arXiv subjects

Jayakanth Ravichandran

Publications and source records attributed to Jayakanth Ravichandran.

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arXiv2021

Direct Observation and Control of Surface Termination in Perovskite Oxide Heterostructures

The interfacial behavior of quantum materials leads to emergent phenomena such as two dimensional electron gases, quantum phase transitions, and metastable functional phases. Probes for in situ and real time surface sensitive characterization are critical for active monitoring and control of epitaxial synthesis, and hence the atomic-scale engineering of heterostructures and superlattices. Termination switching, especially as an interfacial process in ternary complex oxides, has been studied using a variety of probes, often ex situ; however, direct observation of this phenomena is lacking. To address this need, we establish in situ and real time reflection high energy electron diffraction and Auger electron spectroscopy for pulsed laser deposition, which provide structural and compositional information of the surface during film deposition. Using this unique capability, we show, for the first time, the direct observation and control of surface termination in complex oxide heterostructures of SrTiO3 and SrRuO3. Density-functional-theory calculations capture the energetics and stability of the observed structures and elucidate their electronic behavior. This demonstration opens up a novel approach to monitor and control the composition of materials at the atomic scale to enable next-generation heterostructures for control over emergent phenomena, as well as electronics, photonics, and energy applications.

cond-mat.mtrl-sci↗

arXiv2020

Discovery of highly-polarizable semiconductors BaZrS3 and Ba3Zr2S7

There are few known semiconductors exhibiting both strong optical response and large dielectric polarizability. Inorganic materials with large dielectric polarizability tend to be wide-band gap complex oxides. Semiconductors with strong photoresponse to visible and infrared light tend to be weakly polarizable. Interesting exceptions to these trends are halide perovskites and phase-change chalcogenides. Here we introduce complex chalcogenides in the Ba-Zr-S system in perovskite and Ruddlesden-Popper structures as a new family of highly polarizable semiconductors. We report the results of impedance spectroscopy on single crystals that establish BaZrS3 and Ba3Zr2S7 as semiconductors with low-frequency relative dielectric constant ($ε_0$) in the range 50 - 100, and band gap in the range 1.3 - 1.8 eV. Our electronic structure calculations indicate the enhanced dielectric response in perovskite BaZrS3 versus Ruddlesden-Popper Ba3Zr2S7 is primarily due to enhanced IR mode-effective charges, and variations in phonon frequencies along $\langle 001 \rangle$; differences in the Born effective charges and the lattice stiffness are of secondary importance. This combination of covalent bonding in crystal structures more common to complex oxides results in a sizable Fröhlich coupling constant, which suggests that charge carriers are large polarons.

cond-mat.mtrl-sci↗

arXiv2019

Crystal growth and structural analysis of perovskite chalcogenide BaZrS$_3$ and Ruddlesden-Popper phase Ba$_3$Zr$_2$S$_7$

Perovskite chalcogenides are gaining substantial interest as an emerging class of semiconductors for optoelectronic applications. High quality samples are of vital importance to examine their inherent physical properties. We report the successful crystal growth of the model system, BaZrS$_3$ and its Ruddlesden-Popper phase Ba$_3$Zr$_2$S$_7$ by flux method. X-ray diffraction analyses showed space group of $Pnma$ with lattice constants of $a$ = 7.056(3) Å\/, $b$ = 9.962(4) Å\/, $c$ = 6.996(3) Å\/ for BaZrS$_3$ and $P4_2/mnm$ with $a$ = 7.071(2) Å\/, $b$ = 7.071(2) Å\/, $c$ = 25.418(5) Å\/ for Ba$_3$Zr$_2$S$_7$. Rocking curves with full-width-at-half-maximum of 0.011$^\circ$ for BaZrS$_3$ and 0.027$^\circ$ for Ba$_3$Zr$_2$S$_7$ were observed. Pole figure analysis, scanning transmission electron microscopy images and electron diffraction patterns also establish high quality of grown crystals. The octahedra tilting in the corner-sharing octahedra network are analyzed by extracting the torsion angles.

cond-mat.mtrl-sci↗

arXiv2019

In situ Auger electron spectroscopy of complex oxide surfaces grown by pulsed laser deposition

The authors report in situ Auger electron spectroscopy (AES) of the surfaces of complex oxides thin films grown by pulsed laser deposition (PLD). The authors demonstrate the utility of the technique in studying chemical composition by collecting characteristic Auger spectra of elements from samples such as complex oxide thin films and single crystals as well as metal foils. In the case of thin films, AES studies can be performed with single unit cell precision by monitoring thickness during deposition with reflection high energy electron diffraction (RHEED). The authors address some of the challenges in achieving in situ and real time AES studies on complex oxide thin films grown by PLD. Sustained layer-by-layer PLD growth of a CaTiO3/LaMnO3 superlattice allows depth-resolved chemical composition analysis during the growth process. The evolution of the Auger spectra of the elements from individual layers were used to perform chemical analysis with monolayer-depth resolution.

