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Strain is a powerful experimental tool to explore new electronic states and understand unconventional superconductivity. Here, we investigate the effect of uniaxial strain on the nematic and superconducting phase of single crystal FeSe using magnetotransport measurements. We find that the resistivity response to the strain is strongly temperature dependent and it correlates with the sign change in the Hall coefficient being driven by scattering, coupling with the lattice and multiband phenomena. Band structure calculations suggest that under strain the electron pockets develop a large in-plane anisotropy as compared with the hole pocket. Magnetotransport studies at low temperatures indicate that the mobility of the dominant carriers increases with tensile strain. Close to the critical temperature, all resistivity curves at constant strain cross in a single point, indicating a universal critical exponent linked to a strain-induced phase transition. Our results indicate that the superconducting state is enhanced under compressive strain and suppressed under tensile strain, in agreement with the trends observed in FeSe thin films and overdoped pnictides, whereas the nematic phase seems to be affected in the opposite way by the uniaxial strain. By comparing the enhanced superconductivity under strain of different systems, our results suggest that strain on its own cannot account for the enhanced high $T_c$ superconductivity of FeSe systems., Comment: 11 pages, 8 figures

In the vicinity of a quantum critical point, quenched disorder can lead to a quantum Griffiths phase, accompanied by an exotic power-law scaling with a continuously varying dynamical exponent that diverges in the zero-temperature limit. Here, we investigate a nematic quantum critical point in the iron-based superconductor FeSe$_{0.89}$S$_{0.11}$ using applied hydrostatic pressure. We report an unusual crossing of the magnetoresistivity isotherms in the non-superconducting normal state which features a continuously varying dynamical exponent over a large temperature range. We interpret our results in terms of a quantum Griffiths phase caused by nematic islands that result from the local distribution of Se and S atoms. At low temperatures, the Griffiths phase is masked by the emergence of a Fermi liquid phase due to a strong nematoelastic coupling and a Lifshitz transition that changes the topology of the Fermi surface., Comment: 6 pages, 4 figures

Narrow-band gap (NBG) Sn-Pb perovskites with band gaps of ∼1.2 eV, which correspond to a broad photon absorption range up to ∼1033 nm, are highly promising candidates for bottom solar cells in all-perovskite tandem photovoltaics. To exploit their potential, avoiding optical losses in the top layer stacks of the tandem configuration is essential. This study addresses this challenge in two ways (1) removing the hole-transport layer (HTL) and (2) implementing highly transparent hydrogen-doped indium oxide In2O3:H (IO:H) electrodes instead of the commonly used indium tin oxide (ITO). Removing HTL reduces parasitic absorption loss in shorter wavelengths without compromising the photovoltaic performance. IO:H, with an ultra-low near-infrared optical loss and a high charge carrier mobility, results in a remarkable increase in the photocurrent of the semitransparent top and (HTL-free) NBG bottom perovskite solar cells when substituted for ITO. As a result, an IO:H-based four-terminal all-perovskite tandem solar cell (4T all-PTSCs) with a power conversion efficiency (PCE) as high as 24.8% is demonstrated, outperforming ITO-based 4T all-PTSCs with PCE up to 23.3%.

We study the elastoresistance of the highly correlated material CsFe_{2}As_{2} in all symmetry channels. Neutralizing its thermal expansion by means of a piezoelectric-based strain cell is demonstrated to be essential. The elastoresistance response in the in-plane symmetric channel is found to be large, while the response in the symmetry-breaking channels is weaker and provides no evidence for a divergent nematic susceptibility. Rather, our results can be interpreted naturally within the framework of a coherence-incoherence crossover, where the low-temperature coherent state is sensitively tuned by the in-plane atomic distances.

By band engineering the iron chalcogenide Fe(Se,Te) via ab initio calculations, we search for topological surface states and realizations of Majorana bound states. Proposed topological states are expected to occur for nonstoichiometric compositions on a surface Dirac cone where issues like disorder scattering and charge transfer between relevant electronic states have to be addressed. However, this surface Dirac cone is well above the Fermi level. Our goal is to theoretically design a substituted crystal in which the surface Dirac cone is shifted toward the Fermi level by modifying the bulk material without disturbing the surface. Going beyond conventional density functional theory, we apply the Blackman, Esterling, and Berk coherent potential approximation in a mixed basis pseudopotential framework to scan the substitutional phase space of cosubstitutions on the Se sites. We have identified iodine as a promising candidate for intrinsic doping. Our specific proposal is that ${\mathrm{FeSe}}_{0.325}{\mathrm{I}}_{0.175}{\mathrm{Te}}_{0.5}$ is a very likely candidate to exhibit a Dirac cone right at the Fermi energy without inducing strong disorder scattering.

