Showing papers by "Ajay Ram Srimath Kandada published in 2018"

Phonon coherences reveal the polaronic character of excitons in two-dimensional lead-halide perovskites

Abstract: Hybrid organic-inorganic semiconductors feature complex lattice dynamics due to the ionic character of the crystal and the softness arising from non-covalent bonds between molecular moieties and the inorganic network. Here we establish that such dynamic structural complexity in a prototypical two-dimensional lead iodide perovskite gives rise to the coexistence of diverse excitonic resonances, each with a distinct degree of polaronic character. By means of high-resolution resonant impulsive stimulated Raman spectroscopy, we identify vibrational wavepacket dynamics that evolve along different configurational coordinates for distinct excitons and photocarriers. Employing density functional theory calculations, we assign the observed coherent vibrational modes to various low-frequency ($\lesssim 50$\,cm$^{-1}$) optical phonons involving motion in the lead-iodide layers. We thus conclude that different excitons induce specific lattice reorganizations, which are signatures of polaronic binding. This insight on the energetic/configurational landscape involving globally neutral primary photoexcitations may be relevant to a broader class of emerging hybrid semiconductor materials.

Probing femtosecond lattice displacement upon photo-carrier generation in lead halide perovskite

Abstract: Electronic properties and lattice vibrations are expected to be strongly correlated in metal-halide perovskites, due to the soft fluctuating nature of their crystal lattice. Thus, unveiling electron–phonon coupling dynamics upon ultrafast photoexcitation is necessary for understanding the optoelectronic behavior of the semiconductor. Here, we use impulsive vibrational spectroscopy to reveal vibrational modes of methylammonium lead-bromide perovskite under electronically resonant and non-resonant conditions. We identify two excited state coherent phonons at 89 and 106 cm−1, whose phases reveal a shift of the potential energy minimum upon ultrafast photocarrier generation. This indicates the transition to a new geometry, reached after approximately 90 fs, and fully equilibrated within the phonons lifetime of about 1 ps. Our results unambiguously prove that these modes drive the crystalline distortion occurring upon photo-excitation, demonstrating the presence of polaronic effects. The electron–phonon coupling is the key to understand optoelectronic properties in lead halide perovskites but it is difficult to probe. Here Batignani et al. observe two new phonon modes with impulsive vibrational spectroscopy providing the evidence of the polaronic nature of the photo-excitation.

Exciton-polaron spectral structures in two dimensional hybrid lead-halide perovskites

Abstract: Owing to both electronic and dielectric confinement effects, two-dimensional organic-inorganic hybrid perovskites sustain strongly bound excitons at room temperature. Here, we demonstrate that there are non-negligible contributions to the excitonic correlations that are specific to the lattice structure and its polar fluctuations, both of which are controlled via the chemical nature of the organic counter-cation. We present a phenomenological, yet quantitative framework to simulate excitonic absorption lineshapes in single-layer organic-inorganic hybrid perovskites, based on the two-dimensional Wannier formalism. We include four distinct excitonic states separated by $35\pm5$\,meV, and additional vibronic progressions. Intriguingly, the associated Huang-Rhys factors and the relevant phonon energies show substantial variation with temperature and the nature of the organic cation. This points to the hybrid nature of the lineshape, with a form well described by a Wannier formalism, but with signatures of strong coupling to localized vibrations, and polaronic effects perceived through excitonic correlations. Our work highlights the complexity of excitonic properties in this class of nanostructured materials.

