Stereochemically Active Lone Pair Leads to Birefringence in the Vacancy Ordered Cs3Sb2Cl9 Perovskite Single Crystals.

Stereochemically active lone pair (SCALP) cations are attractive units for realizing optical anisotropy. Antimony(III) chloride perovskites with the SCALP have remained largely unknown to date. We synthesized a new vacancy ordered Cs3Sb2Cl9 perovskite single crystals with SbCl6 octahedral linkage containing the SCALP. Remarkably, all-inorganic halide perovskite Cs3Sb2Cl9 single crystals exhibit an exceptional birefringence of 0.12 ± 0.01 at 550 nm. The SCALP brings a large local structural distortion of the SbCl6 octahedra promoting birefringence optical responses in Cs3Sb2Cl9 single crystals. Theoretical calculations reveal that the considerable hybridization of Sb 5s and 5p with Cl 3p states largely contribute to the SCALP. Furthermore, the change in the Sb-Cl-Sb bond angle creates distortion in the SbCl6 octahedral arrangement in the apical and equatorial directions within the crystal structure incorporating the required anisotropy for the birefringence. This work explores pristine inorganic halide perovskite single crystals as a potential birefringent material with prospects in integrated optical devices.

Modulation-doping a correlated electron insulator.

Correlated electron materials (CEMs) host a rich variety of condensed matter phases. Vanadium dioxide (VO2) is a prototypical CEM with a temperature-dependent metal-to-insulator (MIT) transition with a concomitant crystal symmetry change. External control of MIT in VO2-especially without inducing structural changes-has been a long-standing challenge. In this work, we design and synthesize modulation-doped VO2-based thin film heterostructures that closely emulate a textbook example of filling control in a correlated electron insulator. Using a combination of charge transport, hard X-ray photoelectron spectroscopy, and structural characterization, we show that the insulating state can be doped to achieve carrier densities greater than 5 × 1021 cm-3 without inducing any measurable structural changes. We find that the MIT temperature (TMIT) continuously decreases with increasing carrier concentration. Remarkably, the insulating state is robust even at doping concentrations as high as ~0.2 e-/vanadium. Finally, our work reveals modulation-doping as a viable method for electronic control of phase transitions in correlated electron oxides with the potential for use in future devices based on electric-field controlled phase transitions.

Realizing the Lowest Bandgap and Exciton Binding Energy in a Two-Dimensional Lead Halide System.

Finding stable analogues of three-dimensional (3D) lead halide perovskites has motivated the exploration of an ever-expanding repertoire of two-dimensional (2D) counterparts. However, the bandgap and exciton binding energy in these 2D systems are generally considerably higher than those in 3D analogues due to size and dielectric confinement. Such quantum confinements are most prominently manifested in the extreme 2D realization in (A)mPbI4 (m = 1 or 2) series of compounds with a single inorganic layer repeat unit. Here, we explore a new A-site cation, 4,4'-azopyridine (APD), whose size and hydrogen bonding properties endow the corresponding (APD)PbI4 2D compound with the lowest bandgap and exciton binding energy of all such compounds, 2.19 eV and 48 meV, respectively. (APD)PbI4 presents the first example of the ideal Pb-I-Pb bond angle of 180°, maximizing the valence and conduction bandwidths and minimizing the electron and hole effective masses. These effects coupled with a significant increase in the dielectric constant provide an explanation for the unique bandgap and exciton binding energies in this system. Our theoretical results further reveal that the requirement of optimizing the hydrogen bonding interactions between the organic and the inorganic units provides the driving force for achieving the structural uniqueness and the associated optoelectronic properties in this system. Our preliminary investigations in characterizing photovoltaic solar cells in the presence of APD show encouraging improvements in performances and stability.

Elucidating Structure-Property Correlation in Perovskitoid and Antiperovskite Piperidinium Manganese Chloride.

