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Mercouri G. Kanatzidis

Publications and source records attributed to Mercouri G. Kanatzidis.

At least 55 records · Page 3Linked to original sources

Pressure-temperature phase diagram of EuRbFe$_4$As$_4$ superconductor

The pressure dependencies of the magnetic and superconducting transitions, as well as that of the superconducting upper critical field are reported for single crystalline EuRbFe$_4$As$_4$. Resistance measurements were performed under hydrostatic pressures up to 6.21 GPa and in magnetic fields up to 9 T. Zero-field-cool magnetization measurements were performed under hydrostatic pressures up to 1.24 GPa under 20 mT applied field. Superconducting transition temperature, $T_\text c$, up to 6.21 GPa and magnetic transition temperature, $T_\text M$, up to 1.24 GPa were obtained and a pressure-temperature phase diagram was constructed. Our results show that $T_\text c$ is monotonically suppressed upon increasing pressure. $T_\text M$ is linearly increased up to 1.24 GPa. For the studied pressure range, no signs of the crossing of $T_\text M$ and $T_\text c$ lines are observed. The normalized slope of the superconducting upper critical field is gradually suppressed with increasing pressure, which may be due to the continuous change of Fermi-velocity $v_F$ with pressure.

cond-mat.supr-con↗

Ultrafast correlated charge and lattice motion in a hybrid metal halide perovskite

Hybrid organic-inorganic halide perovskites have shown remarkable optoelectronic properties (1-3), believed to originate from correlated motion of charge carriers and the polar lattice forming large polarons (4-7). Few experimental techniques are capable of probing these correlations directly, requiring simultaneous sub-meV energy and femtosecond temporal resolution after absorption of a photon (8). Here we use transient multi-THz spectroscopy, sensitive to the internal motions of charges within the polaron, to temporally and energetically resolve the coherent coupling of charges to longitudinal optical phonons in single crystal CH3NH3PbI3 (MAPI). We observe room temperature quantum beats arising from the coherent displacement of charge from the coupled phonon cloud. Our measurements provide unambiguous evidence of the existence of polarons in MAPI.

cond-mat.mtrl-sci↗

Phonon-pump electronic-probe study of methylammonium lead iodide reveals electronically decoupled organic and inorganic sublattices

Organic-inorganic hybrid perovskites such as methylammonium lead iodide (CH3NH3PbI3) are game-changing semiconductors for solar cells and light-emitting devices owing to their exceptionally long carrier lifetime and diffusion length. Determining whether the large dipole moment of the organic cation and dynamic disorder benefit the optoelectronic properties of CH3NH3PbI3 has been an outstanding challenge. Herein, via transient absorption measurements employing an infrared pump pulse tuned to a methylammonium vibration, we observe slow, nanosecond-long thermal dissipation from the selectively excited organic mode to the entire lattice. Resulting transient electronic signatures, during the period of thermal-nonequilibrium when the induced thermal motions are mostly concentrated on the organic sublattice, reveal that induced motions of the organic cations do not alter absorption or photoluminescence response of CH3NH3PbI3, beyond thermal effects. Our results suggest that the attractive optoelectronic properties of CH3NH3PbI3 mainly derive from the inorganic lead-halide framework.

cond-mat.mtrl-sci↗

Detection of Rashba spin splitting in 2D organic-inorganic perovskite via precessional carrier spin relaxation