Authors acknowledge Diamond Light Source for time on beamline I05-ARPES under Proposal SI23890. L.C.R. acknowledges funding from the Royal Commission for the Exhibition of 1851. We measure the electronic structure of FeSe from within individual orthorhombic domains. Enabled by an angle-resolved photoemission spectroscopy beamline with a highly focused beam spot (nano-ARPES), we identify clear stripelike orthorhombic domains in FeSe with a length scale of approximately 1-5 μm. Our photoemission measurements of the Fermi surface and band structure within individual domains reveal a single electron pocket at the Brillouin zone corner. This result provides clear evidence for a one-electron-pocket electronic structure of FeSe, observed without the application of uniaxial strain, and calls for further theoretical insight into this unusual Fermi surface topology. Our results also showcase the potential of nano-ARPES for the study of correlated materials with local domain structures. Publisher PDF

During the past year, halide double perovskites attracted attention as potential lead-free alternatives to Pb-based halide perovskites. However, none of the compounds discovered so far can match the optoelectronic properties of MAPbI3 (MA = CH3NH3). Here we argue that, from the electronic structure viewpoint, the only option to make Pb-free double perovskites retaining the remarkable properties of MAPbI3 is to combine In and Bi as B(+) and B(3+) cations, respectively. While inorganic double perovskites such as Cs2InBiX6 were found to be unstable due to In(+) oxidizing into In(3+), we show that the +1 oxidation state of In becomes progressively more stable as the A-site cation changes from K to Cs. Hence, we propose the use of MA and FA [FA = CH(NH2)2] to stabilize A2InBiBr6 double perovskites. We show that the optoelectronic properties of A2InBiBr6 are remarkably similar to those of MAPbI3, and explore the mixed-cation (Cs/MA/FA)2InBiBr6 halide double perovskites.

We present a combined study from angle-resolved photoemission and density-functional-theory calculations of the temperature-dependent electronic structure in the excitonic insulator candidate Ta2NiSe5. Our experimental measurements unambiguously establish the normal state as a semimetal with a significant band overlap of >100 meV. Our temperature-dependent measurements indicate how these low-energy states hybridize when cooling through the well-known 327 K phase transition in this system. From our calculations and polarizationdependent photoemission measurements, we demonstrate the importance of a loss of mirror symmetry in enabling the band hybridization, driven by a shearlike structural distortion which reduces the crystal symmetry from orthorhombic to monoclinic. Our results thus point to the key role of the lattice distortion in enabling the phase transition of Ta2NiSe5.

FeSe is a unique superconductor that can be manipulated to enhance its superconductivity using different routes while its monolayer form grown on different substrates reaches a record high temperature for a two-dimensional system. In order to understand the role played by the substrate and the reduced dimensionality on superconductivity, we examine the superconducting properties of exfoliated FeSe thin flakes by reducing the thickness from bulk down towards 9 nm. Magnetotransport measurements performed in magnetic fields up to 16T and temperatures down to 2K help to build up complete superconducting phase diagrams of different thickness flakes. While the thick flakes resemble the bulk behaviour, by reducing the thickness the superconductivity of FeSe flakes is suppressed. In the thin limit we detect signatures of a crossover towards two-dimensional behaviour from the observation of the vortex-antivortex unbinding transition and strongly enhanced anisotropy. Our study provides detailed insights into the evolution of the superconducting properties from three-dimensional bulk behaviour towards the two-dimensional limit of FeSe in the absence of a dopant substrate., 18 pages, 13 figures

Understanding superconductivity requires detailed knowledge of the normal electronic state from which it emerges. A nematic electronic state that breaks the rotational symmetry of the lattice can potentially promote unique scattering relevant for superconductivity. Here, we investigate the normal transport of superconducting FeSe$_{1-x}$S$_x$ across a nematic phase transition using high magnetic fields up to 69 T to establish the temperature and field-dependencies. We find that the nematic state is an anomalous non-Fermi liquid, dominated by a linear resistivity at low temperatures that can transform into a Fermi liquid, depending on the composition $x$ and the impurity level. Near the nematic end point, we find an extended temperature regime with $T^{1.5}$ resistivity. The transverse magnetoresistance inside the nematic phase has as a $H^{1.55}$ dependence over a large magnetic field range and it displays an unusual peak at low temperatures inside the nematic phase. Our study reveals anomalous transport inside the nematic phase, driven by the subtle interplay between the changes in the electronic structure of a multi-band system and the unusual scattering processes affected by large magnetic fields and disorder, Comment: 18 pages, 14 figures

