Siân E. Dutton

Blue-Green Color Tunable Solution Processable Organolead Chloride–Bromide Mixed Halide Perovskites for Optoelectronic Applications

Solution-processed organo-lead halide perovskites are produced with sharp, color-pure electroluminescence that can be tuned from blue to green region of visible spectrum (425–570 nm). This was accomplished by controlling the halide composition of CH3NH3Pb(BrxCl1–x)3 [0 ≤ x ≤ 1] perovskites. The bandgap and lattice parameters change monotonically with composition. The films possess remarkably sharp band edges and a clean bandgap, with a single optically active phase. These chloride–bromide perovskites can potentially be used in optoelectronic devices like solar cells and light emitting diodes (LEDs). Here we demonstrate high color-purity, tunable LEDs with narrow emission full width at half maxima (FWHM) and low turn on voltages using thin-films of these perovskite materials, including a blue CH3NH3PbCl3 perovskite LED with a narrow emission FWHM of 5 nm.

High Open-Circuit Voltages in Tin-Rich Low-Bandgap Perovskite-Based Planar Heterojunction Photovoltaics

Low-bandgap CH3 NH3 (Pbx Sn1-x )I3 (0 ≤ x ≤ 1) hybrid perovskites (e.g., ≈1.5-1.1 eV) demonstrating high surface coverage and superior optoelectronic properties are fabricated. State-of-the-art photovoltaic (PV) performance is reported with power conversion efficiencies approaching 10% in planar heterojunction architecture with small (<450 meV) energy loss compared to the bandgap and high (>100 cm2 V-1 s-1 ) intrinsic carrier mobilities.

Superconductivity at 2.3 K in the misfit compound (PbSe)1.16(TiSe2)2

The structural misfit compound (PbSe)1.16(TiSe2)2 is reported. It is a superconductor with a Tc of 2.3 K. (PbSe)1.16(TiSe2)2 derives from a parent compound, TiSe2, which shows a charge-density wave transition and no superconductivity. The crystal structure, characterized by high-resolution electron microscopy and powder x-ray diffraction, consists of two layers of 1T-TiSe2 alternating with a double layer of (100) PbSe. Transport measurements suggest that the superconductivity is induced by charge transfer from the PbSe layers to the TiSe2 layers.

Quantum Spin Liquid in Frustrated One-Dimensional LiCuSbO4

A quantum magnet, LiCuSbO4, with chains of edge-sharing spin-1/2 CuO6 octahedra is reported. While short-range order is observed for T<10  K, no zero-field phase transition or spin freezing occurs down to 100 mK. Specific heat indicates a distinct high-field phase near the 12 T saturation field. Neutron scattering shows incommensurate spin correlations with q=(0.47±0.01)π/a and places an upper limit of 70  μeV on any spin gap. Exact diagonalization of 16-spin easy-plane spin-1/2 chains with competing ferro- and antiferromagnetic interactions (J1=-75  K, J2=34  K) accounts for the T>2  K data.

Tunable Near-Infrared Luminescence in Tin Halide Perovskite Devices

Infrared emitters are reasonably rare in solution-processed materials. Recently, research into hybrid organo-lead halide perovskite, originally popular in photovoltaics,1-3 has gained traction in light-emitting diodes (LED) due to their low-cost solution processing and good performance.4-9 The lead-based electroluminescent materials show strong colorful emission in the visible region, but lack emissive variants further in the infrared. The concerns with the toxicity of lead may, additionally, limit their wide-scale applications. Here, we demonstrate tunable near-infrared electroluminescence from a lead-free organo-tin halide perovskite, using an ITO/PEDOT:PSS/CH3NH3Sn(Br1-xIx)3/F8/Ca/Ag device architecture. In our tin iodide (CH3NH3SnI3) LEDs, we achieved a 945 nm near-infrared emission with a radiance of 3.4 W sr(-1) m(-2) and a maximum external quantum efficiency of 0.72%, comparable with earlier lead-based devices. Increasing the bromide content in these tin perovskite devices widens the semiconductor bandgap and leads to shorter wavelength emissions, tunable down to 667 nm. These near-infrared LEDs could find useful applications in a range of optical communication, sensing and medical device applications.

