO sensitive film, consisting of very thin (20 nm) crystalline ZnO walls with a large surface-to-volume ratio, was chemically deposited at 90 °C, allowing simple process integration with conventional TFT micro-fabrication processes compatible with wide range of polymeric substrates. The pH sensor showed a near-ideal Nernstian response (∼59 mV/pH), indicating an ideality factor α ∼ 1 according to the conventional site binding model. The present results can pave the way to advanced flexible sensing systems, where sensors and local signal conditioning circuits will be integrated on the same flexible substrate.

Thermal stability of thin CoSi2 layers on polysilicon implanted with As, BF2, and Si

The thermal stability of thin cobalt silicide layers grown on preamorphized chemical vapor deposited silicon layers has been studied in the temperature range between 950 and 1100 °C. The morphology of the starting layers and their evolution during the thermal processes was analyzed by transmission electron microscopy, atomic force microscopy and Rutherford backscattering spectroscopy. The observed increase in sheet resistance with the annealing time has been correlated to the agglomeration process taking into account the dependence of the resistivity on film thickness and carrier mean free path. Sheet resistance measurements have been used to study the agglomeration process of CoSi2 by varying temperature and substrate doping (As, BF2, and Si implants). The process is thermally activated with an activation energy of 4.3 eV for the Si implanted samples. The BF2 implanted substrate show a higher activation energy (∼5.4 eV), while the arsenic implanted a lower one (∼3.6 eV). This difference is attributed to ...

Pseudoepitaxial transrotational structures in 14 nm-thick NiSi layers on (001) silicon

In a system consisting of two different lattices, structural stability is ensured when an epitaxial relationship occurs between them and allows the system to retain the stress whilst avoiding the formation of a polycrystalline film. The phenomenon occurs if the film thickness does not exceed a critical value. Here we show that in spite of its orthorhombic structure, a 14 nm-thick NiSi layer can three-dimensionally adapt to the cubic Si lattice by forming transrotational domains. Each domain arises by the continuous bending of the NiSi lattice, maintaining a close relationship with the substrate structure. The presence of transrotational domains does not cause a roughening of the layer, but instead it improves the structural and electrical stability of the silicide in comparison with a 24 nm-thick layer formed using the same annealing process. These results have relevant implications for the thickness scaling of NiSi layers which are currently used as metallizations of electronic devices.

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.

THERMAL STABILITY OF COBALT SILICIDE STRIPES ON SI (001)

The effect of lateral scaling on the thermal stability of cobalt disilicide has been investigated on Si (001) substrates. Resistance measurements on four terminal resistors, with linewidth dimensions ranging from 1.3 to 0.5 μm, have been performed after annealing in the range between 900 and 1000 °C. The resistance increases faster in the stripes than in blanket regions. This degradation process has been correlated to the morphological change in the strip cross section, as analyzed by transmission electron microscopy and atomic force microscopy. Grain growth, degradation processes at the line edge, and surface and interface roughness have been observed. These analyses show that the lateral constraints of the silicide lines are mainly responsible for the lowering of the silicide thermal stability compared with blanket regions. Moreover, from measurements of agglomerated silicide grains in equilibrium with the substrate, the silicide surface free energy is 2.3 times the free energy of the CoSi2/Si interface.

High-resolution investigation of atomic interdiffusion during Co/Ni/Si phase transition

Silicide formation from Co/Ni/Si thin film structures is attractive to be applied on device to lower the thermal budget necessary to complete the metal reaction. Nevertheless, silicide phase transition in such a system is quite difficult to be fully characterised by conventional techniques due to Ni and Co atom similarity. As a suitable approach to this problematic issue, we show the advantage of studying Co/Ni/Si phase transition by means of in situ sheet resistance analyses during isothermal annealing processes. It has been found that Co/Ni/Si reaction exhibits a double peak in the transition curve, clearly indicating the occurrence of critical stages during the transformation process. Once identified, these stages have been related to the phase distribution and location inside the sample structure by means of Energy Filtered Transmission Electron Microscopy (EFTEM) and Selected Area Electron Diffraction (SAED) analyses. It has been observed that cobalt reaction with silicon starts after a delay time whilst nickel atoms immediately react with silicon. In the second part of the reaction process, cobalt atoms diffuse through the Ni 2 Si grain boundaries and progressively react with silicon. At the equilibrium, CoSi and NiSi phases remain separated, while a ternary Co(Ni)Si 2 compound nucleates at the interface with the substrate.