In the world of semiconductors, organic-inorganic hybrid (OIH) halide perovskite is a new paradigm. Recently, a zealous effort has been made to design new lead-free perovskite-like OIH halides, such as perovskitoids and antiperovskites, for optoelectronic applications. In this context, we have synthesized a perovskitoid compound (Piperidinium)MnCl3 (compound 1) crystallizing in an orthorhombic structure with infinite one-dimensional (1D) chains of MnCl6 octahedra. Interestingly, this compound shows switchable dielectric property governed by an order-disorder structural transition. By controlling the stoichiometry of piperidine, we have synthesized an antiperovskite (Piperidinium)3Cl[MnCl4] (compound 2), the inverse analogue of a perovskite, consisting of zero-dimensional (0D) MnCl4 tetrahedra. This type of organic-inorganic hybrid antiperovskite halide is unique and scarce. Such a dissimilarity in lattice dimensionality and Mn2+ ion coordination ensues fascinating photophysical and magnetic properties. Compound 1 exhibits red emission with a photoluminescence quantum yield (PLQY) of ∼28%. On the other hand, the 0D antiperovskite compound 2 displays green emission with a higher PLQY of 54.5%, thanks to the confinement effect. In addition, the dimensionality of the compounds plays a vital role in the exchange interaction. As a result, compound 1 shows an antiferromagnetic ground state, whereas compound 2 is paramagnetic down to 1.8 K. This emerging structure-property relationship in OIH manganese halides will set the platform for designing new perovskites and antiperovskites.

Exploring Librational Pathways with on-the-Fly Machine-Learning Force Fields: Methylammonium Molecules in MAPbX3 (X = I, Br, Cl) Perovskites.

Two seemingly similar crystal structures of the low-temperature (∼100 K) MAPbX3 (X = I, Br, Cl) perovskites, but with different relative methylammonium (MA) ordering, have appeared as representatives of this orthorhombic phase. Distinguishing them by X-ray diffraction experiments is difficult, and conventional first-principles-based molecular dynamics approaches are often too computationally intensive to be feasible. Therefore, to determine the thermodynamically stable structure, we use a recently introduced on-the-fly machine-learning force field method, which reduces the computation time from years to days. The molecules exhibit a large degree of anharmonic motion depending on temperature: that is, rattling, twisting, and tumbling. We observe the crystal's "librational pathways" while slowly heating it in isothermal-isobaric simulations. Marked differences in the thermal evolution of structural parameters allow us to determine the real structure of the system via a comparison with experimentally determined crystal structures.

Band Gap Reduction in Ferroelectric BaTiO3 Through Heterovalent Cu-Te Co-Doping for Visible-Light Photocatalysis.

It is believed that ferroelectrics may serve as efficient photocatalysts as well as photovoltaic materials but for their large bandgaps which does not allow them to absorb a large part of the solar spectrum. We have explored theoretically within ab-initio density functional theory-based calculations, the efficacy of Cu and Te to co-dope BaTiO3 in reducing its bandgap while retaining its ferroelectric properties. Examining a dopant concentration of 11%, we find an insulating ground state being realized with a band gap reduction of 0.42 eV from the value for undoped BaTiO3 for some doping configurations. Ferroelectric distortions are found to survive even in the presence of doping suggesting possible applications in photocatalysis as well as photovoltaics.

Proximate Quantum Spin Liquid on Designer Lattice.

Complementary to bulk synthesis, here we propose a designer lattice with extremely high magnetic frustration and demonstrate the possible realization of a quantum spin liquid state from both experiments and theoretical calculations. In an ultrathin (111) CoCr2O4 slice composed of three triangular and one kagome cation planes, the absence of a spin ordering or freezing transition is demonstrated down to 0.03 K, in the presence of strong antiferromagnetic correlations in the energy scale of 30 K between Co and Cr sublattices, leading to the frustration factor of ∼1000. Persisting spin fluctuations are observed at low temperatures via low-energy muon spin relaxation. Our calculations further demonstrate the emergence of highly degenerate magnetic ground states at the 0 K limit, due to the competition among multiply altered exchange interactions. These results collectively indicate the realization of a proximate quantum spin liquid state on the synthetic lattice.

Contrasting Behaviors of FA and MA Cations in APbBr3.

It is known that the organic units in hybrid halide perovskites are free to rotate, but it is not clear if this freedom is of any relevance to the structure-property relationship of these compounds. We have employed quasi-elastic neutron scattering using two different spectrometers, thus providing a wide dynamic range to investigate the cation dynamics in methylammonium lead bromide (MAPbBr3) and formamidinium lead bromide (FAPbBr3) over a large temperature range covering all known crystallographic phases of these two compounds. Our results establish a plastic crystal-like phase forming above 30 K within the orthorhombic phase of MAPbBr3 related to 3-fold rotations of MA units around the C-N axis with an activation energy, Ea, of ∼27 meV, which has no counterpart in the FA compound. MA exhibits an additional 4-fold orientational motion of the whole molecule via rotation of the C-N axis itself with an Ea of ∼68 meV common for the high-temperature tetragonal and cubic phases. In contrast, the FA compound exhibits only an isotropic orientational motion of the whole FA unit with Ea ≈ 106 meV within the orthorhombic phase and a substantially reduced common Ea of ∼62 meV for the high-temperature tetragonal and cubic phases. Our results suggest that the rotational dynamics of the organic units, crystallographic phases, and physical properties of these compounds are intimately connected.

