Machine Learning for Predicting Ultralow Thermal Conductivity and High ZT in Complex Thermoelectric Materials.

Efficient and precise calculations of thermal transport properties and figures of merit, alongside a deep comprehension of thermal transport mechanisms, are essential for the practical utilization of advanced thermoelectric materials. In this study, we explore the microscopic processes governing thermal transport in the distinguished crystalline material Tl9SbTe6 by integrating a unified thermal transport theory with machine learning-assisted self-consistent phonon calculations. Leveraging machine learning potentials, we expedite the analysis of phonon energy shifts, higher-order scattering mechanisms, and thermal conductivity arising from various contributing factors, such as population and coherence channels. Our finding unveils an exceptionally low thermal conductivity of 0.31 W m-1 K-1 at room temperature, a result that closely correlates with experimental observations. Notably, we observe that the off-diagonal terms of heat flux operators play a significant role in shaping the overall lattice thermal conductivity of Tl9SbTe6, where the ultralow thermal conductivity resembles that of glass due to limited group velocities. Furthermore, we achieve a maximum ZT value of 3.17 in the c-axis orientation for p-type Tl9SbTe6 at 600 K and an optimal ZT value of 2.26 in the a-axis and b-axis direction for n-type Tl9SbTe6 at 500 K. The crystalline Tl9SbTe6 not only showcases remarkable thermal insulation but also demonstrates impressive electrical properties owing to the dual-degeneracy phenomenon within its valence band. These results not only elucidate the underlying reasons for the exceptional thermoelectric performance of Tl9SbTe6 but also suggest potential avenues for further experimental exploration.

Strong Coupling of Coherent Phonons to Excitons in Semiconducting Monolayer MoTe2.

The coupling of the electron system to lattice vibrations and their time-dependent control and detection provide unique insight into the nonequilibrium physics of semiconductors. Here, we investigate the ultrafast transient response of semiconducting monolayer 2H-MoTe2 encapsulated with hBN using broadband optical pump-probe microscopy. The sub-40 fs pump pulse triggers extremely intense and long-lived coherent oscillations in the spectral region of the A' and B' exciton resonances, up to ∼20% of the maximum transient signal, due to the displacive excitation of the out-of-plane A1g phonon. Ab initio calculations reveal a dramatic rearrangement of the optical absorption of monolayer MoTe2 induced by an out-of-plane stretching and compression of the crystal lattice, consistent with an A1g -type oscillation. Our results highlight the extreme sensitivity of the optical properties of monolayer TMDs to small structural modifications and their manipulation with light.

Coherent Phonons in van der Waals MoSe2/WSe2 Heterobilayers.

The increasing role of two-dimensional (2D) devices requires the development of new techniques for ultrafast control of physical properties in 2D van der Waals (vdW) nanolayers. A special feature of heterobilayers assembled from vdW monolayers is femtosecond separation of photoexcited electrons and holes between the neighboring layers, resulting in the formation of Coulomb force. Using laser pulses, we generate a 0.8 THz coherent breathing mode in MoSe2/WSe2 heterobilayers, which modulates the thickness of the heterobilayer and should modulate the photogenerated electric field in the vdW gap. While the phonon frequency and decay time are independent of the stacking angle between the MoSe2 and WSe2 monolayers, the amplitude decreases at intermediate angles, which is explained by a decrease in the photogenerated electric field between the layers. The modulation of the vdW gap by coherent phonons enables a new technology for the generation of THz radiation in 2D nanodevices with vdW heterobilayers.

Probing gigahertz coherent acoustic phonons in TiO2 mesoporous thin films.

Ultrahigh-frequency acoustic-phonon resonators usually require atomically flat interfaces to avoid phonon scattering and dephasing, leading to expensive fabrication processes, such as molecular beam epitaxy. Mesoporous thin films are based on inexpensive wet chemical fabrication techniques that lead to relatively flat interfaces regardless the presence of nanopores. Here, we report mesoporous titanium dioxide-based acoustic resonators with resonances up to 90 GHz, and quality factors from 3 to 7. Numerical simulations show a good agreement with the picosecond ultrasonics experiments. We also numerically study the effect of changes in the speed of sound on the performance of the resonator. This change could be induced by liquid infiltration into the mesopores. Our findings constitute the first step towards the engineering of building blocks based on mesoporous thin films for reconfigurable optoacoustic sensors.

Coherent Phononics of van der Waals Layers on Nanogratings.

