Giovanna Pellegrino

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.

Implications of TiO2 surface functionalization on polycrystalline mixed halide perovskite films and photovoltaic devices

We exploit TiO2 surface functionalization as a tool to induce the crystallization process of CH3NH3PbI3−xClx perovskite thin films resulting in a reduction of the degree of orientation of the (110) crystallographic planes. Notably, the variation of the film crystalline orientational order does not affect the photovoltaic performances of the perovskite-based devices, whose efficiency remains mostly unchanged. Our findings suggest that other factors are more significant in determining the device efficiency, such as the non-homogenous coverage of the TiO2 surface causing charge recombination at the organic/TiO2 interface, defect distribution on the perovskite bulk and at the interfaces, and transport in the organic or TiO2 layer. This observation represents a step towards the comprehension of the perovskite film peculiarities influencing the photovoltaic efficiency for high performance devices.

Novel synthesis of ZnO/PMMA nanocomposites for photocatalytic applications

The incorporation of nanostructured photocatalysts in polymers is a strategic way to obtain novel water purification systems. This approach takes the advantages of: (1) the presence of nanostructured photocatalyst; (2) the flexibility of polymer; (3) the immobilization of photocatalyst, that avoids the recovery of the nanoparticles after the water treatment. Here we present ZnO-polymer nanocomposites with high photocatalytic performance and stability. Poly (methyl methacrylate) (PMMA) powders were coated with a thin layer of ZnO (80 nm thick) by atomic layer deposition at low temperature (80 °C). Then the method of sonication and solution casting was performed so to obtain the ZnO/PMMA nanocomposites. A complete morphological, structural, and chemical characterization was made by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) analyses. The remarkable photocatalytic efficiency of the nanocomposites was demonstrated by the degradation of methylene blue (MB) dye and phenol in aqueous solution under UV light irradiation. The composites also resulted reusable and stable, since they maintained an unmodified photo-activity after several MB discoloration runs. Thus, these results demonstrate that the proposed ZnO/PMMA nanocomposite is a promising candidate for photocatalytic applications and, in particular, for novel water treatment.

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.

Combined strategy to realize efficient photoelectrodes for low temperature fabrication of dye solar cells.

We implemented a low-temperature approach to fabricate efficient photoanodes for dye-sensitized solar cells, which combines three different nanoarchitectures, namely, a highly conductive and highly transparent AZO film, a thin TiO2-blocking layer, and a mesoporous TiO2 nanorod-based working electrode. All the components were processed at T≤200°C. Both the AZO and the TiO2 blocking layers were deposited by reactive sputtering, whereas the TiO2 nanorods were synthesized by surfactant-assisted wet-chemical routes and processed into photoelectrodes in which the native geometric features assured uniform mesoporous structure with effective nanocrystal interconnectivity suitable to maximize light harvesting and electron diffusion. Because of the optimized structure of the TiO2-blocking/AZO bilayer, and thanks to the good adhesion of the TiO2 nanorods over it, a significant enhancement of the charge recombination resistance was demonstrated, this laying on the basis of the outstanding power conversion efficiency achievable through the use of this photoanodes architecture: a value of 4.6% (N719) was achieved with a 4-μm-thick electrode processed at T=200°C. This value noticeably overcomes the current literature limit got on AZO-based cells (N719), which instead use Nb-doped and thicker blocking layers, and thicker nanostructured photoanodes, which have been even sintered at higher temperatures (450-500°C).

Fiber texturing in nano-crystalline TiO2 thin films deposited at 150 °C by dc-reactive sputtering on fiber-textured [0 0 0 1] ZnO : Al substrates

TiO2 thin films were deposited at an effective surface temperature of 150 °C by dc-reactive magnetron sputtering on ZnO : Al oriented substrates having a fiber texture along the [0 0 0 1] axis, and studied by transmission electron microscopy and x-ray diffraction analyses. The substrate texturing was used to tailor the TiO2 structure in such a way that a porous matrix made of anatase nano-grains (10 nm in diameter) is formed instead of an amorphous layer (as observed at 150 °C on glass). Additionally, we demonstrate that, by adding an ex situ 200 °C annealing, the anatase domains also gain a fiber texture with the axes aligned to that of the substrate. The TiO2/AZO structural coupling is expected to play a crucial role for the carrier transport through the interface as required in dye-sensitized solar cells. Moreover, the low temperatures used render the process compatible with commonly used plastics substrates.

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.