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Daniel B. Straus

Publications and source records attributed to Daniel B. Straus.

9 recordsLinked to original sources

Chirality Transfer to the Magnetic Sublattice in the Hybrid Perovskite (R)-/(S)-3-Fluoropyrrolidinium Copper(II) Chloride

Incorporating chiral organic cations into organic-inorganic hybrid materials has been shown to enable the inorganic sublattice to display chiroptical properties. We report a new two-dimensional magnetic ($S=1/2$) chiral metal halide perovskite, (R)- and (S)-$(C_4H_9FN)_2CuCl_4$ (where $(C_4H_9FN)^+$ is 3-fluoropyrrolidinium), which consists of Cu-Cl inorganic layers separated by $(C_4H_9FN)^+$ organic cations. The presence of the chiral $(C_4H_9FN)^+$ organic cation induces formation of chiral magnetic order, even though the inorganic sublattice itself is nearly structurally centrosymmetric. We also report the racemic variant, containing an equal amount of (R)- and (S)- cations, which shows no evidence of chiral magnetic order. When the magnetic susceptibility is measured perpendicular to inorganic Cu-Cl layer propagation direction, an antiferromagnetic phase transition at N\'eel temperature $T_N = 2.23~K$ is observed in both the chiral and racemic materials, and the existence of the magnetic phase transition is supported by specific heat capacity measurements. Field-induced magnetic chirality is observed through the existence of a second-order magnetoelectric effect in the chiral variant, while no magnetoelectric signal is observed for the racemic material, indicating the absence of magnetic chirality. Our findings demonstrate that materials exhibiting chiral magnetic order can be created through the incorporation of a chiral cation into an organic-inorganic hybrid magnetic material, potentially allowing for the design of tailored materials that combine chiral magnetism with other desirable optical and electronic properties that come from structural chirality.

cond-mat.mtrl-sci

Antiferromagnetic Order in the Rare Earth Halide Perovskites CsEuBr$_3$ and CsEuCl$_3$

Bulk CsEuBr$_3$ and CsEuCl$_3$ are experimentally shown to be magnetic semiconductors that order antiferromagnetically at Neel temperatures of 2.0 K and 1.0 K respectively. Given that nanoparticles and thin films of CsEuCl$_3$ have been reported to order ferromagnetically at a similar temperature, our observation of antiferromagnetic ordering in CsEuBr$_3$ and CsEuCl$_3$ expands the possible applications of halide perovskites to now include spintronic devices where both ferromagnetic and antiferromagnetic devices can be fabricated from a single material. The conclusion that CsEuCl$_3$ can be used as a switchable magnetic material is also supported by our density-functional theory calculations.

cond-mat.mtrl-sci

Magnetic-cations doped into a Double Perovskite Semiconductor

We report two solid solutions based on magnetic ion doping of the double perovskite oxide Sr2GaSbO6: Sr2Ga1-xCrxSbO6 (0.1 < x < 0.4) and Sr2Ga1-xFexSbO6 (0.1 < x < 0.4). All compositions crystallize in the same space group (I4/m) as their undoped parent phase Sr2GaSbO6, with the trivalent magnetic cations Cr3+ or Fe3+ partially substituting for non-magnetic Ga3+ in one of the B-cation sites. The Cr- and Fe-doped phases display dominant antiferromagnetic coupling among the dopant magnetic moments, and exhibit decreasing band gaps with increasing substitution level.

cond-mat.mtrl-sci

Photophysics of Two-Dimensional Semiconducting Organic-Inorganic Metal-Halide Perovskites

2D organic-inorganic hybrid perovskites (2DHPs) consist of alternating anionic metal-halide and cationic organic layers. They have widely tunable structural and optical properties. We review the role of the organic cation in defining the structural and optical properties of 2DHPs through example lead iodide 2DHPs. Even though excitons reside in the metal halide layers, the organic and inorganic frameworks cannot be separated-they must be considered as a single unit to fully understand the photophysics of 2DHPs. We correlate cation-induced distortion and disorder in the inorganic lattice with the resulting optical properties. We also discuss the role of the cation in creating and altering the discrete excitonic structure that appears at cryogenic temperatures in some 2DHPs, including the cation-dependent presence of hot exciton photoluminescence. We conclude our review with an outlook for 2DHPs, highlighting existing gaps in fundamental knowledge as well as potential future applications.

cond-mat.mtrl-sci

Ferromagnetic Double Perovskite Semiconductors with Tunable Properties

We successfully dope the magnetically silent double perovskite semiconductor Sr2GaSbO6 to induce ferromagnetism and tune its band gap, with Ga3+ partially substituted by the magnetic trivalent cation Mn3+, in a rigid cation ordering with Sb5+. Our new ferromagnetic semiconducting Sr2Ga1-xMnxSbO6 double perovskite, which crystallizes in tetragonal symmetry (space group I4/m) and has tunable ferromagnetic ordering temperature and band gap, suggests that magnetic ion doping of double perovskites is a productive avenue towards obtaining materials for application in next-generation oxide-based spintronic devices.

