Publications

The pursuit of structure-property relationships in crystalline metal halide perovskites (MHPs) has yielded an unprecedented combination of advantageous characteristics for wide-ranging optoelectronic applications. While crystalline MHP structures are readily accessible through diffraction-based structure refinements, providing a clear view of associated long-range ordering, the local structures in more recently discovered glassy MHP states remain unexplored. Herein, we utilize a combination of Raman spectroscopy, solid-state nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy, in situ X-ray diffraction (XRD) and pair distribution function (PDF) analysis to investigate the coordination environment in crystalline, glass and melt states of the 2D MHP [(S)-(−)-1-(1-naphthyl)ethylammonium]₂PbBr₄. While crystalline SNPB shows polarization-dependent Raman spectra, the glassy and melt states exhibit broad features and lack polarization dependence. Solid-state NMR reveals disordering at the organic-inorganic interface of the glass due to significant spatial disruption in the tethering ammonium groups and the corresponding dihedral bond angles connecting the naphthyl and ammonium groups, while still preserving substantial naphthyl group registry and remnants of the layering from the crystalline state (deduced from XRD analysis). Moreover, PDF analysis demonstrates the persistence of corner-sharing PbBr₆ octahedra in the inorganic framework of the melt/glass phases, but with a loss of structural coherence over length scales exceeding approximately one octahedron due to disorder in the inter- and intraoctahedra bond angles/lengths. These findings deepen our understanding of diverse MHP structural motifs and how structural alterations within the MHP glass affect properties, offering potential for advancing next-generation phase change materials and devices.

Ortho-terphenyl (OTP) has long been used as a model system to study the glass transition due to its apparent simplicity and a widespread assumption that it is a rigid molecule. Here, we employ terahertz time-domain spectroscopy and low-frequency Raman spectroscopy to investigate the rigidity of OTP by direct observation of the low-frequency vibrational dynamics. These terahertz phonons involve complex large-amplitude atomic motions where intramolecular and intermolecular displacements are often mixed. Comparison of experimental results with density functional theory and ab initio molecular dynamics simulations shows that the assumption of rigidity neglects important implications for the glass transition and must be revisited. These results highlight the significance of terahertz modes on elasticity, which will be even more critical in more complex systems such as biomolecules.

Ternary nitride semiconductors are rapidly emerging as a promising class of materials for energy conversion applications, offering an appealing combination of strong light absorption in the visible range, desirable charge transport characteristics, and good chemical stability. In this work, it is shown that finite-temperature lattice dynamics in CuTaN₂ a prototypical ternary nitride displaying particularly strong visible light absorption exhibit a pronounced anharmonic character that plays an essential role in defining its macroscopic optoelectronic and thermal properties. Low-frequency vibrational modes that are Raman-inactive from symmetry considerations of the average crystal structure and unstable in harmonic phonon calculations are found to appear as intensive Raman features near room temperature. The atomic contributions to the anharmonic vibrations are characterized by combining Raman measurements with molecular dynamics and density functional theory calculations. This analysis reveals that anharmonic lattice dynamics have large ramifications on the fundamental properties of this compound, resulting in uniaxial negative thermal expansion and the opening of its bandgap to a near-optimal value for solar energy harvesting. The atomic-level understanding of anharmonic lattice dynamics, as well as the finding that they strongly influence key properties of this semiconductor at room temperature, have important implications for design of new functional materials, especially within the emerging class of ternary nitride semiconductors.

We have found that the polarization dependence of Raman scattering in organic crystals at finite temperatures can only be described by a fourth-rank tensor formalism. This generalization of the second-rank Raman tensor Formula Presented stems from the effect of off-diagonal components in the crystal self-energy on the light scattering mechanism. We thus establish a novel manifestation of phonon-phonon interaction in inelastic light scattering, markedly separate from the better-known phonon lifetime.

2D hybrid perovskites are currently in the spotlight of material research for light-harvesting and -emitting applications. It remains extremely challenging, however, to externally control their optical response due to the difficulties of introducing electrical doping. Here, an approach of interfacing ultrathin sheets of perovskites with few-layer graphene and hexagonal boron nitride into gate-tunable, hybrid heterostructures, is demonstrated. It allows for bipolar, continuous tuning of light emission and absorption in 2D perovskites by electrically injecting carriers to densities as high as 1012 cm−2. This reveals the emergence of both negatively and positively charged excitons, or trions, with binding energies up to 46 meV, among the highest measured for 2D systems. Trions are shown to dominate light emission and propagate with mobilities reaching 200 cm2 V−1 s−1 at elevated temperatures. The findings introduce the physics of interacting mixtures of optical and electrical excitations to the broad family of 2D inorganicorganic nanostructures. The presented strategy to electrically control the optical response of 2D perovskites highlights it as a promising material platform toward electrically modulated light-emitters, externally guided charged exciton currents, and exciton transistors based on layered, hybrid semiconductors.