Signatures of a Spin-1/2 Cooperative Paramagnet in the Diluted Triangular Lattice of Y_{2}CuTiO_{6}.

We present a combination of thermodynamic and dynamic experimental signatures of a disorder driven dynamic cooperative paramagnet in a 50% site diluted triangular lattice spin-1/2 system: Y_{2}CuTiO_{6}. Magnetic ordering and spin freezing are absent down to 50 mK, far below the Curie-Weiss scale (-θ_{CW}) of ∼134 K. We observe scaling collapses of the magnetic field and temperature dependent magnetic heat capacity and magnetization data, respectively, in conformity with expectations from the random singlet physics. Our experiments establish the suppression of any freezing scale, if at all present, by more than 3 orders of magnitude, opening a plethora of interesting possibilities such as disorder stabilized long range quantum entangled ground states.

Realizing an Asymmetric Supercapacitor Employing Carbon Nanotubes Anchored to Mn3O4 Cathode and Fe3O4 Anode.

A facile route to anchor pseudocapacitive materials on multiwalled carbon nanotubes (CNTs) to realize high-performance electrode materials for asymmetric supercapacitors (ASCs) is reported. The anchoring process is developed after direct decomposition of metal-hexacyanoferrate complex on the CNT surface. Transmission electron microscopy (TEM) analysis reveals that the nanoparticles (NPs) are discretely attached over the CNT surface without forming a uniform layer, thus making most of the entire NP surface available for electrochemical reactions. Accordingly, CNT-Mn3O4 nanocomposite cathode shows significantly improved capacitive performance as compared to pristine CNT electrode, validating the efficacy of designing the composite electrode. With CNT-Fe3O4 nanocomposite as the paired anode, the hybrid ASC delivers a specific capacitance of 135.2 F/g at a scan rate of 10 mV/s within a potential window of 0-1.8 V in the aqueous electrolyte and retains almost 100% of its initial capacitance after 15,000 cycles. The serially connected ASCs can power commercial light-emitting diodes (LEDs) and mobile phones, reflecting their potential in next-generation storage applications.

Synthetic Control on Structure/Dimensionality and Photophysical Properties of Low Dimensional Organic Lead Bromide Perovskite.

Low dimensional lead halide perovskites have attracted huge research interest due to their structural diversity and remarkable photophysical properties. The ability to controllably change dimensionality/structure of perovskites remains highly challenging. Here, we report synthetic control on structure/dimensionality of ethylenediammonium (ED) lead bromide perovskite from a two dimensionally networked (2DN) sheet to a one dimensionally networked (1DN) chain structure. Intercalation of solvent molecules into the perovskite plays a crucial role in directing the final dimensionality/structure. This change in dimensionality reflects strongly in the observed differences in photophysical properties. Upon UV excitation, the 1DN structure emits white light due to easily formed " self-trapped" excitons. 2DN perovskites show band edge blue emission (∼410 nm). Interestingly, Mn2+ incorporated 2DN perovskites show a highly red-shifted Mn2+ emission peak at ∼670 nm. Such a long wavelength Mn2+ emission peak is unprecedented in the perovskite family. This report highlights the synthetic ability to control the dimensionality/structure of perovskite and consequently its photophysical properties.

Evolution of the Local Structure within Chromophoric Mn-O5 Trigonal Bipyramids in YMn1- xIn xO3 with Composition.

We have investigated the local environment around Mn3+ and In3+ ions in YMn1- xIn xO3 chromophores to understand the origin of the intense blue color for small values of x in these solid solutions. While X-ray diffraction results provide an average description of the trigonal bipyramidal (TBP) units about Mn/In atoms with five oxygens surrounding the cation, the X-ray absorption near edge structure (XANES) as well as extended X-ray absorption fine structure (EXAFS) of these materials clearly suggest the presence of two different TBP environments, one of which is similar to MnO5 TBP in YMnO3. EXAFS in conjunction with first-principles calculations show that replacing larger In3+ ions by smaller Mn3+ ones additionally gives rise to another TBP strongly distorted along the axial direction, expanding one of the axial Mn-O bonds by ∼11%. The relative fraction of these two environments changes in close agreement with the global stoichiometry with the elongated TBP, therefore, being dominant in the regime of the low Mn content. This local structural difference is responsible for the intense, but relatively narrow, absorption feature in the red-yellow region of the absorption spectrum, and hence YMn1- xIn xO3 appears blue for small Mn dopings. This distortion is relatively less abundant in Mn-rich compositions, and therefore, such compositions appear black, controlled by the wide absorption feature of the trigonal bipyramid coordination with Mn-O bond lengths that are essentially the same as those in YMnO3, covering the entire visible range. The chromophore properties are, thus, governed by the ratio of these two MnO5 TBP environments, one with a characteristic optical absorption giving it a blue color and the other absorbing over the entire visible range.

