arXiv subjects

Keshav M. Dani

Publications and source records attributed to Keshav M. Dani.

13 recordsLinked to original sources

arXiv2026

Quasiparticle phono-conversion: filming carriers coalescing into excitons

Condensed matter physics is replete with phenomena involving high-energy free particles coalescing into low-energy bound few-particle states. While the cooling of the individual particles is well understood, the crucial step by which cold free carriers form a bound state remains elusive, involving complex energy and momentum relaxation pathways. Here, by combining ultrafast time- and momentum-resolved photoemission spectroscopy on a monolayer WSe$_2$ with the first-principles excitonic-Bloch equations, we resolve the conversion of initially free electrons and holes at the bandedges into bound excitons. With unprecedented energy resolution, we observe the transient \textit{coexistence} of free-carrier and excitonic bands, accompanied by a transfer of spectral weight between the two. We establish the phononic origin of exciton formation and ascribe this coexistence to a sequential relaxation cascade toward the lowest-energy excitonic states, wherein intermediate states remain weakly populated. The efficiency of this process is controlled by valley multiplicity, large-momentum phonon emission and spin-flip processes. By elucidating how bound states emerge from their elementary constituents, our results point to strategies for engineering exciton formation, with direct implications for optical materials and devices that operate with excitons or free carriers.

cond-mat.mtrl-sci↗

arXiv2024

Driving non-trivial quantum phases in conventional semiconductors with intense excitonic fields

Inducing novel quantum phases and topologies in materials using intense light fields is a key objective of modern condensed matter physics, but nonetheless faces significant experimental challenges. Alternately, theory predicts that in the dense limit, excitons - collective excitations composed of Coulomb-bound electron-hole pairs - could also drive exotic quantum phenomena. However, the direct observation of these phenomena requires the resolution of electronic structure in momentum space in the presence of excitons, which became possible only recently. Here, using time- and angle-resolved photoemission spectroscopy of an atomically thin semiconductor in the presence of a high-density of resonantly and coherently photoexcited excitons, we observe the Bardeen-Cooper-Schrieffer (BCS) excitonic state - analogous to the Cooper pairs of superconductivity. We see the valence band transform from a conventional paraboloid into a Mexican-hat like Bogoliubov dispersion - a hallmark of the excitonic insulator phase; and we observe the recently predicted giant exciton-driven Floquet effects. Our work realizes the promise that intense bosonic fields, other than photons, can also drive novel quantum phenomena and phases in materials.

cond-mat.mtrl-sci↗

arXiv2021

Dominating Interlayer Resonant Energy Transfer in Type-II 2D Heterostructure

Type-II heterostructures (HSs) are essential components of modern electronic and optoelectronic devices. Earlier studies have found that in type-II transition metal dichalcogenide (TMD) HSs, the dominating carrier relaxation pathway is the interlayer charge transfer (CT) mechanism. Here, this report shows that, in a type-II HS formed between monolayers of MoSe2 and ReS2, nonradiative energy transfer (ET) from higher to lower work function material (ReS2 to MoSe2) dominates over the traditional CT process with and without a charge-blocking interlayer. Without a charge-blocking interlayer, the HS area shows 3.6 times MoSe2 photoluminescence (PL) enhancement as compared to the MoSe2 area alone. After completely blocking the CT process, more than one order of magnitude higher MoSe2 PL emission was achieved from the HS area. This work reveals that the nature of this ET is truly a resonant effect by showing that in a similar type-II HS formed by ReS2 and WSe2, CT dominates over ET, resulting in a severely quenched WSe2 PL. This study not only provides significant insight into the competing interlayer processes, but also shows an innovative way to increase the PL quantum yield of the desired TMD material using ET process by carefully choosing the right material combination for HS.

cond-mat.mtrl-sci↗

arXiv2021

Moiré-localized interlayer exciton wavefunctions captured by imaging its electron and hole constituents