The anharmonic lattice dynamics of oxide and halide perovskites play a crucial role in their mechanical and optical properties. Raman spectroscopy is one of the key methods used to study these structural dynamics. However, despite decades of research, existing interpretations cannot explain the temperature dependence of the observed Raman spectra. We demonstrate the nonmonotonic evolution with temperature of the scattering intensity and present a model for second-order Raman scattering that accounts for this unique trend. By invoking a low-frequency anharmonic feature, we are able to reproduce the Raman spectral line shapes and integrated intensity temperature dependence. Numerical simulations support our interpretation of this low-frequency mode as a transition between two minima of a double-well potential surface. The model can be applied to other dynamically disordered crystal phases, providing a better understanding of the structural dynamics, leading to favorable electronic, optical, and mechanical properties in functional materials.

We show that formamidinium-based crystals are distinct from methylammonium-based halide perovskite crystals because their inorganic sublattice exhibits intrinsic local static disorder that coexists with a well-defined average crystal structure. Our study combines terahertz-range Raman scattering with single-crystal X-ray diffraction and first-principles calculations to probe the evolution of inorganic sublattice dynamics with temperature in the range of 10300 K. The temperature evolution of the Raman spectra shows that low-temperature, local static disorder strongly affects the crystal structural dynamics and phase transitions at higher temperatures.

A family of salts of R-(+)-(3)-hydroxyquinuclidinium [QH]+, with SO42−, BPh4−, BF4− and PF6− counter-anions, have been prepared by the metathesis of [QH]Cl and metal salts of the corresponding anions. Solid solutions of formula [QH](PF6)x(BF4)1−x for x = 0.9, 0.8, 0.7 have also been obtained. The crystalline materials have been investigated by a combination of solid-state techniques, including variable temperature XRD, thermal analyses, multinuclear (11B, 13C, 15N, 19F, and 31P) solid-state NMR spectroscopy, variable temperature wideline 19F T1 relaxation measurements, and micro-Raman spectroscopy to investigate their thermal stability and phase transition behaviors. It has been shown that the salts [QH]PF6 and [QH]BF4 undergo an orderdisorder solidsolid phase transition to plastic phases, whereas [QH]2SO4·H2O and [QH]BPh4 do not display any plastic phase transition. Doping [QH]BF4 into the [QH]PF6 lattice up to 30% results in the formation of a solid solution that is plastic in an expanded thermal range, thanks to a phenomenon that we describe here for the first time as \u201creordering frustration\u201d.

We employ terahertz-range temperature-dependent Raman spectroscopy and first-principles lattice dynamical calculations to show that the undoped sodium ion conductors Na3PS4 and isostructural Na3PSe4 both exhibit anharmonic lattice dynamics. The anharmonic effects in the compounds involve coupled host latticeNa+ ion dynamics that drive the tetragonal-to-cubic phase transition in both cases, but with a qualitative difference in the anharmonic character of the transition. Na3PSe4 shows an almost purely displacive character with the soft modes disappearing in the cubic phase as the change in symmetry shifts these modes to the Raman-inactive Brillouin zone boundary. Na3PS4 instead shows an orderdisorder character in the cubic phase, with the soft modes persisting through the phase transition and remaining Raman active in the cubic phase, violating Raman selection rules for that phase. Our findings highlight the important role of coupled host latticemobile ion dynamics in vibrational instabilities that are coincident with the exceptional conductivity of these Na+ ion conductors.

Lead-based halide perovskite crystals are shown to have strongly anharmonic structural dynamics. This behavior is important because it may be the origin of their exceptional photovoltaic properties. The double perovskite, Cs2AgBiBr6, has been recently studied as a lead-free alternative for optoelectronic applications. However, it does not exhibit the excellent photovoltaic activity of the lead-based halide perovskites. Therefore, to explore the correlation between the anharmonic structural dynamics and optoelectronic properties in lead-based halide perovskites, the structural dynamics of Cs2AgBiBr6 are investigated and are compared to its lead-based analog, CsPbBr3. Using temperature-dependent Raman measurements, it is found that both materials are indeed strongly anharmonic. Nonetheless, the expression of their anharmonic behavior is markedly different. Cs2AgBiBr6 has well-defined normal modes throughout the measured temperature range, while CsPbBr3 exhibits a complete breakdown of the normal-mode picture above 200 K. It is suggested that the breakdown of the normal-mode picture implies that the average crystal structure may not be a proper starting point to understand the electronic properties of the crystal. In addition to our main findings, an unreported phase of Cs2AgBiBr6 is also discovered below approximate to 37 K.