Why Does CuFeS2 Resemble Gold?

While several potential applications of CuFeS2 quantum dots have already been reported, doubts regarding their optical and physical properties persist. In particular, it is unclear if the quantum dot material is metallic, a degenerately doped semiconductor, or else an intrinsic semiconductor material. Here we examine the physical properties of CuFeS2 quantum dots in order to address this issue. Specifically, we study the bump that is observed in the optical spectra of these quantum dots at ∼500 nm. Using a combination of structural and optical characterization methods, ultrafast spectroscopy, as well as electronic structure calculations, we ascertain that the unusual purple color of CuFeS2 quantum dots as well the golden luster of CuFeS2 films arise from the existence of a plasmon resonance in these materials. While the presence of free carriers causes this material to resemble gold, surface treatments are also described to suppress the plasmon resonance altogether.

Suppression of the Coffee-Ring Effect and Evaporation-Driven Disorder to Order Transition in Colloidal Droplets.

The formation of a ring-like deposit at the periphery of a drying colloidal droplet is a vexing problem in many applications. We show a complete suppression of such deposits when a droplet of aqueous colloidal suspension, deposited on a glass substrate coated with a thin layer of silicone oil, is evaporated. This coating prevents the periphery of the aqueous droplet from getting pinned to the substrate and helps in suppressing the ring formation. It also decreases the surface area of the droplet, thereby decreasing the evaporation rate. These two factors together, driving the colloidal particles slowly to the center of the droplet, contribute to form an ordered crystallite at the end of the evaporation process. Brownian dynamics simulations performed to study ordering in the aggregate show that the spherical colloidal particles form face-centered cubic structures. Experiments and simulations show that slow rates of droplet evaporation and smaller-sized colloidal particles further lead to high-quality ordered colloidal crystallites.

Behavior of Methylammonium Dipoles in MAPbX3 (X = Br and I).

Dielectric constants of MAPbX3 (X = Br, I) in the 1 kHz-1 MHz range show strong temperature dependence near room temperature, in contrast to the nearly temperature-independent dielectric constant of CsPbBr3. This strong temperature dependence for MAPbX3 in the tetragonal phase is attributed to the MA+ dipoles rotating freely within the probing time scale. This interpretation is supported by ab initio molecular dynamics simulations on MAPbI3 that establish these dipoles as randomly oriented with a rotational relaxation time scale of ∼7 ps at 300 K. Further, we probe the intriguing possibility of transient polarization of these dipoles following a photoexcitation process with important consequences on the photovoltaic efficiency, using a photoexcitation pump and second harmonic generation efficiency as a probe with delay times spanning 100 fs-1.8 ns. The absence of a second harmonic signal at any delay time rules out the possibility of any transient ferroelectric state under photoexcitation.

Luminescence, Plasmonic, and Magnetic Properties of Doped Semiconductor Nanocrystals.

Introducing a few atoms of impurities or dopants in semiconductor nanocrystals can drastically alter the existing properties or even introduce new properties. For example, mid-gap states created by doping tremendously affect photocatalytic activities and surface controlled redox reactions, generate new emission centers, show thermometric optical switching, make FRET donors by enhancing the excited state lifetime, and also create localized surface plasmon resonance induced low energy absorption. In addition, researchers have more recently started focusing their attention on doped nanocrystals as an important and alternative material for solar energy conversion to meet the current demand for renewable energy. Moreover, the electrical and magnetic properties of the host are also strongly altered on doping. These beneficial dopant-induced changes suggest that doped nanocrystals with proper selections of dopant-host pairs may be helpful for generating designer materials for a wide range of current technological needs. How properties relate to the doping of a variety of semiconductor nanocrystals are summarized in this Review.

Competing Roles of Substrate Composition, Microstructure, and Sustained Strontium Release in Directing Osteogenic Differentiation of hMSCs.