Interlayer excitons (ILXs) - electron-hole pairs bound across two atomically thin layered semiconductors - have emerged as attractive platforms to study exciton condensation, single-photon emission and other quantum-information applications. Yet, despite extensive optical spectroscopic investigations, critical information about their size, valley configuration and the influence of the moiré potential remains unknown. Here, we captured images of the time- and momentum-resolved distribution of both the electron and the hole that bind to form the ILX in a WSe2/MoS2 heterostructure. We thereby obtain a direct measurement of the interlayer exciton diameter of ~5.4 nm, comparable to the moiré unit-cell length of 6.1 nm. Surprisingly, this large ILX is well localized within the moiré cell to a region of only 1.8 nm - smaller than the size of the exciton itself. This high degree of localization of the interlayer exciton is backed by Bethe-Salpeter equation calculations and demonstrates that the ILX can be localized within small moiré unit cells. Unlike large moiré cells, these are uniform over large regions, thus allowing the formation of extended arrays of localized excitations for quantum technology.

physics.optics↗

arXiv2021

Unraveling the varied nature and roles of defects in hybrid halide perovskites with time-resolved photoemission electron microscopy

With rapidly growing photoconversion efficiencies, hybrid perovskite solar cells have emerged as promising contenders for next generation, low-cost photovoltaic technologies. Yet, the presence of nanoscale defect clusters, that form during the fabrication process, remains critical to overall device operation, including efficiency and long-term stability. To successfully deploy hybrid perovskites, we must understand the nature of the different types of defects, assess their potentially varied roles in device performance, and understand how they respond to passivation strategies. Here, by correlating photoemission and synchrotron-based scanning probe X-ray microscopies, we unveil three different types of defect clusters in state-of-the-art triple cation mixed halide perovskite thin films. Incorporating ultrafast time-resolution into our photoemission measurements, we show that defect clusters originating at grain boundaries are the most detrimental for photocarrier trapping, while lead iodide defect clusters are relatively benign. Hexagonal polytype defect clusters are only mildly detrimental individually, but can have a significant impact overall if abundant in occurrence. We also show that passivating defects with oxygen in the presence of light, a previously used approach to improve efficiency, has a varied impact on the different types of defects. Even with just mild oxygen treatment, the grain boundary defects are completely healed, while the lead iodide defects begin to show signs of chemical alteration. Our findings highlight the need for multi-pronged strategies tailored to selectively address the detrimental impact of the different defect types in hybrid perovskite solar cells.

cond-mat.mtrl-sci↗

arXiv2021

Local Nanoscale Defective Phase Impurities Are the Sites of Degradation in Halide Perovskite Devices

Halide perovskites excel in the pursuit of highly efficient thin film photovoltaics, with power conversion efficiencies reaching 25.5% in single junction and 29.5% in tandem halide perovskite/silicon solar cell configurations. Operational stability of perovskite solar cells remains a barrier to their commercialisation, yet a fundamental understanding of degradation processes, including the specific sites at which failure mechanisms occur, is lacking. Recently, we reported that performance-limiting deep sub-bandgap states appear in nanoscale clusters at particular grain boundaries in state-of-the-art $Cs_{0.05}FA_{0.78}MA_{0.17}Pb(I_{0.83}Br_{0.17})_{3}$ (MA=methylammonium, FA=formamidinium) perovskite films. Here, we combine multimodal microscopy to show that these very nanoscale defect clusters, which go otherwise undetected with bulk measurements, are sites at which degradation seeds. We use photoemission electron microscopy to visualise trap clusters and observe that these specific sites grow in defect density over time under illumination, leading to local reductions in performance parameters. Scanning electron diffraction measurements reveal concomitant structural changes at phase impurities associated with trap clusters, with rapid conversion to metallic lead through iodine depletion, eventually resulting in pinhole formation. By contrast, illumination in the presence of oxygen reduces defect densities and reverses performance degradation at these local clusters, where phase impurities instead convert to amorphous and electronically benign lead oxide. Our work shows that the trapping of charge carriers at sites associated with phase impurities, itself reducing performance, catalyses redox reactions that compromise device longevity. Importantly, we reveal that both performance losses and intrinsic degradation can be mitigated by eliminating these defective clusters.