Halide perovskites exhibit beneficial opto-electronic properties (e.g. long carrier lifetimes and low defect densities), and their dynamic structural instabilities and anharmonic thermal fluctuations are directly implicated in these properties. In this work, we combine in-depth analysis of Raman spectroscopy and ab initio calculations to uncover the critical roles of Group 14 M2+ (M = Pb, Sn, Ge) metal cation s orbital lone pairs in the dynamic instabilities of CsMBr3 and particularly in governing the octahedral tilting. Previous studies concluded that the lone-pair stereochemical activity primarily leads to the off-centering motion of the metal cation, and the tilting is usually ascribed to ionic size effects. Here, we show that the lone-pair stereochemical activity contributes to strong octahedral tilting instabilities that induce liquid-like behavior in all examined crystals, which underlies the robustness of halide perovskites to charged defects. In addition, the lone-pairs induce a local, molecule-like behavior of the Ge2+ with a pyramidal bonding motif in the cubic phase, and they contribute to another phase transition of CsSnBr3 at 60 K. Our findings elucidate the fundamental origin of anharmonicities in halide perovskites and provide the crucial link between chemical composition and optoelectronic properties, opening opportunities for lead-free and solution-processable photovoltaics.

Two-dimensional hybrid perovskites are currently in the spotlight of condensed matter and nanotechnology research due to their intriguing optoelectronic and vibrational properties with emerging potential for light-harvesting and light-emitting applications. While it is known that these natural quantum wells host tightly bound excitons, the mobilities of these fundamental optical excitations at the heart of the optoelectronic applications are barely explored. Here, we directly monitor the diffusion of excitons through ultrafast emission microscopy from liquid helium to room temperature in hBN-encapsulated two-dimensional hybrid perovskites. We find very fast diffusion with characteristic hallmarks of free exciton propagation for all temperatures above 50 K. In the cryogenic regime, we observe nonlinear, anomalous behavior with an exceptionally rapid expansion of the exciton cloud followed by a very slow and even negative effective diffusion. We discuss our findings in view of efficient exciton-phonon coupling, highlighting two-dimensional hybrids as promising platforms for basic research and optoelectronic applications.

The family of 2D Ruddlesden-Popper perovskites is currently attracting great interest of the scientific community as highly promising materials for energy harvesting and light emission applications. Despite the fact that these materials are known for decades, only recently has it become apparent that their optical properties are driven by the exciton-phonon coupling, which is controlled by the organic spacers. However, the detailed mechanism of this coupling, which gives rise to complex absorption and emission spectra, is the subject of ongoing controversy. In this work we show that the particularly rich, absorption spectra of (PEA)(2)(CH3NH3)(n-1)PbnI3n+1 (where PEA stands for phenylethylammonium and n = 1, 2, 3), are related to a vibronic progression of excitonic transition. In contrast to other two-dimensional perovskites, we observe a coupling to a high-energy (40 meV) phonon mode probably related to the torsional motion of the NH3+ head of the organic spacer.

Coherent anti-Stokes Raman scattering (CARS) has found wide applications in biomedical research. Compared with alternatives, single-beam CARS is especially attractive at low frequencies. Yet, currently existing schemes necessitate a relatively complicated setup to perform high-resolution spectroscopy. Here we show that the spectral sharp edge formed by an ultra-steep long-pass filter is sufficient for performing CARS spectroscopy, simplifying the system significantly. We compare the sensitivity of the presented methodology with available counterparts both theoretically and experimentally. Importantly, we show that this method, to the best of our knowledge, is the simplest and most suitable for vibrational imaging and spectroscopy in the very low-frequency regime (

We demonstrate the formation of large sheets of layered organic-inorganic perovskite (OIPC) crystals, as thin as a single unit cell, prepared by mechanical exfoliation. The resulting two-dimensional OIPC nanosheets of 2.4 nm thickness are direct semiconductors with an optical band gap of 2.4 eV. They exhibit unusually strong light-matter interaction with an optical absorption as high as 25% at the main excitonic resonance, as well as bright photoluminescence. We extract an exciton binding energy of 490 meV from measurement of the series of excited exciton states. The properties of the excitons are shown to be strongly influenced by the changes in the dielectric surroundings. The environmental sensitivity of these ultrathin OIPC sheets is further reflected in the strong suppression of a thermally driven phase transition present in the bulk crystals.