The strong spin-orbit interaction in the organic-inorganic perovskites tied to the incorporation of heavy elements (\textit{e.g.} Pb, I) makes these materials interesting for applications in spintronics. Due to a lack of inversion symmetry associated with distortions of the metal-halide octahedra, the Rashba effect (used \textit{e.g.} in spin field-effect transistors and spin filters) has been predicted to be much larger in these materials than in traditional III-V semiconductors such as GaAs, supported by the recent observation of a near record Rashba spin splitting in CH$_3$NH$_3$PbBr$_3$ using angle-resolved photoemission spectroscopy (ARPES). More experimental studies are needed to confirm and quantify the presence of Rashba effects in the organic-inorganic perovskite family of materials. Here we apply time-resolved circular dichroism techniques to the study of carrier spin dynamics in a 2D perovskite thin film [(BA)$_2$MAPb$_2$I$_7$; BA = CH$_3$(CH$_2$)$_3$NH$_3$, MA = CH$_3$NH$_3$]. Our findings confirm the presence of a Rashba spin splitting via the dominance of precessional spin relaxation induced by the Rashba effective magnetic field. The size of the Rashba spin splitting in our system was extracted from simulations of the measured spin dynamics incorporating LO-phonon and electron-electron scattering, yielding a value of 10 meV at an electron energy of 50 meV above the band gap, representing a 20 times larger value than in GaAs quantum wells.

cond-mat.mtrl-sci↗

In-Plane Mechanical Properties of Ultrathin 2D Hybrid Organic-Inorganic Perovskites

Two-dimensional (2D) hybrid organic-inorganic perovskites (HOIPs) are new members of the 2D materials family with wide tunability, highly dynamic structural features and excellent physical properties. Ultrathin 2D HOIPs and their heterostructures with other 2D materials have been exploited for study of new physical phenomena and novel device applications. The in-plane mechanical properties of 2D ultrathin HOIPs are critical for understanding the coupling between mechanical and other physical fields and for integrated devices applications. Here we report for the first time the in-plane mechanical properties of ultrathin freestanding 2D lead iodide perovskite membranes and their dependence on the membrane thickness. The in-plane Young's moduli of 2D HOIPs are smaller than that of conventional covalently bonded 2D materials. Both the Young's modulus and breaking strength first decrease and then plateau as the thickness increases from monolayer to 4 layers due to interlayer slippage during deformation. Our results show that ultrathin 2D HOIPs exhibit outstanding breaking strength/Young's Modulus ratio compared to many other widely used engineering materials and polymeric flexible substrates, which renders them suitable for application into flexible electronic devices.

cond-mat.mtrl-sci↗

Out-of-Plane Mechanical Properties of 2D Hybrid Organic-Inorganic Perovskites by Nanoindentation

2D layered hybrid organic-inorganic perovskites (HOIPs) have demonstrated improved stability and promising photovoltaic performance. The mechanical properties of such functional materials are both fundamentally and practically important to achieve both high performance and mechanical stable (flexible) devices. Here we report the mechanical properties of a series of 2D layered lead iodide HOIPs and investigate the role of structural sub-units (e.g., variation of the length of the organic spacer molecules -R and the number of inorganic layer -n) on the mechanical properties. While 2D HOIPs have much lower nominal elastic moduli and hardness than 3D HOIPs, larger n number and shorter R lead to stiffer materials. DFT simulations showed a similar trend to the experimental results. We compared these findings with other 2D layered crystals and shed light on routes to further tune the out-of-plane mechanical properties of 2D layered HOIPs.

cond-mat.mtrl-sci↗

Emphanitic anharmonicity in PbSe at high temperature and the anomalous electronic properties in the PbQ (Q=S, Se, Te) system

The temperature dependence of the local structure of PbSe has been investigated using pair distribution function (PDF) analysis of x-ray and neutron powder diffraction data and density functional theory (DFT) calculations. Observation of non-Gaussian PDF peaks at high temperature indicates the presence of significant anharmonicity, which can be modeled as Pb off-centering along [100] directions that grows on warming similar to the behavior seen in PbTe and PbS and sometimes called emphanisis. Interestingly, the emphanitic response is smaller in PbSe than in both PbS and PbTe indicating a non-monotonic response with chalcogen atomic number in the PbQ (Q=S, Se, Te) series. The DFT calculations indicate a correlation between band gap and the amplitude of [100] dipolar distortion, suggesting that emphanisis may be behind the anomalous composition and temperature dependencies of the band gaps in this series.