cond-mat.mtrl-sci

Widely Spaced Planes of Magnetic Dimers in the Ba6Y2Rh2Ti2O17-δ Hexagonal Perovskite

We report the synthesis and initial characterization of Ba6Y2Rh2Ti2O17-δ, a previously unreported material with a hexagonal symmetry structure. Face-sharing RhO6 octahedra form triangular planes of Rh2O9 dimers that are widely separated in the perpendicular direction. The material displays a small effective magnetic moment, due to the Rh ions present, and a negative Curie-Weiss temperature. The charge transport and optical band gaps are very similar, near 0.16 eV. A large upturn in the heat capacity at temperatures below 1 K, suppressed by applied magnetic fields larger than {μ0H = 2 Tesla, is observed. A large T-linear term in the specific heat (γ=166 mJ/mol f.u-K2) is seen, although the material is insulating at low temperatures. These results suggest the possibility of a spin liquid ground state in this material.

cond-mat.str-el

Understanding the Instability of the Halide Perovskite CsPbI$_3$ through Temperature-Dependent Structural Analysis

Despite the tremendous interest in halide perovskites in solar cells, the reason that the all-inorganic perovskite CsPbI$_3$ is unstable at room temperature remains mysterious. Here single-crystal X-ray diffraction and powder pair distribution function (PDF) measurements characterize bulk perovskite CsPbI$_3$ from 100 to 295 K to elucidate its thermodynamic instability. While Cs occupies a single site from 100 to 150 K, it splits between two sites from 175 to 295 K with the second site having a lower effective coordination number, which along with other structural parameters suggests that Cs rattles in its coordination polyhedron. PDF measurements reveal that on the length scale of the unit cell, the Pb-I octahedra concurrently become greatly distorted, with one of the I-Pb-I angles approaching 82° compared to the ideal 90°. The rattling of Cs, low number of Cs-I contacts, and high degree of octahedral distortion cause the instability of perovskite-phase CsPbI$_3$. These results provide detailed structural information that may help to engineer greater stability of CsPbI$_3$ and other all-inorganic perovskites for use in solar cells.

cond-mat.mtrl-sci

Tailoring Hot Exciton Dynamics in 2D Hybrid Perovskites through Cation Modification

We report a family of two-dimensional hybrid perovskites (2DHPs) based on phenethylammonium lead iodide ((PEA)$_2$PbI$_4$) that show complex structure in their low-temperature excitonic absorption and photoluminescence (PL) spectra as well as hot exciton PL. We replace the 2-position (ortho) H on the phenyl group of the PEA cation with F, Cl, or Br to systematically increase the cation's cross-sectional area and mass and study changes in the excitonic structure. These single atom substitutions substantially change the observable number of and spacing between discrete resonances in the excitonic absorption and PL spectra and drastically increase the amount of hot exciton PL that violates Kasha's rule by over an order of magnitude. To fit the progressively larger cations, the inorganic framework distorts and is strained, reducing the Pb-I-Pb bond angles and increasing the 2DHP band gap. Correlation between the 2DHP structure and steady-state and time-resolved spectra suggests the complex structure of resonances arises from one or two manifolds of states, depending on the 2DHP Pb-I-Pb bond angle (as)symmetry, and the resonances within a manifold are regularly spaced with an energy separation that decreases as the mass of the cation increases. The uniform separation between resonances and the dynamics that show excitons can only relax to the next-lowest state are consistent with a vibronic progression caused by a vibrational mode on the cation. These results demonstrate that simple changes to the structure of the cation can be used to tailor the properties and dynamics of the confined excitons without directly modifying the inorganic framework.

physics.app-ph

Kinetically Stable Single Crystals of Perovskite-Phase CsPbI${_3}$

We use solid-state methods to synthesize single crystals of perovskite-phase cesium lead iodide ($γ$-CsPbI3) that are kinetically stable at room temperature. Single crystal X-ray diffraction characterization shows that the compound is orthorhombic with the GdFeO3 structure at room temperature. Unlike conventional semiconductors, the optical absorption and the joint density-of-states of bulk $γ$-CsPbI3 is greatest near the band edge and decreases beyond Eg for at least 1.9 eV. Bulk $γ$-CsPbI3 does not show an excitonic resonance and has an optical band gap of 1.63(3) eV, ~90 meV smaller than has been reported in thin films; these and other differences indicate that previously-measured thin film $γ$-CsPbI3 shows signatures of quantum confinement. By flowing gases over $γ$-CsPbI3 during in situ powder X-ray diffraction measurements, we confirm that $γ$-CsPbI3 is stable to oxygen but rapidly and catalytically converts to non-perovskite $δ$-CsPbI3 in the presence of moisture. Our results on bulk $γ$-CsPbI3 provide vital parameters for theoretical and experimental investigations into perovskite-phase CsPbI3 that will the guide the design and synthesis of atmospherically stable inorganic halide perovskites.

physics.app-ph