Gas Flow Sputtering of Pt/C Films and their Performance in Electrocatalytic Hydrogen Evolution Reaction.

A single step deposition technique of Pt/C films for electrocatalytic applications is presented. The hollow cathode gas flow sputtering (GFS) method allows a catalyst production within few minutes without further steps. The herein presented films consist of small Pt nanocrystals (2-5 nm) deposited in a matrix of nanocrystalline carbon. The films show a low and stable overpotential under acidic conditions in the hydrogen evolution reaction (HER). Relatively low Pt-mass activity (<1 mA/µgPt ) is attributed to the yet too high Pt-content in the films. Another issue discovered in this work is a non-graphitic state of carbon resulting in its high resistivity. Still, the GFS deposition technique providing by nature high deposition rates and a substance-to-material yield of 80-90 % is advantageous than other sputtering techniques and especially chemical methods in that sense. This technique is scalable to areas in the range of square meters and thus represents an attractive way to efficiently produce large-scale cathode coatings for industrial electrolysers.

Hidden polymorphism of FAPbI3 discovered by Raman spectroscopy.

Formamidinium lead iodide (FAPbI3) can be used in its cubic, black form as a light absorber material in single-junction solar cells. It has a band-gap (1.5 eV) close to the maximum of the Shockley-Queisser limit, and reveals a high absorption coefficient. Its high thermal stability up to 320 °C has also a downside, which is the instability of the photo-active form at room temperature (RT). Thus, the black α-phase transforms at RT with time into a yellow non-photo-active δ-phase. The black phase can be recovered by annealing of the yellow state. In this work, a polymorphism of the α-phase at room temperature was found: as-synthesized (αi), degraded (αδ) and thermally recovered (αrec). They differ in the Raman spectra and PL signal, but not in the XRD patterns. Using temperature-dependent Raman spectroscopy, we identified a structural change in the αi-polymorph at ca. 110 °C. Above 110 °C, the FAPbI3 structure has undoubtedly cubic Pm3[combining macron]m symmetry (high-temperature phase: αHT). Below that temperature, the αi-phase was suggested to have a distorted perovskite structure with Im3[combining macron] symmetry. Thermally recovered FAPbI3 (αrec) also demonstrated the structural transition to αHT at the same temperature (ca. 110 °C) during its heating. The understanding of hybrid perovskites may bring additional assets in the development of new and stable structures.

Vibrational dynamics in lead halide hybrid perovskites investigated by Raman spectroscopy.

Lead halide perovskite semiconductors providing record efficiencies of solar cells have usually mixed compositions doped in A- and X-sites to enhance the phase stability. The cubic form of formamidinium (FA) lead iodide reveals excellent opto-electronic properties but transforms at room temperature (RT) into a hexagonal structure which does not effectively absorb visible light. This metastable form and the mechanism of its stabilization by Cs+ and Br- incorporation are poorly characterized and insufficiently understood. We report here the vibrational properties of cubic FAPbI3 investigated by DFT calculations on phonon frequencies and intensities, and micro-Raman spectroscopy. The effects of Cs+ and Br- partial substitution are discussed. We support our results with the study of FAPbBr3 which expands the identification of vibrational modes to the previously unpublished low frequency region (<500 cm-1). Our results show that the incorporation of Cs+ and Br- leads to the coupling of the displacement of the A-site components and weakens the bonds between FA+ and the PbX6 octahedra. We suggest that the enhancement of α-FAPbI3 stability can be a product of the release of tensile stresses in the Pb-X bond, which is reflected in a red-shift of the low frequency region of the Raman spectrum (<200 cm-1).