Sensitivity of the Magnetic Properties of the ZnCr2O4 and MgCr2O4 Spinels to Nonstoichiometry

We report that small amounts of metal atom non-stoichiometry are possible in the ZnCr2O4 and MgCr2O4 spinels. The non-stoichiometry, though less than 2%, significantly impacts TN and the nature of the magnetic correlations above TN. The Zn1+xCr2-xO4 spinel is particularly sensitive. While stoichiometric ZnCr2O4 displays antiferromagnetic short range correlations in the susceptibility above TN, ferromagnetic correlations are observed in non-stoichiometric, hole doped Zn1+xCr2-xO4. The Mg1+xCr2-xO4 spinels are less profoundly affected by non-stoichiometry, though significant changes are also observed. We contrast the magnetic properties of Zn1+xCr2-xO4 and Mg1+xCr2-xO4 (x=0, 0.02, 0.04) with those of materials with the equivalent amounts of isovalent non-magnetic Ga3+ substituted on the Cr3+ site to separate the effects of static site disorder and hole doping.

Thin, Flexible Supercapacitors Made from Carbon Nanofiber Electrodes Decorated at Room Temperature with Manganese Oxide Nanosheets

We report the fabrication and electrochemical performance of a flexible thin film supercapacitor with a novel nanostructured composite electrode. The electrode was prepared by in situ coprecipitation of two-dimensional (2D) MnO2 nanosheets at room temperature in the presence of carbon nanofibers (CNFs). The highest specific capacitance of 142 F/g was achieved for CNFs-MnO2 electrodes in sandwiched assembly with PVA-H4SiW12O40nH2O polyelectrolyte separator.

Use of in situ neutron diffraction to monitor high-temperature, solid/H2-gas reactions

For the first time, the chemistry in H(2) gas of a perovskite-like material, Pr(2)Sr(2)CrNiO(8), has been monitored at temperatures up to approximately 700 degrees C, in situ, by neutron powder diffraction.

Spin-flop and antiferromagnetic phases of the ferromagnetic half-twist ladder compounds Ba3Cu3In4O12 and Ba3Cu3Sc4O12.

The title compounds have dominant ferromagnetic exchange interactions within one-dimensional (1D) half-twist ladders of s = 1/2 Cu(2+) ions and antiferromagnetic (AFM) interactions between ladders, leading to ordered 3D phases at temperatures below 20 K. Here we show that a microscopic 1D model of the paramagnetic (PM) phase combined with a phenomenological model based on sublattice magnetization describes the observed temperature and field dependent magnetism. The model identifies AFM, spin-flop and PM phases whose boundaries have sharp features in the experimental magnetization M(T,H) and specific heat C(P)(T,H). Exact diagonalization of the 1D model, possible for 24 spins due to special structural features of half-twist ladders, yields the magnetization and spin susceptibility of the PM phase. AFM interactions between ladders are included at the mean-field level using the field, H(AF), obtained from modelling the ordered phases. Isotropic exchange J1 =- 135 K and g-tensor g = 2.1 within ladders, plus exchange and anisotropy fields H(AF) and H(A), describe the ordered phases and are almost quantitative for the PM phase.

Dominant ferromagnetism in the spin-1/2 half-twist ladder 334 compounds, Ba3Cu3In4O12 and Ba3Cu3Sc4O12.

The magnetic properties of polycrystalline samples of Ba(3)Cu(3)In(4)O(12) (In-334) and Ba(3)Cu(3)Sc(4)O(12) (Sc-334) are reported. Both 334 phases have a structure derived from perovskite, with CuO(4) squares interconnected to form half-twist ladders along the c-axis. The Cu-O-Cu angles, ~90°, and the positive Weiss temperatures indicate the presence of significant ferromagnetic (FM) interactions along the Cu ladders. At low temperatures, T < 20 K, sharp transitions in the magnetic susceptibility and heat capacity measurements indicate three-dimensional (3D) antiferromagnetic (AFM) ordering at T(N). T(N) is suppressed on application of a field and a complex magnetic phase diagram with three distinct magnetic regimes below the upper critical field can be inferred from our measurements. The magnetic interactions are discussed in relation to a modified spin-1/2 FM-AFM model and the 334 half-twist ladder is compared to other two-rung ladder spin-1/2 systems.