The full H-T phase diagram in the nematic superconductor FeSe is mapped out using specific-heat and thermal-expansion measurements down to 0.7 K and up to 30 T for both field directions. A clear thermodynamic signal of an underlying vortex-melting transition is found in both datasets and could be followed down to low temperatures. The existence of significant Gaussian thermal superconducting fluctuations is demonstrated by a scaling analysis, which also yields the mean-field upper critical field Hc2(T). For both field orientations, Hc2(T) shows Pauli-limiting behavior. Whereas the temperature dependence of the vortex-melting line is well described by the model of Houghton et al., Phys. Rev. B 40, 6763 (1989) down to the lowest temperatures for H $\perp$ FeSe layers, the vortex-melting line exhibits an unusual behavior for fields parallel to the planes, where the Pauli limitation is much stronger. Here, the vortex-melting anomaly is only observed down to T*= 2-3 K, and then merges with the Hc2(T) line as predicted by Adachi and Ikeda, Phys. Rev. B 68 184510 (2003). Below T*, Hc2(T) also exhibits a slight upturn possibly related to the occurence of a Fulde-Ferrell-Larkin-Ovchinnikov (FFLO) state., 7 figures, 11 pages

The nematic electronic state and its associated critical fluctuations have emerged as a potential candidate for the superconducting pairing in various unconventional superconductors. However, in most materials their coexistence with magnetically ordered phases poses a significant challenge in determining their importance. Here, by combining chemical and hydrostatic physical pressure in FeSe0.89S0.11, we access a nematic quantum phase transition isolated from any other competing magnetic phases. From quantum oscillations in high magnetic fields, we trace the evolution of the Fermi surface and electronic correlations as a function of applied pressure and detect a Lifshitz transition that separates two distinct superconducting regions. One emerges from the nematic phase with a small Fermi surface and strong electronic correlations, while the other one has a large Fermi surface and weak correlations that promotes nesting and stabilization of a magnetically ordered phase at high pressures. The absence of mass divergence at the nematic quantum phase transition suggests that the nematic fluctuations could be quenched by the strong coupling to the lattice or local strain effects. A direct consequence is the weakening of superconductivity at the nematic quantum phase transition in the absence of magnetically driven fluctuations.

We report on the lattice and spin dynamics in monopnictide CrAs using polarized Raman scattering. This system exhibits a first-order magnetostructural phase transition at ${T}_{N}\ensuremath{\sim}265\phantom{\rule{0.16em}{0ex}}\mathrm{K}$, below which the magnetic moments of Cr form an incommensurate double helical magnetic structure while the unit-cell volume abruptly expands. Across the transition, the frequencies of the fully symmetric ${A}_{g}$ phonons strongly renormalize, which along with the results of first-principles calculations suggests the presence of a sizeable coupling of the phonons to the magnetic degrees of freedom in this compound. In addition, we observe two broad modes at around 350 and $1700\phantom{\rule{0.16em}{0ex}}\mathrm{c}{\mathrm{m}}^{\ensuremath{-}1}$ in the magnetic phase, which we associate with two-magnon Raman scattering. This work provides one of the few examples of magnetic Raman scattering from a noncollinear magnet.

Vapour deposition of metal halide perovskite by co-evaporation of precursors has the potential to achieve large-area high-efficiency solar cells on an industrial scale, yet little is known about the growth of metal halide perovskites by this method at the current time. Here, we report the fabrication of MAPbI3 films with average thicknesses from 2 – 320 nm by co-evaporation. We analyze the film properties using X-ray diffraction, optical absorption and photoluminescence (PL) to provide insights into the nucleation and growth of MAPbI3 films on quartz substrates. We find that the perovskite initially forms crystallite islands of around 8 nm in height, which may be the cause of the persistent small grain sizes reported for evaporated metal halide perovskites that hinder device efficiency and stability. As more material is added, islands coalesce until full coverage of the substrate is reached at around 10 nm average thickness. We also find that quantum confinement induces substantial shifts to the PL wavelength when the average thickness is below 40 nm, offering dual-source vapour deposition as an alternative method of fabricating nanoscale structures for LEDs and other devices.

In this work, passivation interlayers are investigated that enable high open-circuit voltage (V OC ) in wide-bandgap perovskite (WBP) solar cells. The interlayers are fabricated by processing a thin film of a large cation precursor on top of a 3D WBP thin-film (E G ~ 1.72 eV). The large cations n-butylammonium bromide (BABr) and ethylammonium bromide (EABr) show promising performance in WBP solar cells with stable power output conversion efficiencies of up to 19.4% and 17.9%, respectively. The corresponding V OC of these devices reaches values up to 1.31 V and 1.27 V for BABr and EABr, respectively. Compared to the reference devices without passivation interlayer (V OC ~ 1.23 V), this corresponds to an improvement in V OC of up to around 80 meV (BABr) and 40 meV (EABr), respectively. This enhancement in V OC originates from a reduction in non-radiative recombination losses. For the case of BABr, we reported already in a previous publication that a hybrid 2D/3D perovskite heterostructures is formed. Building on these results, in this proceeding paper we compare the performance of WBP solar cells using the large cation BABr and EABr for the processing of a passivation interlayers.

