Octupole strength in the neutron-rich calcium isotopes

Low-lying excited states of the neutron-rich calcium isotopes $^{48-52}$Ca have been studied via $\gamma$-ray spectroscopy following inverse-kinematics proton scattering on a liquid hydrogen target using the GRETINA $\gamma$-ray tracking array. The energies and strengths of the octupole states in these isotopes are remarkably constant, indicating that these states are dominated by proton excitations.Comment: 15 pages, 3 figure

Spectroscopy of 54^{54}Ti and the systematic behavior of low energy octupole states in Ca and Ti isotopes

Excited states of the $N=32$ nucleus $^{54}$Ti have been studied, via both inverse-kinematics proton scattering and one-neutron knockout from $^{55}$Ti by a liquid hydrogen target, using the GRETINA $\gamma$-ray tracking array. Inelastic proton-scattering cross sections and deformation lengths have been determined. A low-lying octupole state has been tentatively identified in $^{54}$Ti for the first time. A comparison of $(p,p')$ results on low-energy octupole states in the neutron-rich Ca and Ti isotopes with the results of Random Phase Approximation calculations demonstrates that the observed systematic behavior of these states is unexpected.Comment: 7 pages, 8 figure

Spectroscopy of 54^{54}Ti and the systematic behavior of low energy octupole states in Ca and Ti isotopes

Excited states of the $N=32$ nucleus $^{54}$Ti have been studied, via both inverse-kinematics proton scattering and one-neutron knockout from $^{55}$Ti by a liquid hydrogen target, using the GRETINA $\gamma$-ray tracking array. Inelastic proton-scattering cross sections and deformation lengths have been determined. A low-lying octupole state has been tentatively identified in $^{54}$Ti for the first time. A comparison of $(p,p')$ results on low-energy octupole states in the neutron-rich Ca and Ti isotopes with the results of Random Phase Approximation calculations demonstrates that the observed systematic behavior of these states is unexpected.Comment: 7 pages, 8 figure

The Impact of Atmosphere on the Local Luminescence Properties of Metal Halide Perovskite Grains.

Metal halide perovskites are exceptional candidates for inexpensive yet high-performing optoelectronic devices. Nevertheless, polycrystalline perovskite films are still limited by nonradiative losses due to charge carrier trap states that can be affected by illumination. Here, in situ microphotoluminescence measurements are used to elucidate the impact of light-soaking individual methylammonium lead iodide grains in high-quality polycrystalline films while immersing them with different atmospheric environments. It is shown that emission from each grain depends sensitively on both the environment and the nature of the specific grain, i.e., whether it shows good (bright grain) or poor (dark grain) luminescence properties. It is found that the dark grains show substantial rises in emission, while the bright grain emission is steady when illuminated in the presence of oxygen and/or water molecules. The results are explained using density functional theory calculations, which reveal strong adsorption energies of the molecules to the perovskite surfaces. It is also found that oxygen molecules bind particularly strongly to surface iodide vacancies which, in the presence of photoexcited electrons, lead to efficient passivation of the carrier trap states that arise from these vacancies. The work reveals a unique insight into the nature of nonradiative decay and the impact of atmospheric passivation on the microscale properties of perovskite films

Real-Time Observation of Iodide Ion Migration in Methylammonium Lead Halide Perovskites

Organic-inorganic metal-halide perovskites (e.g. CH3NH3PbI3-xClx) emerged as a promising opto-electronic material. However, the Shockley–Queisser Limit for the power conversion efficiency (PCE) of perovskite-based photovoltaic devices has still not been reached, which was attributed to non-radiative recombination pathways, as suggested by photoluminescence (PL) inactive (or dark) areas on perovskite films. Although these observations have been related to the presence of ions/defects, the underlying fundamental physics and detailed microscopic processes, concerning trap/defect status, ion migration, etc., still remain poorly understood. Here we utilize correlated wide-field PL microscopy and impedance spectroscopy (IS) on perovskite films to in-situ investigate both the spatial and temporal evolution of these PL inactive areas under external electrical fields. We attribute the formation of PL inactive domains to the migration and accumulation of iodine ions under external fields. Hence we are able to characterize the kinetic processes and determine the drift velocities of these ions. In addition, we show that I2 vapor directly affects the PL quenching of a perovskite film, which provides evidence that the migration/segregation of iodide ions plays an important role in the PL quenching and consequently limits the PCE of organometal halide based perovskite photovoltaic devices

Efficient perovskite solar cells by metal ion doping

Realizing the theoretical limiting power conversion efficiency (PCE) in perovskite solar cells requires a better understanding and control over the fundamental loss processes occurring in the bulk of the perovskite layer and at the internal semiconductor interfaces in devices. One of the main challenges is to eliminate the presence of charge recombination centres throughout the film which have been observed to be most densely located at regions near the grain boundaries. Here, we introduce aluminium acetylacetonate to the perovskite precursor solution, which improves the crystal quality by reducing the microstrain in the polycrystalline film. At the same time, we achieve a reduction in the non-radiative recombination rate, a remarkable improvement in the photoluminescence quantum efficiency (PLQE) and a reduction in the electronic disorder deduced from an Urbach energy of only 12.6 meV in complete devices. As a result, we demonstrate a PCE of 19.1% with negligible hysteresis in planar heterojunction solar cells comprising all organic p and n-type charge collection layers. Our work shows that an additional level of control of perovskite thin film quality is possible via impurity cation doping, and further demonstrates the continuing importance of improving the electronic quality of the perovskite absorber and the nature of the heterojunctions to further improve the solar cell performance