cond-mat.mtrl-sci↗

arXiv2019

In Praise and in Search of Highly-Polarizable Semiconductors

The dielectric response of materials underpins electronics and photonics. Established semiconductor materials have a narrow range of dielectric susceptibility, with low-frequency values on the order of 10. Strong and variable dielectric response in wide-band gap materials is associated with complex crystal structures and heavier elements. Based on underlying chemical trends, we hypothesize that chalcogenides in crystal structures common to complex oxides may feature many highly-polarizable semiconductors. Research on these materials is motivated by fundamental inquiry into electrons and phonons in solids, and by potential applications in photonics, high-frequency communications, and photovoltaics.

cond-mat.mtrl-sci↗

arXiv2019

Linear Dichroism Conversion in Quasi One-Dimensional Perovskite Chalcogenide

Anisotropic photonic materials with linear dichroism are crucial components in many sensing, imaging and communication applications. Such materials play an important role as polarizers, filters and wave-plates in photonic devices and circuits. Conventional crystalline materials with optical anisotropy typically show unidirectional linear dichroism over a broad wavelength range. The linear dichroism conversion phenomenon has not been observed in crystalline materials. Here, we report the investigation of the unique linear dichroism conversion phenomenon in quasi-one-dimensional (quasi-1D) hexagonal perovskite chalcogenide BaTiS3. The material shows record level of optical anisotropy within the visible wavelength range. In contrast to conventional anisotropic optical materials, the linear dichroism polarity in BaTiS3 makes an orthogonal change at an optical wavelength corresponding to the photon energy of 1.78 eV. First principle calculations reveal that this anomalous linear dichroism conversion behavior originates from different selection rules of the optical transitions from the parallel bands in the BaTiS3 material. Wavelength dependent polarized Raman spectroscopy further confirms this phenomenon. Such material with linear dichroism conversion property can facilitate new ability to control and sense the energy and polarization of light, and lead to novel photonic devices such as polarization-wavelength selective detectors and lasers for multispectral imaging, sensing and optical communication applications.

cond-mat.mtrl-sci↗

arXiv2019

Band gap evolution in Ruddlesden-Popper phases

We investigate the variation of the band gap across the Ruddlesden-Popper (RP) series (An+1BnX3n+1) in model chalcogenide, oxide, and halide materials to understand the factors influencing band gap evolution. In contrast to the oxides and halides, we find the band gap of the chalcogenides evolve differently with the thickness of the perovskite blocks in these natural superlattices. We show that octahedral rotations (i.e. deviation of the B-X-B bond angles from 180) and quantum confinement effects compete to decide the band gap evolution of RP phases. The insights gained here will allow us to rationally design layered perovskite phases for electronics and optoelectronics.

cond-mat.mtrl-sci↗

arXiv2018

Ultra-low Power Microwave Oscillators based on Phase Change Oxides as Solid-State Neurons

Neuro-inspired computing architectures are one of the leading candidates to solve complex, large-scale associative learning problems. The two key building blocks for neuromorphic computing are the synapse and the neuron, which form the distributed computing and memory units. Solid state implementations of these units remain an active area of research. Specifically, voltage or current controlled oscillators are considered a minimal representation of neurons for hardware implementations. Such oscillators should demonstrate synchronization and coupling dynamics for demonstrating collective learning behavior, besides the desirable individual characteristics such as scaling, power, and performance. To this end, we propose the use of nanoscale, epitaxial heterostructures of phase change oxides and oxides with metallic conductivity as a fundamental unit of an ultralow power, tunable electrical oscillator capable of operating in the microwave regime. Our simulations show that optimized heterostructure design with low thermal boundary resistance can result in operation frequency of up to 3 GHz and power consumption as low as 15 fJ/cycle with rich coupling dynamics between the oscillators.

physics.app-ph↗

arXiv2018

Epitaxial Growth and Electrical Properties of VO2 on LSAT (111) substrate

We report the epitaxial growth and the electrical properties, especially the metal-to-insulator transition (MIT), of vanadium dioxide (VO2) thin films synthesized on LSAT (111) ([LaAlO3]0.3[Sr2AlTaO6]0.7) substrates by pulsed laser deposition. X-ray diffraction studies show that the epitaxial relationship between the VO2 thin films and LSAT substrate is given as VO2(020)||LSAT(111) and VO2[001]||LSAT[11-2]. We observed a sharp four orders of magnitude change in the longitudinal resistance for the VO2 thin films around the transition temperature. We also measured distinct Raman spectra below and above the transition point indicating a concomitant structural transition between the insulator and metallic phases, in agreement with past investigations.