Superconductivity in FeSe has recently attracted a great deal of attention because it emerges out of an electronic nematic state of elusive character. Here we study both the electronic normal state and the superconducting gap structure using heat-capacity measurements on high-quality single crystals. The specific-heat curve, from 0.4 K to ${T}_{c}=9.1\phantom{\rule{0.16em}{0ex}}\mathrm{K}$, is found to be consistent with a recent gap determination using Bogoliubov quasiparticle interference [P. O. Sprau et al., Science 357, 75 (2017)]; however, only if nodes are introduced on either the electron or the hole Fermi-surface sheets. Our analysis, which is consistent with quantum-oscillation measurements, relies on the presence of one hole and one electron band only, and thus the fate of the theoretically predicted second electron pocket remains mysterious.

Metal halide perovskites are promising candidates for use in light emitting diodes (LEDs), due to their potential for color tunable and high luminescence efficiency. While recent advances in perovskite-based light emitting diodes have resulted in external quantum efficiencies exceeding 12.4% for the green emitters, and infrared emitters based on 3D/2D mixed dimensional perovskites have exceeded 20%, the external quantum efficiencies of the red and blue emitters still lag behind. A critical issue to date is creating highly emissive and stable perovskite emitters with the desirable emission band gap to achieve full-color displays and white LEDs. Herein, we report the preparation and characterization of a highly luminescent and stable suspension of cubic-shaped methylammonium lead triiodide (CH3NH3PbI3) perovskite nanocrystals, where we synthesize the nanocrystals via a ligand-assisted reprecipitation technique, using an acetonitrile/methylamine compound solvent system to solvate the ions and toluene as the antisolvent to induce crystallization. Through tuning the ratio of the ligands, the ligand to toluene ratio, and the temperature of the toluene, we obtain a solution of CH3NH3PbI3 nanocrystals with a photoluminescence quantum yield exceeding 93% and tunable emission between 660 and 705 nm. We also achieved red emission at 635 nm by blending the nanocrystals with bromide salt and obtained perovskite-based light emitting diodes with maximum electroluminescent external quantum efficiency of 2.75%.

We report an Fe $L$-edge resonant inelastic x-ray scattering (RIXS) study of the unusual superconductor $\ensuremath{\beta}$-FeSe. The high-energy resolution of this RIXS experiment ($\ensuremath{\approx}55\phantom{\rule{3.33333pt}{0ex}}\mathrm{meV}$ FWHM) made it possible to resolve low-energy excitations of the Fe $3d$ manifold. These include a broad peak which shows dispersive trends between 100 and 200 meV along the $(\ensuremath{\pi},0)$ and $(\ensuremath{\pi},\ensuremath{\pi})$ directions of the one-Fe square reciprocal lattice, and which can be attributed to paramagnon excitations. The multiband valence state of FeSe is among the most metallic in which such excitations have been discerned by soft x-ray RIXS.

The power conversion efficiency (PCE) of lead-halide perovskite solar cells (PSCs) is reported to increase over a period of days after their fabrication while they are stored in the dark. The effects underlying this spontaneous enhancement thus far are not understood. This work investigates the phenomenon for a variety of multi-cation-halide PSCs with different perovskite compositions and architectures. The observations reveal that spontaneous enhancement is not restricted to specific charge transport layers or perovskite compositions. The highest PCE observed in this study is an enhanced stable PCE of 19% (increased by 4% absolute). An increased open-circuit voltage is the primary contributor to the improved efficiency. Using time-resolved photoluminescence measurements, the initially present low-energy states are identified which disappear over a storage period of a few days. Furthermore, trap states probed by the thermally stimulated current technique exist in pristine PSCs and strikingly decrease for stored devices. In addition, the ideality factor approaches unity and X-ray diffraction analyses show lattice strain relaxation over the same period of time. These observations indicate that spontaneous enhancement of the PCE of PSCs is based on a reduction in trap-assisted non-radiative recombination possibly due to strain relaxation. Considering the demonstrated generality of spontaneous enhancement for different compositions of multi-cation-halide PSCs, our results highlight the importance of determining the absolute PCE increase initiated by spontaneous enhancement for developing high-efficiency PSCs.