Exciton-polaron spectral structures in two-dimensional hybrid lead-halide perovskites

Abstract: Owing to both electronic and dielectric confinement effects, two-dimensional organic-inorganic hybrid perovskites sustain strongly bound excitons at room temperature. Here, we demonstrate that there are non-negligible contributions to the excitonic correlations that are specific to the lattice structure and its polar fluctuations, both of which are controlled via the chemical nature of the organic countercation. We present a phenomenological yet quantitative framework to simulate excitonic absorption line shapes in single-layer organic-inorganic hybrid perovskites, based on the two-dimensional Wannier formalism. We include four distinct excitonic states separated by $35\ifmmode\pm\else\textpm\fi{}5\phantom{\rule{0.28em}{0ex}}\mathrm{meV}$, and additional vibronic progressions. Intriguingly, the associated Huang-Rhys factors and the relevant phonon energies show substantial variation with temperature and the nature of the organic cation. This points to the hybrid nature of the line shape, with a form well described by a Wannier formalism, but with signatures of strong coupling to localized vibrations, and polaronic effects perceived through excitonic correlations. Our work highlights the complexity of excitonic properties in this class of nanostructured materials.

Stable biexcitons in two-dimensional metal-halide perovskites with strong dynamic lattice disorder

Abstract: With strongly bound and stable excitons at room temperature, single-layer, two-dimensional organic-inorganic hybrid perovskites are viable semiconductors for light-emitting quantum optoelectronics applications. In such a technological context, it is imperative to comprehensively explore all the factors---chemical, electronic, and structural---that govern strong multiexciton correlations. Here, by means of two-dimensional coherent spectroscopy, we examine excitonic many-body effects in pure, single-layer (${\mathrm{PEA})}_{2}{\mathrm{PbI}}_{4}$ (PEA = phenylethylammonium). We determine the binding energy of biexcitons---correlated two-electron, two-hole quasiparticles---to be $44\ifmmode\pm\else\textpm\fi{}5$ meV at room temperature. The extraordinarily high values are similar to those reported in other strongly excitonic two-dimensional materials such as transition-metal dichalcogenides. Importantly, we show that this binding energy increases by $\ensuremath{\sim}25%$ upon cooling to 5 K. Our work highlights the importance of multiexciton correlations in this class of technologically promising, solution-processable materials, in spite of the strong effects of lattice fluctuations and dynamic disorder.

Probing dynamical symmetry breaking using quantum-entangled photons

Abstract: We present an input/output analysis of photon-correlation experiments whereby a quantum mechanically entangled bi-photon state interacts with a material sample placed in one arm of a Hong–Ou–Mandel apparatus. We show that the output signal contains detailed information about subsequent entanglement with the microscopic quantum states in the sample. In particular, we apply the method to an ensemble of emitters interacting with a common photon mode within the open-system Dicke model. Our results indicate considerable dynamical information concerning spontaneous symmetry breaking can be revealed with such an experimental system.

Lattice vibrations and dynamic disorder in two-dimensional hybrid lead-halide perovskites

Abstract: By means of non-resonant Raman spectroscopy and density functional theory calculations, we measure and assign the vibrational spectrum of two distinct two-dimensional lead-iodide perovskite derivatives. These two samples are selected in order to probe the effects of the organic cation on lattice dynamics. One templating cation is composed of a phenyl-substituted ammonium derivative, while the other contains a linear alkyl group. We find that modes that directly involve the organic cation are more prevalent in the phenyl-substituted derivative. Comparison of the temperature dependence of the Raman spectra reveals differences in the nature of dynamic disorder, with a strong dependence on the molecular nature of the organic moiety.

Photon entanglement entropy as a probe of many-body correlations and fluctuations

Abstract: Recent theoretical and experiments have explored the use of entangled photons as a spectroscopic probe of material systems. We develop here a theoretical description for entropy production in the scattering of an entangled biphoton state within an optical cavity. We develop this using perturbation theory by expanding the biphoton scattering matrix in terms of single-photon terms in which we introduce the photon-photon interaction via a complex coupling constant, $\xi$. We show that the von Neumann entropy provides a succinct measure of this interaction. We then develop a microscopic model and show that in the limit of fast fluctuations, the entanglement entropy vanishes whereas in the limit the coupling is homogeneous broadened, the entanglement entropy depends upon the magnitude of the fluctuations and reaches a maximum.