Sian Elizabeth Dutton

Preparation of Single-Phase Films of CH3NH3Pb(I1–xBrx)3 with Sharp Optical Band Edges

Organometallic lead-halide perovskite-based solar cells now approach 18% efficiency. Introducing a mixture of bromide and iodide in the halide composition allows tuning of the optical bandgap. We prepare mixed bromide-iodide lead perovskite films CH3NH3Pb(I1-xBrx)3 (0 ≤ x ≤ 1) by spin-coating from solution and obtain films with monotonically varying bandgaps across the full composition range. Photothermal deflection spectroscopy, photoluminescence, and X-ray diffraction show that following suitable fabrication protocols these mixed lead-halide perovskite films form a single phase. The optical absorption edge of the pure triiodide and tribromide perovskites is sharp with Urbach energies of 15 and 23 meV, respectively, and reaches a maximum of 90 meV for CH3NH3PbI1.2Br1.8. We demonstrate a bromide-iodide lead perovskite film (CH3NH3PbI1.2Br1.8) with an optical bandgap of 1.94 eV, which is optimal for tandem cells of these materials with crystalline silicon devices.

Mg(PF6)2-Based Electrolyte Systems: Understanding Electrolyte–Electrode Interactions for the Development of Mg-Ion Batteries

Mg(PF6)2-based electrolytes for Mg-ion batteries have not received the same attention as the analogous LiPF6-based electrolytes used in most Li-ion cells owing to the perception that the PF6(-) anion decomposes on and passivates Mg electrodes. No synthesis of the Mg(PF6)2 salt has been reported, nor have its solutions been studied electrochemically. Here, we report the synthesis of the complex Mg(PF6)2(CH3CN)6 and its solution-state electrochemistry. Solutions of Mg(PF6)2(CH3CN)6 in CH3CN and CH3CN/THF mixtures exhibit high conductivities (up to 28 mS·cm(-1)) and electrochemical stability up to at least 4 V vs Mg on Al electrodes. Contrary to established perceptions, Mg electrodes are observed to remain electrochemically active when cycled in the presence of these Mg(PF6)2-based electrolytes, with no fluoride (i.e., MgF2) formed on the Mg surface. Stainless steel electrodes are found to corrode when cycled in the presence of Mg(PF6)2 solutions, but Al electrodes are passivated. The electrolytes have been used in a prototype Mg battery with a Mg anode and Chevrel (Mo3S4)-phase cathode.

Studies of the Room‐Temperature Multiferroic Pb(Fe0.5Ta0.5)0.4(Zr0.53Ti0.47)0.6O3: Resonant Ultrasound Spectroscopy, Dielectric, and Magnetic Phenomena

Recently, lead iron tantalate/lead zirconium titanate (PZTFT) was demonstrated to possess large, but unreliable, magnetoelectric coupling at room temperature. Such large coupling would be desirable for device applications but reproducibility would also be critical. To better understand the coupling, the properties of all 3 ferroic order parameters, elastic, electric, and magnetic, believed to be present in the material across a range of temperatures, are investigated. In high temperature elastic data, an anomaly is observed at the orthorhombic mm2 to tetragonal 4mm transition, Tot = 475 K, and a softening trend is observed as the temperature is increased toward 1300 K, where the material is known to become cubic. Thermal degradation makes it impossible to measure elastic behavior up to this temperature, however. In the low temperature region, there are elastic anomalies near ≈40 K and in the range 160–245 K. The former is interpreted as being due to a magnetic ordering transition and the latter is interpreted as a hysteretic regime of mixed rhombohedral and orthorhombic structures. Electrical and magnetic data collected below room temperature show anomalies at remarkably similar temperature ranges to the elastic data. These observations are used to suggest that the three order parameters in PZTFT are strongly coupled.

Electronic and magnetic properties of superconducting LnO1-x F x BiS2 (Ln = La, Ce, Pr, and Nd) from first principles.