cond-mat.mtrl-sci↗

Spin Quenching Assisted by a Strongly Anisotropic Compression Behavior in MnP

We studied the crystal structure and spin state of MnP under high pressure with synchrotron X-ray diffraction and X-ray emission spectroscopy. MnP has an exceedingly strong anisotropy in compressibility, with the primary compressible direction along the b axis of the Pnma structure. X-ray emission spectroscopy reveals a pressure-driven quenching of the spin state in MnP. Firstprinciples calculations suggest that the strongly anisotropic compression behavior significantly enhances the dispersion of the Mn d-orbitals and the splitting of the d orbital levels compared to the hypothetical isotropic compression behavior. Thus, we propose spin quenching results mainly from the significant enhancement of the itinerancy of d electrons and partly from spin rearrangement occurring in the split d-orbital levels near the Fermi level. This explains the fast suppression of magnetic ordering in MnP under high pressure. The spin quenching lags behind the occurrence of superconductivity at ~8 GPa implying that spin fluctuations govern the electron pairing for superconductivity.

cond-mat.supr-con↗

Lattice thermal transport in group II-alloyed PbTe

PbTe, one of the most promising thermoelectric materials, has recently demonstrated thermoelectric figure of merit ($ZT$) of above 2.0 when alloyed with group II elements. The improvements are due mainly to significant reduction of lattice thermal conductivity ($κ_{l}$), which was in turn attributed to nanoparticle precipitates. However, a fundamental understanding of various phonon scattering mechanisms within the bulk alloy is still lacking. In this work, we apply the newly-developed density-functional-theory (DFT)-based compressive sensing lattice dynamics (CSLD) approach to model lattice heat transport in PbTe, MTe, and Pb$_{0.94}$M$_{0.06}$Te (M=Mg, Ca, Sr and Ba), compare our results with experimental measurements, with focus on strain effect and mass disorder scattering. We find that (1) CaTe, SrTe and BaTe in the rock-salt structure exhibit much higher $κ_{l}$ than PbTe, while MgTe in the same structure shows anomalously low $κ_{l}$; (2) lattice heat transport of PbTe is extremely sensitive to static strain induced by alloying atoms in solid solution form; (3) mass disorder scattering plays a major role in reducing $κ_{l}$ for Mg/Ca/Sr-alloyed PbTe through strongly suppressing the lifetimes of intermediate- and high-frequency phonons, while for Ba-alloyed PbTe, precipitated nanoparticles are also important.

cond-mat.mtrl-sci↗

Correlated local dipoles in PbTe

We present a combined single-crystal x-ray diffuse scattering and ab-initio molecular dynamics study of lead telluride, PbTe. Well-known for its thermoelectric and narrow-gap semiconducting properties, PbTe recently achieved further notoriety following the report of an unusual off-centering of the lead atoms, accompanied by a local symmetry breaking, on heating. This observation, which was named emphanisis, ignited considerable controversy regarding the details of the underlying local structure and the appropriate interpretation of the total scattering experiments. In this study, we demonstrate close agreement between our diffuse scattering measurements and our calculations, which allows us to analyze features such as higher-order correlations that are accessible in the simulations but not experimentally. This allowed us to discover an unusual correlated local dipole formation extending over several unit cells with an associated local reduction of the cubic symmetry in both our x-ray diffuse scattering measurements and our molecular dynamics simulations. Importantly, when averaged spatially or temporally, the most probable positions for the ions are at the centers of their coordination polyhedra. Our results therefore clarify the nature of the local symmetry breaking, and reveal the source of the earlier controversy regarding the existence or absence of off-centering. Finally, we provide an interpretation of the behavior in terms of coupled soft optical and acoustic modes, which is linked also to the high thermoelectric performance of PbTe.

cond-mat.mtrl-sci↗

Changes in charge density vs changes in formal oxidation states: The case of Sn halide perovskites and their ordered vacancy analogues

