Phonon-Phonon Interactions in the Polarization Dependence of Raman Scattering.

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 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.

Mechanistic View on the Order-Disorder Phase Transition in Amphidynamic Crystals.

We combine temperature-dependent low-frequency Raman measurements and first-principles calculations to obtain a mechanistic understanding of the order-disorder phase transition of 2,7-di-tert-butylbenzo[b]benzo[4,5]thieno[2,3-d]thiophene (ditBu-BTBT) and 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS-pentacene) semiconducting amphidynamic crystals. We identify the lattice normal modes associated with the phase transition by following the position and width of the Raman peaks with temperature and identifying peaks that exhibit nonlinear dependence toward the phase transition temperature. Our findings are interpreted according to the "hardcore mode" model previously used to describe order-disorder phase transitions in inorganic and hybrid crystals with a Brownian sublattice. Within the framework of this model, ditBu-BTBT exhibits an ideal behavior where only one lattice mode is associated with the phase transition. TIPS-pentacene deviates strongly from the model due to strong interactions between lattice modes. We discuss the origin of the different behaviors and suggest side-chain engineering as a tool to control polymorphism in amphidynamic crystals.

Chemical Modifications Suppress Anharmonic Effects in the Lattice Dynamics of Organic Semiconductors.

The lattice dynamics of organic semiconductors has a significant role in determining their electronic and mechanical properties. A common technique to control these macroscopic properties is to chemically modify the molecular structure. These modifications are known to change the molecular packing, but their effect on the lattice dynamics is relatively unexplored. Therefore, we investigate how chemical modifications to a core [1]benzothieno[3,2-b]benzothiophene (BTBT) semiconducting crystal affect the evolution of the crystal structural dynamics with temperature. Our study combines temperature-dependent polarization-orientation (PO) low-frequency Raman measurements with first-principles calculations and single-crystal X-ray diffraction measurements. We show that chemical modifications can indeed suppress specific expressions of vibrational anharmonicity in the lattice dynamics. Specifically, we detect in BTBT a gradual change in the PO Raman response with temperature, indicating a unique anharmonic expression. This anharmonic expression is suppressed in all examined chemically modified crystals (ditBu-BTBT and diC8-BTBT, diPh-BTBT, and DNTT). In addition, we observe solid-solid phase transitions in the alkyl-modified BTBTs. Our findings indicate that π-conjugated chemical modifications are the most effective in suppressing these anharmonic effects.

Tapered Optical Fibers Coated with Rare-Earth Complexes for Quantum Applications.

Crystals and fibers doped with rare-earth (RE) ions provide the basis for most of today's solid-state optical systems, from lasers and telecom devices to emerging potential quantum applications such as quantum memories and optical to microwave conversion. The two platforms, doped crystals and doped fibers, seem mutually exclusive, each having its own strengths and limitations, the former providing high homogeneity and coherence and the latter offering the advantages of robust optical waveguides. Here we present a hybrid platform that does not rely on doping but rather on coating the waveguide-a tapered silica optical fiber-with a monolayer of complexes, each containing a single RE ion. The complexes offer an identical, tailored environment to each ion, thus minimizing inhomogeneity and allowing tuning of their properties to the desired application. Specifically, we use highly luminescent Yb3+[Zn(II)MC (QXA)] complexes, which isolate the RE ion from the environment and suppress nonradiative decay channels. We demonstrate that the beneficial optical transitions of the Yb3+ are retained after deposition on the tapered fiber and observe an excited-state lifetime of over 0.9 ms, on par with state-of-the-art Yb-doped inorganic crystals.

Anharmonic Lattice Dynamics in Sodium Ion Conductors.

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 lattice-Na+ 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 order-disorder 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 lattice-mobile ion dynamics in vibrational instabilities that are coincident with the exceptional conductivity of these Na+ ion conductors.

Strongly Anharmonic Octahedral Tilting in Two-Dimensional Hybrid Halide Perovskites.

Recent investigations of two-dimensional (2D) hybrid organic-inorganic halide perovskites (HHPs) indicate that their optical and electronic properties are dominated by strong coupling to thermal fluctuations. While the optical properties of 2D-HHPs have been extensively studied, a comprehensive understanding of electron-phonon interactions is limited because little is known about their structural dynamics. This is partially because the unit cells of 2D-HHPs contain many atoms. Therefore, the thermal fluctuations are complex and difficult to elucidate in detail. To overcome this challenge, we use polarization-orientation Raman spectroscopy and ab initio calculations to compare the structural dynamics of the prototypical 2D-HHPs [(BA)2PbI4 and (PhE)2PbI4] to their three-dimensional (3D) counterpart, MAPbI3. Comparison to the simpler, 3D MAPbI3 crystal shows clear similarities with the structural dynamics of (BA)2PbI4 and (PhE)2PbI4 across a wide temperature range. The analogy between the 3D and 2D crystals allows us to isolate the effect of the organic cation on the structural dynamics of the inorganic scaffold of the 2D-HHPs. Furthermore, using this approach, we uncover the mechanism of the order-disorder phase transition of (BA)2PbI4 (274 K) and show that it involves relaxation of octahedral tilting coupled to anharmonic thermal fluctuations. These anharmonic fluctuations are important because they induce charge carrier localization and affect the optoelectronic performance of these materials.

Anharmonic Lattice Vibrations in Small-Molecule Organic Semiconductors.

The intermolecular lattice vibrations in small-molecule organic semiconductors have a strong impact on their functional properties. Existing models treat the lattice vibrations within the harmonic approximation. In this work, polarization-orientation (PO) Raman measurements are used to monitor the temperature-evolution of the symmetry of lattice vibrations in anthracene and pentacene single crystals. Combined with first-principles calculations, it is shown that at 10 K, the lattice dynamics of the crystals are indeed harmonic. However, as the temperature is increased, specific lattice modes gradually lose their PO dependence and become more liquid-like. This finding is indicative of a dynamic symmetry breaking of the crystal structure and shows clear evidence of the strongly anharmonic nature of these vibrations. Pentacene also shows an apparent phase transition between 80 and 150 K, indicated by a change in the vibrational symmetry of one of the lattice modes. These findings lay the groundwork for accurate predictions of the electronic properties of high-mobility organic semiconductors at room temperature.

Sub-second hyper-spectral low-frequency vibrational imaging via impulsive Raman excitation.

Real-time vibrational microscopy has been recently demonstrated by various techniques, most of them utilizing the well-known schemes of coherent anti-stokes Raman scattering and stimulated Raman scattering. These techniques readily provide valuable chemical information mostly in the higher vibrational frequency regime (>400 cm-1). Addressing the low vibrational frequency regime (<200 cm-1) is challenging due to the usage of spectral filters that are required to isolate the signal from the Rayleigh scattered excitation field. In this Letter, we report on rapid, high-resolution, low-frequency (<130 cm-1) vibrational microscopy using impulsive coherent Raman excitation. By combining impulsive excitation with a fast acousto-optic delay line, we detect the Raman-induced optical Kerr lensing and spectral shift effects with a 25 µs pixel dwell time to produce shot-noise limited, low-frequency hyper-spectral images of various samples.

Simplified approach to low-frequency coherent anti-Stokes Raman spectroscopy using a sharp spectral edge filter.

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 (<200 cm-1).