A density functional theory study of the BiS2 superconductors containing rare-earths: LnO1-x F x BiS2 (Ln  =  La, Ce, Pr, and Nd) is presented. We find that CeO0.5F0.5BiS2 has competing ferromagnetic and weak antiferromagnetic tendencies, the first one corresponding to experimental results. We show that PrO0.5F0.5BiS2 has a strong tendency for magnetic order, which can be ferromagnetic or antiferromagnetic depending on subtle differences in 4f orbital occupations. We demonstrate that NdO0.5F0.5BiS2 has a stable magnetic ground state with weak tendency to order. Finally, we show that the change of rare earth does not affect the Fermi surface, and predict that CeOBiS2 should display a pressure induced phase transition to a metallic, if not superconducting, phase under pressure.

Effects of stoichiometric doping in superconducting Bi-O-S compounds

Newly discovered Bi-O-S compounds remain an enigma in attempts to understand their electronic properties. A recent study of Bi4O4S3 has shown it to be a mixture of two phases, Bi2OS2 and Bi3O2S3, the latter being superconducting (Phelan et al 2013 J. Am. Chem. Soc. 135 5372-4). Using density functional theory, we explore the electronic structure of both the phases and the effect of the introduction of extra BiS2 bilayers. Our results demonstrate that the S2 layers dope the bismuth-sulphur bands and this causes metallisation. The bands at the Fermi level are of clear two-dimensional character. One band manifold is confined to the two adjacent, square-lattice bismuth-sulphur planes, a second manifold is confined to the square lattice of sulphur dimers. We show that the introduction of extra BiS2 bilayers does not influence the electronic structure. Finally, we also show that spin-orbit coupling does not have any significant effect on the states close to the Fermi level at the energy scale considered.

Elastic and magnetoelastic relaxation behaviour of multiferroic (ferromagnetic + ferroelectric + ferroelastic) Pb(Fe0.5Nb0.5)O3 perovskite.

Resonant Ultrasound Spectroscopy has been used to characterize elastic and anelastic anomalies in a polycrystalline sample of multiferroic Pb(Fe(0.5)Nb(0.5))O(3) (PFN). Elastic softening begins at ~550 K, which is close to the Burns temperature marking the development of dynamical polar nanoregions. A small increase in acoustic loss at ~425 K coincides with the value of T(*) reported for polar nanoregions starting to acquire a static or quasi-static component. Softening of the shear modulus by ~30-35% through ~395-320 K, together with a peak in acoustic loss, is due to classical strain/order parameter coupling through the cubic → tetragonal → monoclinic transition sequence of ferroelectric/ferroelastic transitions. A plateau of high acoustic loss below ~320 K is due to the mobility under stress of a ferroelastic microstructure but, instead of the typical effects of freezing of twin wall motion at some low temperature, there is a steady decrease in loss and increase in elastic stiffness below ~85 K. This is attributed to freezing of a succession of strain-coupled defects with a range of relaxation times and is consistent with a report in the literature that PFN develops a tweed microstructure over a wide temperature interval. No overt anomaly was observed near the expected Néel point, ~145 K, consistent with weak/absent spin/lattice coupling but heat capacity measurements showed that the antiferromagnetic transition is actually smeared out or suppressed. Instead, the sample is weakly ferromagnetic up to ~560 K, though it has not been possible to exclude definitively the possibility that this could be due to some magnetic impurity. Overall, evidence from the RUS data is of a permeating influence of static and dynamic strain relaxation effects which are attributed to local strain heterogeneity on a mesoscopic length scale. These, in turn, must have a role in determining the magnetic properties and multiferroic character of PFN.

Emergent order in the kagome Ising magnet Dy 3 Mg 2 Sb 3 O 14

The Ising model—in which degrees of freedom (spins) are binary valued (up/down)—is a cornerstone of statistical physics that shows rich behaviour when spins occupy a highly frustrated lattice such as kagome. Here we show that the layered Ising magnet Dy3Mg2Sb3O14 hosts an emergent order predicted theoretically for individual kagome layers of in-plane Ising spins. Neutron-scattering and bulk thermomagnetic measurements reveal a phase transition at ∼0.3 K from a disordered spin-ice-like regime to an emergent charge ordered state, in which emergent magnetic charge degrees of freedom exhibit three-dimensional order while spins remain partially disordered. Monte Carlo simulations show that an interplay of inter-layer interactions, spin canting and chemical disorder stabilizes this state. Our results establish Dy3Mg2Sb3O14 as a tuneable system to study interacting emergent charges arising from kagome Ising frustration.