Strontium releasing bioactive ceramics constitute an important class of biomaterials for osteoporosis treatment. In the present study, we evaluated the synthesis, phase assemblage, and magnetic properties of strontium hexaferrite, SrFe12O19, (SrFe) nanoparticles. On the biocompatibility front, the size- and dose-dependent cytotoxicity of SrFe against human mesenchymal stem cells (hMSCs) were investigated. After establishing their non-toxic nature, we used the strontium hexaferrite nanoparticles (SrFeNPs) in varying amount (x = 0, 10, and 20 wt %) to consolidate bioactive composites with hydroxyapatite (HA) by multi-stage spark plasma sintering (SPS). Rietveld refinement of these spark plasma sintered composites revealed a near complete decomposition of SrFe12O19 to magnetite (Fe3O4) along with a marked increase in the unit cell volume of HA, commensurate with strontium-doped HA. The cytocompatibility of SrHA-Fe composites with hMSCs was assessed using qualitative and quantitative morphological analysis along with phenotypic and genotypic expression for stem cell differentiation. A marked decrease in the stemness of hMSCs, indicated by reduced vimentin expression and acquisition of osteogenic phenotype, evinced by alkaline phosphatase (ALP) and collagen deposition was recorded on SrHA-Fe composites in osteoinductive culture. A significant upregulation of osteogenic marker genes (Runx2, ALP and OPN) was detected in case of the SrHA-Fe composites, whereas OCN and Col IA expression were similarly high for baseline HA. However, matrix mineralization was elevated on SrHA-Fe composites in commensurate with the release of Sr2+ and Fe2+. Summarizing, the current work is the first report of strontium hexaferrite as a non-toxic nanobiomaterial. Also, SrHA-based iron oxide composites can potentially better facilitate bone formation, when compared to pristine HA.

Unusual Dirac Fermions on the Surface of a Noncentrosymmetric α-BiPd Superconductor.

Combining multiple emergent correlated properties such as superconductivity and magnetism within the topological matrix can have exceptional consequences in garnering new and exotic physics. Here, we study the topological surface states from a noncentrosymmetric α-BiPd superconductor by employing angle-resolved photoemission spectroscopy and first-principles calculations. We observe that the Dirac surface states of this system have several interesting and unusual properties, compared to other topological surface states. The surface state is strongly anisotropic and the in-plane Fermi velocity varies rigorously on rotating the crystal about the y axis. Moreover, it acquires an unusual band gap as a function of k_{y}, possibly due to hybridization with bulk bands, detected upon varying the excitation energy. The coexistence of all the functional properties in addition to the unusual surface state characteristics make this an interesting material.

Is CH3NH3PbI3 Polar?

In view of the continued controversy concerning the polar/nonpolar nature of the hybrid perovskite system, CH3NH3PbI3, we report the first investigation of a time-resolved pump-probe measurement of the second harmonic generation efficiency as well as using its more traditional form as a sensitive probe of the absence/presence of the center of inversion in the system both in its excited and ground states, respectively. Our results clearly show that SHG efficiency, if nonzero, is below the limit of detection, strongly indicative of a nonpolar or centrosymmetric structure. Our results on the same samples, based on temperature dependent single crystal X-ray diffraction and P-E loop measurements, are entirely consistent with the above conclusion of a centrosymmetric structure for this compound in all three phases, namely the high temperature cubic phase, the intermediate temperature tetragonal phase and the low temperature orthorhombic phase. It is important to note that all our experimental probes are volume averaging and performed on bulk materials, suggesting that basic material properties of CH3NH3PbI3 are consistent with a centrosymmetric, nonpolar structure.

Role of Polar Phonons in the Photo Excited State of Metal Halide Perovskites.

The development of high efficiency perovskite solar cells has sparked a multitude of measurements on the optical properties of these materials. For the most studied methylammonium(MA)PbI3 perovskite, a large range (6-55 meV) of exciton binding energies has been reported by various experiments. The existence of excitons at room temperature is unclear. For the MAPbX3 perovskites we report on relativistic Bethe-Salpeter Equation calculations (GW-BSE). This method is capable to directly calculate excitonic properties from first-principles. At low temperatures it predicts exciton binding energies in agreement with the reported 'large' values. For MAPbI3, phonon modes present in this frequency range have a negligible contribution to the ionic screening. By calculating the polarization in time from finite temperature molecular dynamics, we show that at room temperature this does not change. We therefore exclude ionic screening as an explanation for the experimentally observed reduction of the exciton binding energy at room temperature and argue in favor of the formation of polarons.