Shifting the Fermi energy in solids by doping, defect formation or gating generally results in changes in the charge density distribution, which reflect the ability of the bonding pattern in solids to adjust to such external perturbations. In the ionic limit, such changes are described by the formal oxidation states (FOS) whereby a single atom type is presumed to absorb the full burden of the perturbation (change in charge) of the whole compound. In this picture, when the solar absorber CsSnI3 loses 50 % of its Sn atoms thereby forming the ordered vacancy compound Cs2SnI6, the Sn is said to change from Sn2+ to Sn4+. In reality, the charge redistribution is more complex. To understand the electronic properties of these two groups and to gauge the trends in s-electron charge on the nucleus, we studied the 113/216 compound pairs CsSnCl3/Cs2SnCl6; CsSnBr3/Cs2SnBr6, and CsSnI3/Cs2SnI6. We have calculated the electronic structure of these three compound pairs, complementing them by CsSnF3/Cs2SnF6 in the hypothetical cubic structure for completing the chemical trends. These materials were also synthesized by chemical routes and characterized by X-ray diffraction, Mossbauer spectroscopy and K-edge X-ray Absorption Spectroscopy. We find that in going from 113 to 216 there is a decrease in the s charge on Sn, in agreement with the FOS picture. However, at the same time, we observe an increase of the p charge via downshift of the otherwise unoccupied p level, an effect that tends to replenish much of the lost s charge. This effect is theoretically explained as a self-regulating response [H. Raebiger, S. Lany, and A. Zunger, Nature 453, 763 (2008)] whereby the system re-hybridizes to minimize the effect of the charge perturbation created by vacancy formation. Our work clarifies the relation between FOS and charge transfer that can be applied to a wide variety of materials.

cond-mat.mtrl-sci↗

Local polar fluctuations in lead halide perovskite crystals

Hybrid lead-halide perovskites have emerged as an excellent class of photovoltaic materials. Recent reports suggest that the organic molecular cation is responsible for local polar fluctuations that inhibit carrier recombination. We combine low frequency Raman scattering with first-principles molecular dynamics (MD) to study the fundamental nature of these local polar fluctuations. Our observations of a strong central peak in both hybrid (CH$_3$NH$_3$PbBr$_3$) and all-inorganic (CsPbBr$_3$) lead-halide perovskites show that anharmonic, local polar fluctuations are intrinsic to the general lead-halide perovskite structure, and not unique to the dipolar organic cation. MD simulations show that head-to-head Cs motion coupled to Br face expansion, on a few hundred femtosecond time scale, drives the local polar fluctuations in CsPbBr$_3$.

cond-mat.mtrl-sci↗

Enhanced Structural Stability and Photo Responsiveness of CH3NH3SnI3 Perovskite via Pressure-Induced Amorphization and Recrystallization

An organic-inorganic halide perovskite of CH3NH3SnI3 with significantly improved structural stability is obtained via pressure-induced amorphization and recrystallization. In situ high-pressure resistance measurements reveal an increased electrical conductivity by 300% in the pressure-treated perovskite. Photocurrent measurements also reveal a substantial enhancement in visible-light responsiveness. The mechanism underlying the enhanced properties is demonstrated to be associated with the improved structural stability.

cond-mat.mtrl-sci↗

(CaO)(FeSe): A Layered Wide Gap Oxychalcogenide Semiconductor

A new iron-oxychalcogenide (CaO)(FeSe) was obtained which crystallizes in the orthorhombic space group Pnma (No. 62) with a = 5.9180(12) Å, b = 3.8802(8) Å, c = 13.193(3) Å. The unique structure of (CaO)(FeSe) is built up of a quasi-two-dimensional network of corrugated infinite layers of corner-shared FeSe2O2 tetrahedra that extend in the ab-plane. The corrugated layers composed of corner-shared FeSe2O2 tetrahedra stack along the c-axis with Ca2+ cations sandwiched between the layers. Optical spectroscopy and resistivity measurements reveal semiconducting behavior with an indirect optical band gap of around 1.8 eV and an activation energy of 0.19(1) eV. Electronic band structure calculations at the density function level predict a magnetic configuration as ground state and confirm the presence of an indirect wide gap in (CaO)(FeSe).