cond-mat.mtrl-sci↗

arXiv2018

Thermal Stability Study of Transition Metal Perovskite Sulfides

Transition metal perovskite chalcogenides, a class of materials with rich tunability in functionalities, are gaining increased attention as candidate materials for renewable energy applications. Perovskite oxides are considered excellent n-type thermoelectric materials. Compared to oxide counterparts, we expect the chalcogenides to possess more favorable thermoelectric properties such as lower lattice thermal conductivity and smaller band gap, making them promising material candidates for high temperature thermoelectrics. Thus, it is necessary to study the thermal properties of these materials in detail, especially thermal stability, to evaluate their potential. In this work, we report the synthesis and thermal stability study of five compounds, α-SrZrS$_3$, β-SrZrS$_3$, BaZrS$_3$, Ba$_2$ZrS$_4$, and Ba$_3$Zr$_2$S$_7$. These materials cover several structural types including distorted perovskite, needle-like, and Ruddlesden-Popper phases. Differential scanning calorimeter and thermo-gravimetric analysis measurements were performed up to 1200°C in air. Structural and chemical characterizations such as X-ray diffraction, Raman spectroscopy, and energy dispersive analytical X-ray spectroscopy were performed on all the samples before and after the heat treatment to understand the oxidation process. Our studies show that perovskite chalcogenides possess excellent thermal stability in air at least up to 600°C.

cond-mat.mtrl-sci↗

arXiv2018

Ideal Bandgap in a 2D Ruddlesden-Popper Perovskite Chalcogenide for Single-junction Solar Cells

Transition metal perovskite chalcogenides (TMPCs) are explored as stable, environmentally friendly semiconductors for solar energy conversion. They can be viewed as the inorganic alternatives to hybrid halide perovskites, and chalcogenide counterparts of perovskite oxides with desirable optoelectronic properties in the visible and infrared part of the electromagnetic spectrum. Past theoretical studies have predicted large absorption coefficient, desirable defect characteristics, and bulk photovoltaic effect in TMPCs. Despite recent progresses in polycrystalline synthesis and measurements of their optical properties, it is necessary to grow these materials in high crystalline quality to develop a fundamental understanding of their optical properties and evaluate their suitability for photovoltaic application. Here, we report the growth of single crystals of a two-dimensional (2D) perovskite chalcogenide, Ba3Zr2S7, with a natural superlattice-like structure of alternating double-layer perovskite blocks and single-layer rock salt structure. The material demonstrated a bright photoluminescence peak at 1.28 eV with a large external luminescence efficiency of up to 0.15%. We performed time-resolved photoluminescence spectroscopy on these crystals and obtained an effective recombination time of ~65 ns. These results clearly show that 2D Ruddlesden-Popper phases of perovskite chalcogenides are promising materials to achieve single-junction solar cells.

cond-mat.mtrl-sci↗

arXiv2018

Mid-wave and Long-wave IR Linear Dichroism in a Hexagonal Perovskite Chalcogenide

Mid-wave infrared (IR) and long-wave IR spectral ranges are of growing interest in various applications such as thermal imaging, thermography-based remote sensing, and night vision. Materials widely used for IR photodetectors in this regime include cadmium mercury telluride alloys and nanostructures of compound semiconductor. The materials development for IR optics will drive down the cost of IR optical systems and enable larger scale deployment. Here, we report a mid-wave IR responsive material composed of earth abundant and non-toxic elements, Sr1+xTiS3. It has a highly anisotropic quasi-one-dimensional structure similar to hexagonal perovskites. We grew large, high quality single crystals and studied its anisotropic optical properties. We observed two distinct optical absorption edges at ~2.5 um and ~5 um, respectively, for linear polarizations along two principal axes. The material demonstrated strong and broadband linear dichroism spanning mid-wave IR and long-wave IR, with a dichroitic ratio of up to 22.

cond-mat.mtrl-sci↗

arXiv2018

Band-Gap Control via Structural and Chemical Tuning of Transition Metal Perovskite Chalcogenides

Transition metal perovskite chalcogenides (TMPC) are a new class of semiconductor materials with broad tunability of physical properties due to their chemical and structural flexibility. Theoretical calculations show that band gaps of TMPCs are tunable from Far IR to UV spectrum. Amongst these materials, more than a handful of materials have energy gap and very high absorption coefficients, which are appropriate for optoelectronic applications, especially solar energy conversion. Despite several promising theoretical predictions, very little experimental studies on their physical properties are currently available, especially optical properties. We report a new synthetic route towards high quality bulk ceramic TMPCs and systematic study of three phases, SrZrS3 in two different room temperature stabilized phases and one of BaZrS3. All three materials were synthesized with a catalyzed solid-state reaction process in sealed ampoules. Structural and chemical characterizations establish high quality of the samples, which is confirmed by the intense room temperature photoluminescence (PL) spectra showing direct band gaps around 1.53eV, 2.13eV and 1.81eV respectively. The potential of these materials for solar energy conversion was evaluated by measurement of PL quantum efficiency and estimate of quasi Fermi level splitting.