We use high-resolution angle-resolved photoemission spectroscopy to map the three-dimensional momentum dependence of the superconducting gap in FeSe. We find that on both the hole and electron Fermi surfaces, the magnitude of the gap follows the distribution of dyz orbital weight. Furthermore, we theoretically determine the momentum dependence of the superconducting gap by solving the linearized gap equation using a tight-binding model which quantitatively describes both the experimental band dispersions and orbital characters. By considering a Fermi surface only including one electron pocket, as observed spectroscopically, we obtain excellent agreement with the experimental gap structure. Our finding of a scaling between the superconducting gap and the dyz orbital weight supports the interpretation of superconductivity mediated by spin fluctuations in FeSe. Publisher PDF

We investigate the influence of solvent drenching in hybrid organic–inorganic perovskite (CH3NH3PbX) crystallization process with a non-solvent, toluene, during film fabrication process. We use three different precursor compositions, CH3NH3I (MAI):PbI2, 3MAI:PbI2 and 3MAI:PbCl2 to unravel the crystallization mechanism with toluene drenching. The mixed halide precursor (3MAI:PbCl2) results in the highest quality films with the toluene treatment, including high surface coverage, large grains, long PL lifetimes and high photoluminescence quantum efficiency (PLQE). The neat halide-based precursors (MAI:PbI2 and 3MAI:PbI2) with the treatment have increased photo-physical properties (PL lifetime and PLQE) and a surface coverage, but slightly decrease grain size in the film, while the 3MAI:PbI2 precursor has still formed numerous pinholes in the film. Mechanistically, we visually observe that the toluene drenching accelerates the nucleation at early stage of crystallization in 3MAI:PbCl2 precursor. X-ray diffraction pattern in this stage confirms the formation of both MAPbI3 and MAPbCl3, nucleation. During the crystallization process MAPbCl3 is transformed into MAPbI3 phase by the anion exchange. Toluene treatment strongly affects the ratio of MAPbI3 and MAPbCl3, nucleation and hence plays a critical role in deciding the final film morphology, their optoelectronic properties and hence their device performances.

Lead halide perovskites are materials with excellent optoelectronic and photovoltaic properties. However, some hurdles remain prior to commercialization of these materials, such as chemical stability, phase stability, sensitivity to moisture, and potential issues due to the toxicity of lead. Here, we report a new type of lead-free perovskite related compound, Cs2PdBr6. This compound is solution processable, exhibits long-lived photoluminescence, and an optical band gap of 1.6 eV. Density functional theory calculations indicate that this compound has dispersive electronic bands, with electron and hole effective masses of 0.53 and 0.85 me, respectively. In addition, Cs2PdBr6 is resistant to water, in contrast to lead-halide perovskites, indicating excellent prospects for long-term stability. These combined properties demonstrate that Cs2PdBr6 is a promising novel compound for optoelectronic applications.

Iron-based chalcogenides are complex superconducting systems in which orbitally-dependent electronic correlations play an important role. Here, using high-resolution angle-resolved photoemission spectroscopy, we investigate the effect of these electronic correlations outside the nematic phase in the tetragonal phase of superconducting FeSe1-xSx (x = 0; 0:18; 1). With increasing sulfur substitution, the Fermi velocities increase significantly and the band renormalizations are suppressed towards a factor of 1.5-2 for FeS. Furthermore, the chemical pressure leads to an increase in the size of the quasi-two dimensional Fermi surface, compared with that of FeSe, however, it remains smaller than the predicted one from first principle calculations for FeS. Our results show that the isoelectronic substitution is an effective way to tune electronic correlations in FeSe1-xSx, being weakened for FeS with a lower superconducting transition temperature. This suggests indirectly that electronic correlations could help to promote higher-Tc superconductivity in FeSe., 4 pages, 3 figures

Due to its highly tunable unconventional superconductivity, FeSe is one of the most intriguing materials among the iron-based superconductors. In addition, it exhibits a tetragonal to orthorhombic ``nematic'' phase transition in the absence of static magnetic order. This article presents a set of tight-binding parameters, optimized directly with respect to experimental angle-resolved photoemission spectroscopy (ARPES) data obtained at 100 K. It thus provides a quantitatively accurate model of the electronic structure of the tetragonal phase of FeSe and, hence, a coherent foundation for the understanding of the unique physical properties of this system. The authors go on to predict a feature that has so far remained unnoticed in simpler DFT-based tight-binding-model analyses, namely, a significant temperature dependence of the chemical potential in FeSe. This is confirmed by performing ARPES on FeSe single crystals, whereby a 25-meV rigid chemical potential shift is detected across the entire Brillouin zone over the temperature range between 100 K and 300 K. The finding has important implications for any future theoretical models of nematicity and superconductivity in FeSe and related materials.