cond-mat.mtrl-sci↗

arXiv2021

Nanoscale Chemical Heterogeneity Dominates the Optoelectronic Response over Local Electronic Disorder and Strain in Alloyed Perovskite Solar Cells

Halide perovskites perform remarkably in optoelectronic devices including tandem photovoltaics. However, this exceptional performance is striking given that perovskites exhibit deep charge carrier traps and spatial compositional and structural heterogeneity, all of which should be detrimental to performance. Here, we resolve this long-standing paradox by providing a global visualisation of the nanoscale chemical, structural and optoelectronic landscape in halide perovskite devices, made possible through the development of a new suite of correlative, multimodal microscopy measurements combining quantitative optical spectroscopic techniques and synchrotron nanoprobe measurements. We show that compositional disorder dominates the optoelectronic response, while nanoscale strain variations even of large magnitude (~1 %) have only a weak influence. Nanoscale compositional gradients drive carrier funneling onto local regions associated with low electronic disorder, drawing carrier recombination away from trap clusters associated with electronic disorder and leading to high local photoluminescence quantum efficiency. These measurements reveal a global picture of the competitive nanoscale landscape, which endows enhanced defect tolerance in devices through spatial chemical disorder that outcompetes both electronic and structural disorder.

physics.app-ph↗

arXiv2020

Experimental measurement of the intrinsic excitonic wavefunction

An exciton, a two-body composite quasiparticle formed of an electron and hole, is a fundamental optical excitation in condensed-matter systems. Since its discovery nearly a century ago, a measurement of the excitonic wavefunction has remained beyond experimental reach. Here, we directly image the excitonic wavefunction in reciprocal space by measuring the momentum distribution of electrons photoemitted from excitons in monolayer WSe2. By transforming to real space, we obtain a visual of the distribution of the electron around the hole in an exciton. Further, by also resolving the energy coordinate, we confirm the elusive theoretical prediction that the photoemitted electron exhibits an inverted energy-momentum dispersion relationship reflecting the valence band where the partner hole remains, rather than that of conduction-band states of the electron.

cond-mat.mes-hall↗

arXiv2020

Directly visualizing the momentum forbidden dark excitons and their dynamics in atomically thin semiconductors

Resolving the momentum degree of freedom of excitons - electron-hole pairs bound by the Coulomb attraction in a photoexcited semiconductor, has remained a largely elusive goal for decades. In atomically thin semiconductors, such a capability could probe the momentum forbidden dark excitons, which critically impact proposed opto-electronic technologies, but are not directly accessible via optical techniques. Here, we probe the momentum-state of excitons in a WSe2 monolayer by photoemitting their constituent electrons, and resolving them in time, momentum and energy. We obtain a direct visual of the momentum forbidden dark excitons, and study their properties, including their near-degeneracy with bright excitons and their formation pathways in the energy-momentum landscape. These dark excitons dominate the excited state distribution - a surprising finding that highlights their importance in atomically thin semiconductors.