cond-mat.mtrl-sci↗

arXiv2018

Unexpected Termination Switching and Polarity Compensation in LaAlO3/SrTiO3 heterostructures

Polar crystals composed of charged ionic planes cannot exist in nature without acquiring surface changes to balance an ever-growing dipole. The necessary changes can manifest structurally or electronically. An electronic asymetry has long been observed in the LaAlO3/SrTiO3 system. Electron accumulation is observed near the LaAlO3/TiO2-SrTiO3 interface, while the LaAlO3/SrO-SrTiO3 stack is insulating. Here, we observe evidence for an asymmetry in the surface chemical termination for nominally stoichiometric LaAlO3 films in contact with the two different surface layers of SrTiO3 crystals, TiO2 and SrO. Using several element specific probes, we find that the surface termination of LaAlO3 remains AlO2 irrespective of the starting termination of SrTiO3 substrate surface. We use a combination of cross-plane tunneling measurements and first principles calcula- tions to understand the effects of this unexpected termination on band alignments and polarity compensation of LaAlO3/SrTiO3 heterostructures. An asymmetry in LaAlO3 polarity compensation and resulting electronic properties will fundamentally limit atomic level control of oxide heterostructures.

cond-mat.mtrl-sci↗

arXiv2017

Controlled Electrochemical Intercalation of Graphene/h-BN van der Waals Heterostructures

Electrochemical intercalation is a powerful method for tuning the electronic properties of layered solids. In this work, we report an electro-chemical strategy to controllably intercalate lithium ions into a series of van der Waals (vdW) heterostructures built by sandwiching graphene between hexagonal boron nitride (h-BN). We demonstrate that encapsulating graphene with h-BN eliminates parasitic surface side reactions while simultaneously creating a new hetero-interface that permits intercalation between the atomically thin layers. To monitor the electrochemical process, we employ the Hall effect to precisely monitor the intercalation reaction. We also simultaneously probe the spectroscopic and electrical transport properties of the resulting intercalation compounds at different stages of intercalation. We achieve the highest carrier density $> 5 \times 10^{13} cm^{-2}$ with mobility $> 10^3 cm^2/(Vs)$ in the most heavily intercalated samples, where Shubnikov-de Haas quantum oscillations are observed at low temperatures. These results set the stage for further studies that employ intercalation in modifying properties of vdW heterostructures.

cond-mat.mes-hall↗

arXiv2010

High temperature thermoelectric response of double-doped SrTiO$_3$ epitaxial films

SrTiO$_3$ is a promising $n$-type oxide semiconductor for thermoelectric energy conversion. Epitaxial thin films of SrTiO$_3$ doped with both La and oxygen vacancies have been synthesized by pulsed laser deposition (PLD). The thermoelectric and galvanomagnetic properties of these films have been characterized at temperatures ranging from 300 K to 900 K and are typical of a doped semiconductor. Thermopower values of double-doped films are comparable to previous studies of La doped single crystals at similar carrier concentrations. The highest thermoelectric figure of merit ($ZT$) was measured to be 0.28 at 873 K at a carrier concentration of $2.5\times10^{21}$ cm$^{-3}$.

cond-mat.mtrl-sci↗

arXiv2010

Built-in and induced polarization across LaAlO$_3$/SrTiO$_3$ heterojunctions

Ionic crystals terminated at oppositely charged polar surfaces are inherently unstable and expected to undergo surface reconstructions to maintain electrostatic stability. Essentially, an electric field that arises between oppositely charged atomic planes gives rise to a built-in potential that diverges with thickness. In ultra thin film form however the polar crystals are expected to remain stable without necessitating surface reconstructions, yet the built-in potential has eluded observation. Here we present evidence of a built-in potential across polar \lao ~thin films grown on \sto ~substrates, a system well known for the electron gas that forms at the interface. By performing electron tunneling measurements between the electron gas and a metallic gate on \lao ~we measure a built-in electric field across \lao ~of 93 meV/Å. Additionally, capacitance measurements reveal the presence of an induced dipole moment near the interface in \sto, illuminating a unique property of \sto ~substrates. We forsee use of the ionic built-in potential as an additional tuning parameter in both existing and novel device architectures, especially as atomic control of oxide interfaces gains widespread momentum.

cond-mat.mtrl-sci↗