Strain engineering can be used to control the physical properties of two-dimensional van der Waals (2D-vdW) crystals. Coherent phonons, which carry dynamical strain, could push strain engineering to control classical and quantum phenomena in the unexplored picosecond temporal and nanometer spatial regimes. This intriguing approach requires the use of coherent GHz and sub-THz 2D phonons. Here, we report on nanostructures that combine nanometer thick vdW layers and nanogratings. Using an ultrafast pump-probe technique, we generate and detect in-plane coherent phonons with frequency up to 40 GHz and hybrid flexural phonons with frequency up to 10 GHz. The latter arises from the periodic modulation of the elastic coupling of the vdW layer at the grooves and ridges of the nanograting. This creates a new type of a tailorable 2D periodic phononic nanoobject, a flexural phononic crystal, offering exciting prospects for the ultrafast manipulation of states in 2D materials in emerging quantum technologies.

Optically Induced Coherent Phonons in Bismuth Oxyiodide (BiOI) Nanoplatelets.

Bismuth oxyiodide (BiOI) is a promising material for photocatalysis combining intriguing optical and structural properties. We show that excitation by a femtosecond laser pulse creates coherent phonons inducing a time-variant oscillating modulation of the optical density. We find that the two underlying frequencies originate from lattice vibrations along the [001] crystallographic axis, the stacking direction of oppositely charged layers in BiOI. This is consistent with a subpicosecond charge separation driven by a built-in dipolar field. This partially screens the field, launching coherent phonons. Further, we determine the two major dephasing mechanisms that lead to the loss of vibronic coherence: (i) the anharmonic decay of an optical phonon into two acoustic phonons and (ii) phonon-carrier scattering. Our results provide a direct demonstration of the presence of an electric field in BiOI along the [001] axis and show its role in efficient charge separation that is crucial for photocatalytic applications of BiOI.

Protected Long-Distance Guiding of Hypersound Underneath a Nanocorrugated Surface.

In nanoscale communications, high-frequency surface acoustic waves are becoming effective data carriers and encoders. On-chip communications require acoustic wave propagation along nanocorrugated surfaces which strongly scatter traditional Rayleigh waves. Here, we propose the delivery of information using subsurface acoustic waves with hypersound frequencies of ∼20 GHz, which is a nanoscale analogue of subsurface sound waves in the ocean. A bunch of subsurface hypersound modes are generated by pulsed optical excitation in a multilayer semiconductor structure with a metallic nanograting on top. The guided hypersound modes propagate coherently beneath the nanograting, retaining the surface imprinted information, at a distance of more than 50 µm which essentially exceeds the propagation length of Rayleigh waves. The concept is suitable for interfacing single photon emitters, such as buried quantum dots, carrying coherent spin excitations in magnonic devices and encoding the signals for optical communications at the nanoscale.

Strongly Coupled Coherent Phonons in Single-Layer MoS2.

We present a transient absorption setup combining broadband detection over the visible-UV range with high temporal resolution (∼20 fs) which is ideally suited to trigger and detect vibrational coherences in different classes of materials. We generate and detect coherent phonons (CPs) in single-layer (1L)-MoS2, as a representative semiconducting 1L-transition metal dichalcogenide (TMD), where the confined dynamical interaction between excitons and phonons is unexplored. The coherent oscillatory motion of the out-of-plane A'1 phonons, triggered by the ultrashort laser pulses, dynamically modulates the excitonic resonances on a time scale of few tens of fs. We observe an enhancement by almost 2 orders of magnitude of the CP amplitude when detected in resonance with the C exciton peak, combined with a resonant enhancement of CP generation efficiency. Ab initio calculations of the change in the 1L-MoS2 band structure induced by the A'1 phonon displacement confirm a strong coupling with the C exciton. The resonant behavior of the CP amplitude follows the same spectral profile of the calculated Raman susceptibility tensor. These results explain the CP generation process in 1L-TMDs and demonstrate that CP excitation in 1L-MoS2 can be described as a Raman-like scattering process.

Picosecond ultrasonics with miniaturized semiconductor lasers.

There is a great desire to extend ultrasonic techniques to the imaging and characterization of nanoobjects. This can be achieved by picosecond ultrasonics, where by using ultrafast lasers it is possible to generate and detect acoustic waves with frequencies up to terahertz and wavelengths down to nanometers. In our work we present a picosecond ultrasonics setup based on miniaturized mode-locked semiconductor lasers, whose performance allows us to obtain the necessary power, pulse duration and repetition rate. Using such a laser, we measure the ultrasonic echo signal with picosecond resolution in a 112 nm thick Al film deposited on a semiconductor substrate. We show that the obtained signal is as good as the signal obtained with a standard bulky mode-locked Ti-Sa laser. The experiments pave the way for designing integrated portable picosecond ultrasonic setups on the basis of miniaturized semiconductor lasers.

High-Frequency Elastic Coupling at the Interface of van der Waals Nanolayers Imaged by Picosecond Ultrasonics.