We have accurately determined the exciton binding energy and reduced mass of single crystals of methylammonium lead tri-iodide using magneto-reflectivity at very high magnetic fields. The single crystal has excellent optical properties with a narrow line width of $\sim 3$meV for the excitonic transitions and a 2s transition which is clearly visible even at zero magnetic field. The exciton binding energy of $16 \pm 2$meV in the low temperature orthorhombic phase is almost identical to the value found in polycrystalline samples, crucially ruling out any possibility that the exciton binding energy depends on the grain size. In the room temperature tetragonal phase, an upper limit for the exciton binding energy of $12 \pm 4$ meV is estimated from the evolution of 1s-2s splitting at high magnetic field., 5 pages, 4 figures

We report a high-resolution laser-based angle-resolved photoemission spectroscopy (laser-ARPES) study of single crystals of FeSe, focusing on the temperature-dependence of the hole-like bands around the ${\rm \Gamma}$ point. As the system cools through the tetragonal-orthorhombic "nematic" structural transition at 90~K, the splitting of the $d_{xz}$/$d_{yz}$ bands is observed to increase by a magnitude of 13 meV. Moreover, the onset of a $\sim$10 meV downward shift of the $d_{xy}$ band is also at 90~K. These measurements provide clarity on the nature, magnitude and temperature-dependence of the band shifts at the ${\rm \Gamma}$ point in the nematic phase of FeSe.

We present herein an experimental screening study that assesses how partially replacing Pb in methylammonium lead triiodide perovskite films with nine different alternative, divalent metal species, B = {Co, Cu, Fe, Mg, Mn, Ni, Sn, Sr, and Zn}, influences photovoltaic performance and optical properties. Our findings indicate the perovskite film is tolerant to most of the considered homovalent metal species with lead-cobalt compositions yielding the highest power conversion efficiencies when less than 6% of the Pb2+ ions are replaced. Through subsequent materials characterisation, we demonstrate for the first time that partially substituting Pb2+ at the B-sites of the perovskite lattice is not restricted to Group IV elements but is also possible with at least Co2+. Moreover, adjusting the molar ratio of Pb:Co in the mixed-metal perovskite affords new opportunities to tailor the material properties while maintaining stabilised device efficiencies above 16% in optimised solar cells. Specifically, crystallographic analysis reveals that Co2+ incorporates into the perovskite lattice and increasing its concentration can mediate a crystal structure transition from the cubic to tetragonal phase at room-temperature. Likewise, Co2+ substitution continually modifies the perovskite work function and band edge energies without either changing the band gap or electronically doping the intrinsic material. By leveraging this orthogonal dimension of electronic tunability, we achieve remarkably high open-circuit voltages up to 1.08 V with an inverted device architecture by shifting the perovskite into a more favourable energetic alignment with the PEDOT:PSS hole transport material.

The presence of ${d}_{xz}\text{\ensuremath{-}}{d}_{yz}$ orbital ordering is often considered a hallmark of the nematic phase of Fe-based superconductors, including FeSe, but the details of the order parameter remain controversial. Here, we report a high-resolution angle-resolved photoemission spectroscopy study of single crystals of FeSe, accounting for the photon-energy dependence and making a detailed analysis of the temperature dependence. We find that the hole pocket undergoes a fourfold-symmetry-breaking distortion in the nematic phase below 90 K, but, in contrast, the changes to the electron pockets do not require fourfold symmetry breaking. Instead, there is an additional separation of the existing ${d}_{xy}$ and ${d}_{xz/yz}$ bands, which themselves are not split within resolution. These observations lead us to propose a scenario of ``unidirectional nematic bond ordering'' to describe the low-temperature electronic structure of FeSe, supported by good agreement with ten-orbital tight-binding model calculations.

We report a high-resolution angle-resolved photo-emission spectroscopy study of the evolution of the electronic structure of FeSe1-xSx single crystals. Isovalent S substitution onto the Se site constitutes a chemical pressure which subtly modifies the electronic structure of FeSe at high temperatures and induces a suppression of the tetragonal-symmetry-breaking structural transition temperature from 87K to 58K for x=0.15. With increasing S substitution, we find smaller splitting between bands with dyz and dxz orbital character and weaker anisotropic distortions of the low temperature Fermi surfaces. These effects evolve systematically as a function of both S substitution and temperature, providing strong evidence that an orbital ordering is the underlying order parameter of the structural transition in FeSe1-xSx. Finally, we detect the small inner hole pocket for x=0.12, which is pushed below the Fermi level in the orbitally-ordered low temperature Fermi surface of FeSe., Latex, 5 pages, 4 figures