Inversion symmetry and bulk Rashba effect in methylammonium lead iodide perovskite single crystals

Methylammonium lead iodide perovskite (MAPbI_3) exhibits long charge carrier lifetimes that are linked to its high efficiency in solar cells. Yet, the mechanisms governing these unusual carrier dynamics are not completely understood. A leading hypothesis—disproved in this work—is that a large, static bulk Rashba effect slows down carrier recombination. Here, using second harmonic generation rotational anisotropy measurements on MAPbI_3 crystals, we demonstrate that the bulk structure of tetragonal MAPbI_3 is centrosymmetric with I4/mcmspace group. Our calculations show that a significant Rashba splitting in the bandstructure requires a non-centrosymmetric lead iodide framework, and that incorrect structural relaxations are responsible for the previously predicted large Rashba effect. The small Rashba splitting allows us to compute effective masses in excellent agreement with experiment. Our findings rule out the presence of a large static Rashba effect in bulk MAPbI_3, and our measurements find no evidence of dynamic Rashba effects

Maximizing and stabilizing luminescence from halide perovskites with potassium passivation

Metal halide perovskites are of great interest for various high-performance optoelectronic applications. The ability to tune the perovskite bandgap continuously by modifying the chemical composition opens up applications for perovskites as coloured emitters, in building-integrated photovoltaics, and as components of tandem photovoltaics to increase the power conversion efficiency. Nevertheless, performance is limited by non-radiative losses, with luminescence yields in state-of-the-art perovskite solar cells still far from 100 per cent under standard solar illumination conditions. Furthermore, in mixed halide perovskite systems designed for continuous bandgap tunability2 (bandgaps of approximately 1.7 to 1.9 electronvolts), photoinduced ion segregation leads to bandgap instabilities. Here we demonstrate substantial mitigation of both non-radiative losses and photoinduced ion migration in perovskite films and interfaces by decorating the surfaces and grain boundaries with passivating potassium halide layers. We demonstrate external photoluminescence quantum yields of 66 per cent, which translate to internal yields that exceed 95 per cent. The high luminescence yields are achieved while maintaining high mobilities of more than 40 square centimetres per volt per second, providing the elusive combination of both high luminescence and excellent charge transport. When interfaced with electrodes in a solar cell device stack, the external luminescence yield—a quantity that must be maximized to obtain high efficiency—remains as high as 15 per cent, indicating very clean interfaces. We also demonstrate the inhibition of transient photoinduced ion-migration processes across a wide range of mixed halide perovskite bandgaps in materials that exhibit bandgap instabilities when unpassivated. We validate these results in fully operating solar cells. Our work represents an important advance in the construction of tunable metal halide perovskite films and interfaces that can approach the efficiency limits in tandem solar cells, coloured-light-emitting diodes and other optoelectronic applications.M.A.-J. thanks Nava Technology Limited and Nyak Technology Limited for their funding and technical support. Z.A.-G. acknowledges funding from a Winton Studentship, and ICON Studentship from the Lloyd’s Register Foundation. This project has received funding from the European Union’s Seventh Framework Programme (FP7/2007-2013) under REA grant agreement number PIOF-GA-2013-622630, the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (grant agreement number 756962), and the Royal Society and Tata Group (UF150033). We thank the Engineering and Physical Sciences Research Council (EPSRC) for support. XMaS is a mid-range facility at the European Synchrotron Radiation Facility supported by the EPSRC and we are grateful to the XMaS beamline team staff for their support. We thank Diamond Light Source for access to beamline I09 and staff member T.-L. Lee as well as U. Cappel for assistance during the HAXPES measurements. S.C., C.D. and G.D. acknowledge funding from the ERC under grant number 25961976 PHOTO EM and financial support from the European Union under grant number 77 312483 ESTEEM2. M.A. thanks the president of the UAE’s Distinguished Student Scholarship Program, granted by the Ministry of Presidential Affairs. H.R. and B.P. acknowledge support from the Swedish research council (2014-6019) and the Swedish foundation for strategic research. E.M.H. and T.J.S. were supported by the Netherlands Organization for Scientific Research under the Echo grant number 712.014.007

The Role of Ionic Liquid Electrolyte in an Aluminum–Graphite Electrochemical Cell

Using first-principles calculations and molecular dynamics simulation, we study the working mechanism in an aluminum–graphite electrochemical cell, which was recently reported to exhibit attractive performance. We exclude the possibility of Al³⁺ cation intercalation into graphite as in standard Li-ion batteries. Instead, we show that the AlCl₄^– anion intercalation mechanism is thermodynamically feasible. By including the ionic liquid electrolyte in the overall redox reaction, we are able to reproduce the high voltage observed in experiment. The active involvement of electrolyte in the reaction suggests that the evaluation of energy density needs to take the electrolyte into consideration. Our proposed structural model is consistent with the new peaks appearing in X-ray diffraction from the intercalation compound. The high rate capability is explained by the ultralow diffusion barriers of the AlCl₄ intercalant. With the clarified working mechanism, it becomes clear that the high voltage of the Al–graphite cell is a result of the thermodynamic instability of the AlCl₄-intercalated graphite