cond-mat.mtrl-sci↗

arXiv2018

Symmetry and optical selection rules in graphene quantum dots

Graphene quantum dots (GQD's) have optical properties which are very different from those of an extended graphene sheet. In this Article we explore how the size, shape and edge--structure of a GQD affect its optical conductivity. Using representation theory, we derive optical selection rules for regular-shaped dots, starting from the symmetry properties of the current operator. We find that, where the x- and y-components of the current operator transform with the same irreducible representation (irrep) of the point group - for example in triangular or hexagonal GQD's - the optical conductivity is independent of the polarisation of the light. On the other hand, where these components transform with different irreps - for example in rectangular GQD's - the optical conductivity depends on the polarisation of light. We find that GQD's with non-commuting point-group operations - for example dots of rectangular shape - can be distinguished from GQD's with commuting point-group operations - for example dots of triangular or hexagonal shape - by using polarized light. We carry out explicit calculations of the optical conductivity of GQD's described by a simple tight--binding model and, for dots of intermediate size, \textcolor{blue}{($10 \lesssim L \lesssim 50\ \text{nm}$)} find an absorption peak in the low--frequency range of the spectrum which allows us to distinguish between dots with zigzag and armchair edges. We also clarify the one-dimensional nature of states at the van Hove singularity in graphene, providing a possible explanation for very high exciton-binding energies. Finally we discuss the role of atomic vacancies and shape asymmetry.

cond-mat.mtrl-sci↗

arXiv2018

High-temperature terahertz optical diode effect without magnetic order in polar FeZnMo$_3$O$_8$

We present a terahertz spectroscopic study of polar ferrimagnet FeZnMo$_3$O$_8$. Our main finding is a giant high-temperature optical diode effect, or nonreciprocal directional dichroism, where the transmitted light intensity in one direction is over 100 times lower than intensity transmitted in the opposite direction. The effect takes place in the paramagnetic phase with no long-range magnetic order in the crystal, which contrasts sharply with all existing reports of the terahertz optical diode effect in other magnetoelectric materials, where the long-range magnetic ordering is a necessary prerequisite. In \fzmo, the effect occurs resonantly with a strong magnetic dipole active transition centered at 1.27 THz and assigned as electron spin resonance between the eigenstates of the single-ion anisotropy Hamiltonian. We propose that the optical diode effect in paramagnetic FeZnMo$_3$O$_8$ is driven by signle-ion terms in magnetoelectric free energy.

cond-mat.str-el↗

arXiv2017

Similar ultrafast dynamics of several dissimilar Dirac and Weyl semimetals

Recent years have seen the rapid discovery of solids whose low-energy electrons have a massless, linear dispersion, such as Weyl, line-node, and Dirac semimetals. The remarkable optical properties predicted in these materials show their versatile potential for optoelectronic uses. However, little is known of their response in the picoseconds after absorbing a photon. Here we measure the ultrafast dynamics of four materials that share non-trivial band structure topology but that differ chemically, structurally, and in their low-energy band structures: ZrSiS, which hosts a Dirac line node and Dirac points; TaAs and NbP, which are Weyl semimetals; and Sr$_{1-y}$Mn$_{1-z}$Sb$_2$, in which Dirac fermions coexist with broken time-reversal symmetry. After photoexcitation by a short pulse, all four relax in two stages, first sub-picosecond, and then few-picosecond. Their rapid relaxation suggests that these and related materials may be suited for optical switches and fast infrared detectors. The complex change of refractive index shows that photoexcited carrier populations persist for a few picoseconds.

cond-mat.mtrl-sci↗

arXiv2017

Terahertz frequency magnetoelectric effect in Ni doped CaBaCo$_4$O$_7$

We present a study of terahertz frequency magnetoelectric effect in ferrimagnetic pyroelectric CaBaCo$_4$O$_7$ and its Ni-doped variants. The terahertz absorption spectrum of these materials consists of spin excitations and low-frequency infrared-active phonons. We studied the magnetic-field-induced changes in the terahertz refractive index and absorption in magnetic fields up to 17 T. We find that the magnetic field modulates the strength of infrared-active optical phonons near 1.2 and 1.6 THz. We use the Lorentz model of the dielectric function to analyze the measured magnetic-field dependence of the refractive index and absorption. We propose that most of the magnetoelectric effect is contributed by the optical phonons near 1.6 THz and higher-frequency resonances. Our experimental results can be used to construct and validate more detailed theoretical descriptions of magnetoelectricity in CaBaCo$_{4-x}$Ni$_x$O$_7$.

cond-mat.str-el↗