Perovskites for tandem solar cells Improving the performance of conventional single-crystalline silicon solar cells will help increase their adoption. The absorption of bluer light by an inexpensive overlying solar cell in a tandem arrangement would provide a step in the right direction by improving overall efficiency. Inorganic-organic perovskite cells can be tuned to have an appropriate band gap, but these compositions are prone to decomposition. McMeekin et al. show that using cesium ions along with formamidinium cations in lead bromide–iodide cells improved thermal and photostability. These improvements lead to high efficiency in single and tandem cells. Science , this issue p. 151

Muon spin rotation measurements have been performed on a powder sample ofα-RuCl3, a layered material in which Ru ions are arranged on a honeycomb lattice and which previously has been proposed to be close to a quantum spin liquid ground state. Our data reveal two distinct transitions at 11 and 14 K, which we interpret as originating from the onset of three-dimensional order and in-plane magnetic order, respectively. We identify, with the help of density functional theory calculations, likely muon stopping sites and combine these with dipolar field calculations to show that the two measured muon rotation frequencies are consistent with two inequivalent muon sites within a zigzag antiferromagnetic structure proposed previously.

The recent discovery of lead-free halide double perovskites with band gaps in the visible represents an important step forward in the design of environmentally friendly perovskite solar cells. Within this new family of semiconductors, Cs2BiAgCl6 and Cs2BiAgBr6 are stable compounds crystallizing in the elpasolite structure. Following the recent computational discovery and experimental synthesis of these compounds, a detailed investigation of their electronic properties is warranted in order to establish their potential as optoelectronic materials. In this work, we perform many-body perturbation theory calculations and obtain high accuracy band gaps for both compounds. In addition, we report on the synthesis of Cs2BiAgBr6 single crystals, which are stable in ambient conditions. From our complementary theoretical and experimental analysis, we are able to assign the indirect character of the band gaps and obtain both experimental and theoretical band gaps of these novel semiconductors that are in close agreement.

© 2016 The Royal Society of Chemistry. Interfacial engineering has been shown to play a vital role in boosting the performance of perovskite solar cells in the past few years. Here we demonstrate that caesium bromide (CsBr), as an interfacial modifier between the electron collection layer and the CH3NH3PbI3-xClx absorber layer, can effectively enhance the stability of planar heterojunction devices under ultra violet (UV) light soaking. Additionally, the device performance is improved due to the alleviated defects at the perovskite-titania heterojunction and enhanced electron extraction.

Lead-based halide perovskites are emerging as the most promising class of materials for next generation optoelectronics. However, despite the enormous success of lead-halide perovskite solar cells, the issues of stability and toxicity are yet to be resolved. Here we report on the computational design and the experimental synthesis of a new family of Pb-free inorganic halide double-perovskites based on bismuth or antimony and noble metals. Using first-principles calculations we show that this hitherto unknown family of perovskites exhibits very promising optoelectronic properties, such as tunable band gaps in the visible range and low carrier effective masses. Furthermore, we successfully synthesize the double perovskite Cs2BiAgCl6, we perform structural refinement using single-crystal X-ray diffraction, and we characterize its optical properties via optical absorption and photoluminescence measurements. This new perovskite belongs to the Fm-3m space group, and consists of BiCl6 and AgCl6 octahedra alternating in a rock-salt face-centered cubic structure. From UV-Vis and PL measurements we obtain an indirect gap of 2.2 eV. The new compound is very stable under ambient conditions., Comment: GV and MRF contributed equally to this work

Magnetoresistivity ${\ensuremath{\rho}}_{xx}$ and Hall resistivity ${\ensuremath{\rho}}_{xy}$ in ultrahigh magnetic fields up to 88 T are measured down to 0.15 K to clarify the multiband electronic structure in high-quality single crystals of superconducting FeSe. At low temperatures and high fields we observe quantum oscillations in both resistivity and the Hall effect, confirming the multiband Fermi surface with small volumes. We propose a novel approach to identify from magnetotransport measurements the sign of the charge carriers corresponding to a particular cyclotron orbit in a compensated metal. The observed significant differences in the relative amplitudes of the quantum oscillations between the ${\ensuremath{\rho}}_{xx}$ and ${\ensuremath{\rho}}_{xy}$ components, together with the positive sign of the high-field ${\ensuremath{\rho}}_{xy}$, reveal that the largest pocket should correspond to the hole band. The low-field magnetotransport data in the normal state suggest that, in addition to one hole and one almost compensated electron band, the orthorhombic phase of FeSe exhibits an additional tiny electron pocket with a high mobility.