Although the topography of van de Waals (vdW) layers and heterostructures can be imaged by scanning probe microscopy, high-frequency interface elastic properties are more difficult to assess. These can influence the stability, reliability, and performance of electronic devices that require uniform layers and interfaces. Here, we use picosecond ultrasonics to image these properties in vdW layers and heterostructures based on well-known exfoliable materials, i.e., InSe, hBN, and graphene. We reveal a strong, uniform elastic coupling between vdW layers over a wide range of frequencies of up to tens of gigahertz (GHz) and in-plane areas of 100 µm2. In contrast, the vdW layers can be weakly coupled to their supporting substrate, behaving effectively as free-standing membranes. Our data and analysis demonstrate that picosecond ultrasonics offers opportunities to probe the high-frequency elastic coupling of vdW nanolayers and image both "perfect" and "broken" interfaces between different materials over a wide frequency range, as required for future scientific and technological developments.

Hierarchical Coherent Phonons in a Superatomic Semiconductor.

The coupling of phonons to electrons and other phonons plays a defining role in material properties, such as charge and energy transport, light emission, and superconductivity. In atomic solids, phonons are delocalized over the 3D lattice, in contrast to molecular solids where localized vibrations dominate. Here, a hierarchical semiconductor that expands the phonon space by combining localized 0D modes with delocalized 2D and 3D modes is described. This material consists of superatomic building blocks (Re6 Se8 ) covalently linked into 2D sheets that are stacked into a layered van der Waals lattice. Using transient reflectance spectroscopy, three types of coherent phonons are identified: localized 0D breathing modes of isolated superatom, 2D synchronized twisting of superatoms in layers, and 3D acoustic interlayer deformation. These phonons are coupled to the electronic degrees of freedom to varying extents. The presence of local phonon modes in an extended crystal opens the door to controlling material properties from hierarchical phonon engineering.

Ultrafast Spectroscopy of Fano-Like Resonance between Optical Phonon and Excitons in CdSe Quantum Dots: Dependence of Coherent Vibrational Wave-Packet Dynamics on Pump Fluence.

The main goal of the present work is to study the coherent phonon in strongly confined CdSe quantum dots (QDs) under varied pump fluences. The main characteristics of coherent phonons (amplitude, frequency, phase, spectrogram) of CdSe QDs under the red-edge pump of the excitonic band [1S(e)-1S3/2(h)] are reported. We demonstrate for the first time that the amplitude of the coherent optical longitudinal-optical (LO) phonon at 6.16 THz excited in CdSe nanoparticles by a femtosecond unchirped pulse shows a non-monotone dependence on the pump fluence. This dependence exhibits the maximum at pump fluence ~0.8 mJ/cm². At the same time, the amplitudes of the longitudinal acoustic (LA) phonon mode at 0.55 THz and of the coherent wave packet of toluene at 15.6, 23.6 THz show a monotonic rise with the increase of pump fluence. The time frequency representation of an oscillating signal corresponding to LO phonons revealed by continuous wavelet transform (CWT) shows a profound destructive quantum interference close to the origin of distinct (optical phonon) and continuum-like (exciton) quasiparticles. The CWT spectrogram demonstrates a nonlinear chirp at short time delays, where the chirp sign depends on the pump pulse fluence. The CWT spectrogram reveals an anharmonic coupling between optical and acoustic phonons.

Thickness-Dependent Coherent Phonon Frequency in Ultrathin FeSe/SrTiO3 Films.

Ultrathin FeSe films grown on SrTiO3 substrates are a recent milestone in atomic material engineering due to their important role in understanding unconventional superconductivity in Fe-based materials. By using femtosecond time- and angle-resolved photoelectron spectroscopy, we study phonon frequencies in ultrathin FeSe/SrTiO3 films grown by molecular beam epitaxy. After optical excitation, we observe periodic modulations of the photoelectron spectrum as a function of pump-probe delay for 1-unit-cell, 3-unit-cell, and 60-unit-cell thick FeSe films. The frequencies of the coherent intensity oscillations increase from 5.00 ± 0.02 to 5.25 ± 0.02 THz with increasing film thickness. By comparing with previous works, we attribute this mode to the Se A1g phonon. The dominant mechanism for the phonon softening in 1-unit-cell thick FeSe films is a substrate-induced lattice strain. Our results demonstrate an abrupt phonon renormalization due to a lattice mismatch between the ultrathin film and the substrate.

Ultrafast switching of hard X-rays.

A new concept for shortening hard X-ray pulses emitted from a third-generation synchrotron source down to few picoseconds is presented. The device, called the PicoSwitch, exploits the dynamics of coherent acoustic phonons in a photo-excited thin film. A characterization of the structure demonstrates switching times of ≤ 5 ps and a peak reflectivity of ∼10(-3). The device is tested in a real synchrotron-based pump-probe experiment and reveals features of coherent phonon propagation in a second thin film sample, thus demonstrating the potential to significantly improve the temporal resolution at existing synchrotron facilities.