Theory and Practice: Bulk Synthesis of C3B and its H2‐ and Li‐Storage Capacity

Previous theoretical studies of C3B have suggested that boron-doped graphite is a promising H2- and Li-storage material, with large maximum capacities. These characteristics could lead to exciting applications as a lightweight H2-storage material for automotive engines and as an anode in a new generation of batteries. However, for these applications to be realized a synthetic route to bulk C3B must be developed. Here we show the thermolysis of a single-source precursor (1,3-(BBr2)2C6H4) to produce graphitic C3B, thus allowing the characteristics of this elusive material to be tested for the first time. C3B was found to be compositionally uniform but turbostratically disordered. Contrary to theoretical expectations, the H2- and Li-storage capacities are lower than anticipated, results that can partially be explained by the disordered nature of the material. This work suggests that to model the properties of graphitic materials more realistically, the possibility of disorder must be considered.

Formation of Long-Lived Color Centers for Broadband Visible Light Emission in Low-Dimensional Layered Perovskites

We investigate the origin of the broadband visible emission in layered hybrid lead-halide perovskites and its connection with structural and photophysical properties. We study ⟨001⟩ oriented thin films of hexylammonium (HA) lead iodide, (C6H16N)2PbI4, and dodecylammonium (DA) lead iodide, (C12H28N)2PbI4, by combining first-principles simulations with time-resolved photoluminescence, steady-state absorption and X-ray diffraction measurements on cooling from 300 to 4 K. Ultrafast transient absorption and photoluminescence measurements are used to track the formation and recombination of emissive states. In addition to the excitonic photoluminescence near the absorption edge, we find a red-shifted, broadband (full-width at half-maximum of about 0.4 eV), emission band below 200 K, similar to emission from ⟨110⟩ oriented bromide 2D perovskites at room temperature. The lifetime of this sub-band-gap emission exceeds that of the excitonic transition by orders of magnitude. We use X-ray diffraction measurements to study the changes in crystal lattice with temperature. We report changes in the octahedral tilt and lattice spacing in both materials, together with a phase change around 200 K in DA2PbI4. DFT simulations of the HA2PbI4 crystal structure indicate that the low-energy emission is due to interstitial iodide and related Frenkel defects. Our results demonstrate that white-light emission is not limited to ⟨110⟩ oriented bromide 2D perovskites but a general property of this class of system, and highlight the importance of defect control for the formation of low-energy emissive sites, which can provide a pathway to design tailored white-light emitters.

Elastic and anelastic relaxation behaviour of perovskite multiferroics II : PbZr0.53Ti0.47O3 (PZT)–PbFe0.5Ta0.5O3 (PFT)

Elastic and anelastic properties of ceramic samples of multiferroic perovskites with nominal compositions across the binary join PbZr0.53Ti0.47O3–PbFe0.5Ta0.5O3 (PZT–PFT) have been assembled to create a binary phase diagram and to address the role of strain relaxation associated with their phase transitions. Structural relationships are similar to those observed previously for PbZr0.53Ti0.47O3–PbFe0.5Nb0.5O3 (PZT–PFN), but the magnitude of the tetragonal shear strain associated with the ferroelectric order parameter appears to be much smaller. This leads to relaxor character for the development of ferroelectric properties in the end member PbFe0.5Ta0.5O3. As for PZT–PFN, there appear to be two discrete instabilities rather than simply a reorientation of the electric dipole in the transition sequence cubic–tetragonal–monoclinic, and the second transition has characteristics typical of an improper ferroelastic. At intermediate compositions, the ferroelastic microstructure has strain heterogeneities on a mesoscopic length scale and, probably, also on a microscopic scale. This results in a wide anelastic freezing interval for strain-related defects rather than the freezing of discrete twin walls that would occur in a conventional ferroelastic material. In PFT, however, the acoustic loss behaviour more nearly resembles that due to freezing of conventional ferroelastic twin walls. Precursor softening of the shear modulus in both PFT and PFN does not fit with a Vogel–Fulcher description, but in PFT there is a temperature interval where the softening conforms to a power law suggestive of the role of fluctuations of the order parameter with dispersion along one branch of the Brillouin zone. Magnetic ordering appears to be coupled only weakly with a volume strain and not with shear strain but, as with multiferroic PZT–PFN perovskites, takes place within crystals which have significant strain heterogeneities on different length scales.