The 5 K superconductor La2Sb shares some structural similarities with the iron-pnictides and -chalgogenides, especially the so-called 122-compounds, despite lacking a 3d-metal component. In order to look for similarities and dissimilarities of this layered metal pnictide with the higher-Tc Fe-based superconductors, we have performed a combined experimental and theoretical investigation of the effects of hydrostatic pressure. Magnetic measurements reveal a linear increase of Tc with pressure at a rate dTc/dP=(0.71±0.01)KGPa−1. Band structure calculations show that (i) the states at the Fermi level have predominantly La 5d character and (ii) that the density of states increases linearly with increasing pressure. By using these theoretical results and a BCS formalism, a quantitative description of the experimentally revealed pressure dependence of Tc is possible within a reasonable range of parameters. Our results indicate that La2Sb, despite its structural similarities to the 122 Fe-based superconductors, exhibits a BCS-type of superconductivity.

One of the key requirements for good thermoelectric materials is a low lattice thermal conductivity. Here we present a combined neutron scattering and theoretical investigation of the lattice dynamics in the type I clathrate system Ba-Ge-Ni, which fulfills this requirement. We observe a strong hybridization between phonons of the Ba guest atoms and acoustic phonons of the Ge-Ni host structure over a wide region of the Brillouin zone, which is in contrast with the frequently adopted picture of isolated Ba atoms in Ge-Ni host cages. It occurs without a strong decrease of the acoustic phonon lifetime, which contradicts the usual assumption of strong anharmonic phonon--phonon scattering processes. Within the framework of ab initio density-functional theory calculations we interpret these hybridizations as a series of anticrossings which act as a low-pass filter, preventing the propagation of acoustic phonons. To highlight the effect of such a phononic low-pass filter on the thermal transport, we compute the contribution of acoustic phonons to the thermal conductivity of Ba${}_{8}$Ge${}_{40}$Ni${}_{6}$ and compare it to those of pure Ge and a Ge${}_{46}$ empty-cage model system.

Room-temperature films of black-phase cesium lead iodide (CsPbI3) are widely thought to be trapped in a cubic perovskite polymorph. Here, we challenge this assumption. We present structural refinement of room-temperature black-phase CsPbI3 in an orthorhombic polymorph. We demonstrate that this polymorph is adopted by both powders and thin films of black-phase CsPbI3, fabricated either by high- or low-temperature processes. We perform electronic band structure calculations for the orthorhombic polymorph and find agreement with experimental data and close similarities with orthorhombic methylammonium lead iodide. We investigate the structural transitions and thermodynamic stability of the various polymorphs of CsPbI3 and show that the orthorhombic polymorph is the most stable among its other perovskite polymorphs, but it remains less stable than the yellow nonperovskite polymorph.

A$_2$BB$^\prime$X$_6$ halide double perovskites based on bismuth and silver have recently been proposed as potential environmentally-friendly alternatives to lead-based hybrid halide perovskites. In particular, Cs$_2$BiAgX$_6$ (X = Cl, Br) have been synthesized and found to exhibit band gaps in the visible range. However, the band gaps of these compounds are indirect, which is not ideal for applications in thin film photovoltaics. Here, we propose a new class of halide double perovskites, where the B$^{3+}$ and B$^{+}$ cations are In$^{3+}$ and Ag$^{+}$, respectively. Our first-principles calculations indicate that the hypothetical compounds Cs$_2$InAgX$_6$ (X = Cl, Br, I) should exhibit direct band gaps between the visible (I) and the ultraviolet (Cl). Based on these predictions, we attempt to synthesize Cs$_2$InAgCl$_6$ and Cs$_2$InAgBr$_6$, and we succeed to form the hitherto unknown double perovskite Cs$_2$InAgCl$_6$. X-ray diffraction yields a double perovskite structure with space group $Fm\overline{3}m$. The measured band gap is 3.3 eV, and the compound is found to be photosensitive and turns reversibly from white to orange under ultraviolet illumination. We also perform an empirical analysis of the stability of Cs$_2$InAgX$_6$ and their mixed halides based on Goldschmidt's rules, and we find that it should also be possible to form Cs$_2$InAg(Cl$_{1-x}$Br$_{x}$)$_6$ for $x

We use angle-resolved photoemission spectroscopy (ARPES) to explore the electronic structure of single crystals of FeSe over a wide range of binding energies and study the effects of strong electron-electron correlations. We provide evidence for the existence of ``Hubbard-like bands'' at high binding energies consisting of incoherent many-body excitations originating from Fe $3d$ states in addition to the renormalized quasiparticle bands near the Fermi level. Many high-energy features of the observed ARPES data can be accounted for when incorporating the effects of strong local Coulomb interactions in calculations of the spectral function via dynamical mean-field theory, including the formation of a Hubbard-like band. This shows that over the energy scale of several eV, local correlations arising from the on-site Coulomb repulsion and Hund's coupling are essential for a proper understanding of the electronic structure of FeSe and other related iron-based superconductors.