cond-mat.mtrl-sci↗

La1-xBi1+xS3 (x~0.08): An n-Type Semiconductor

The new bismuth chalcogenide La0.92Bi1.08S3 crystallizes in the monoclinic space group C2/m with a = 28.0447(19) Å, b = 4.0722(2) Å, c = 14.7350(9) Å, and $β$ = 118.493(5)°. The structure of La0.92Bi1.08S3 is built up of NaCl-type Bi2S5 blocks, and BiS4 and LaS5 infinitely long chains forming a compact three-dimensional framework with parallel tunnels. Optical spectroscopy and resistivity measurements reveal a semiconducting behavior with a band gap of ~ 1 eV and activation energy for transport of 0.36(1) eV. Thermopower measurements suggest the majority carriers of La0.92Bi1.08S3 are electrons. Heat capacity measurements indicate no phase transitions from 2 to 300 K. Band structure calculations at the density functional theory level confirm the semiconducting nature and the indirect gap of La0.92Bi1.08S3.

cond-mat.mtrl-sci↗

Intrinsic femtosecond charge generation dynamics in a single crystal organometal halide perovskite

Hybrid metal-organic perovskite solar cells have astounded the solar cell community with their rapid rise in efficiency over the past three years. Despite this success, the basic processes governing the photogeneration of free charges, particularly their dynamics and efficiency, remain unknown. Here we use ultrabroadband pulses of THz frequency light to see the intrinsic photophysical properties of single crystal lead halide perovskite just femtoseconds after a photon is first absorbed. Our spectra reveal the dynamics and efficiencies of free charge creation, the remarkable ease in which they move through the lattice and the complicated interplay between free and bound charges in these materials.

cond-mat.mtrl-sci↗

Nanoscale $β$-Nuclear Magnetic Resonance Depth Imaging of Topological Insulators

Considerable evidence suggests that variations in the properties of topological insulators (TIs) at the nanoscale and at interfaces can strongly affect the physics of topological materials. Therefore, a detailed understanding of surface states and interface coupling is crucial to the search for and applications of new topological phases of matter. Currently, no methods can provide depth profiling near surfaces or at interfaces of topologically inequivalent materials. Such a method could advance the study of interactions. Herein we present a non-invasive depth-profiling technique based on $β$-NMR spectroscopy of radioactive $^8$Li$^+$ ions that can provide "one-dimensional imaging" in films of fixed thickness and generates nanoscale views of the electronic wavefunctions and magnetic order at topological surfaces and interfaces. By mapping the $^8$Li nuclear resonance near the surface and 10 nm deep into the bulk of pure and Cr-doped bismuth antimony telluride films, we provide signatures related to the TI properties and their topological non-trivial characteristics that affect the electron-nuclear hyperfine field, the metallic shift and magnetic order. These nanoscale variations in $β$-NMR parameters reflect the unconventional properties of the topological materials under study, and understanding the role of heterogeneities is expected to lead to the discovery of novel phenomena involving quantum materials.

cond-mat.mtrl-sci↗

Understanding Bulk Defects in Topological Insulators from Nuclear-Spin Interactions

Non-invasive local probes are needed to characterize bulk defects in binary and ternary chalcogenides. These defects contribute to the non-ideal behavior of topological insulators. We have studied bulk electronic properties via $^{125}$Te NMR in Bi$_2$Te$_3$, Sb$_2$Te$_3$, Bi$_{0.5}$Sb$_{1.5}$Te$_3$, Bi$_2$Te$_2$Se and Bi$_2$Te$_2$S. A distribution of defects gives rise to asymmetry in the powder lineshapes. We show how the Knight shift, line shape and spin-lattice relaxation report on carrier density, spin-orbit coupling and phase separation in the bulk. The present study confirms that the ordered ternary compound Bi$_2$Te$_2$Se is the best TI candidate material at the present time. Our results, which are in good agreement with transport and ARPES studies, help establish the NMR probe as a valuable method to characterize the bulk properties of these materials.

cond-mat.mtrl-sci↗