Singlet fission is a form of multiple exciton generation in which two triplet excitons are produced from the decay of a photoexcited singlet exciton. In a small number of organic materials, most notably pentacene, this conversion process has been shown to occur with unity quantum yield on sub-ps timescales. However, a poorly understood mechanism for fission along with strict energy and geometry requirements have so far limited the observation of this process to a few classes of organic materials, with only a subset of these (most notably the polyacenes) showing both efficient fission and long-lived triplets. Here, we utilize novel organic materials to investigate how the efficiency of the fission process depends on the coupling and the energetic driving force between chromophores in both intra-and intermolecular singlet fission materials. We demonstrate how the triplet yield can be accurately quantified using a combination of traditional transient spectroscopies and recently developed excited state saturable absorption techniques. These results allow us to gain mechanistic insight into the fission process and suggest general strategies for generating new materials that can undergo efficient fission.

The interface level alignment of alkyl and alkenyl monolayers, covalently bound to oxide-free Si substrates of various doping levels, is studied using X-ray photoelectron spectroscopy. Using shifts in the C 1s and Si 2p photoelectron peaks as a sensitive probe, we find that charge distribution around the covalent Si-C bond dipole changes according to the initial position of the Fermi level within the Si substrate. This shows that the interface dipole is not fixed but rather changes with the doping level. These results set limits to the applicability of simple models to describe level alignment at interfaces and show that the interface bond and dipole may change according to the electrostatic potential at the interface.

An eight-orders of magnitude enhancement in current across Hg/X-styrene-Si junctions is caused by merely altering a substituent, X. Interface states are passivated and, depending on X, the Si Schottky junction encompasses the full range from Ohmic to strongly rectifying. This powerful electrostatic molecular effect has immediate implications for interface band alignment and sensing.

We report near-perfect transfer of the electrical properties of oxide-free Si surface, modified by a molecular monolayer, to the interface of a junction made with that modified Si surface. Such behavior is highly unusual for a covalent, narrow bandgap semiconductor, such as Si. Short, ambient atmosphere, room temperature treatment of oxide-free Si(100) in hydroquinone (HQ)/alkyl alcohol solutions, fully passivates the Si surface, while allowing controlled change of the resulting surface potential. The junctions formed, upon contacting such surfaces with Hg, a metal that does not chemically interact with Si, follow the Schottky-Mott model for metal-semiconductor junctions closer than ever for Si-based junctions. Two examples of such ideal behavior are demonstrated: a) Tuning the molecular surface dipole over 400 mV, with only negligible band bending, by changing the alkyl chain length. Because of the excellent passivation this yields junctions with Hg with barrier heights that follow the change in the Si effective electron affinity nearly ideally. b) HQ/methanol passivation of Si is accompanied by a large surface dipole, which suffices, as interface dipole, to drive the Si into strong inversion as shown experimentally via its photovoltaic effect. With only ∼0.3 nm molecular interlayer between the metal and the Si, our results proves that it is passivation and prevention of metal-semiconductor interactions that allow ideal metal-semiconductor junction behavior, rather than an insulating transport barrier.

One of the major problems in molecular electronics is how to make electronically conducting contact to the "soft" organic and biomolecules without altering the molecules. As a result, only a small number of metals can be applied, mostly by special deposition methods with severe limitations. Transferring a predefined thin metal leaf onto a molecular layer provides a nondestructive, noninvasive contacting method that is, in principle, applicable to many types of metal and a variety of metal/molecules combinations. Here we report a modification of our earlier lift-off, float-on (LOFO) method, using as a basis its offspring, the polymer-assisted lift-off (PALO) method, where a backing polymer enables simultaneous deposition of multiple contacts as well as reduces wrinkles in the thin metal leaf. The modified PALO (MoPALO) method, reported here, adds lithography steps to obviate the need to punch through the polymer, as is done to complete PALO contacts. Morphological characterization of the electrodes indicates highly uniform, wrinkle-free contacts of negligible roughness. The good electrical performance of the MoPALO contacts was proven with metal/organic-monolayer/semiconductor (MOMS) junctions, which are known to be very sensitive to molecular degradation and metal penetration. We also show how MoPALO contacts enabled us to compare the effect of varying the metal work function and contact area on the current-voltage characteristics of MOMS devices.