Pierre-Adrien Mante

Electron–acoustic phonon coupling in single crystal CH3NH3PbI3 perovskites revealed by coherent acoustic phonons

Despite the great amount of attention CH3NH3PbI3 has received for its solar cell application, intrinsic properties of this material are still largely unknown. Mobility of charges is a quintessential property in this aspect; however, there is still no clear understanding of electron transport, as reported values span over three orders of magnitude. Here we develop a method to measure the electron and hole deformation potentials using coherent acoustic phonons generated by femtosecond laser pulses. We apply this method to characterize a CH3NH3PbI3 single crystal. We measure the acoustic phonon properties and characterize electron-acoustic phonon scattering. Then, using the deformation potential theory, we calculate the carrier intrinsic mobility and compare it to the reported experimental and theoretical values. Our results reveal high electron and hole mobilities of 2,800 and 9,400 cm2 V−1 s−1, respectively. Comparison with literature values of mobility demonstrates the potential role played by polarons in charge transport in CH3NH3PbI3.

Probing Hydrophilic Interface of Solid/Liquid-Water by Nanoultrasonics

Despite the numerous devoted studies, water at solid interfaces remains puzzling. An ongoing debate concerns the nature of interfacial water at a hydrophilic surface, whether it is more solid-like, ice-like, or liquid-like. To answer this question, a complete picture of the distribution of the water molecule structure and molecular interactions has to be obtained in a non-invasive way and on an ultrafast time scale. We developed a new experimental technique that extends the classical acoustic technique to the molecular level. Using nanoacoustic waves with a femtosecond pulsewidth and an ångström resolution to noninvasively diagnose the hydration structure distribution at ambient solid/water interface, we performed a complete mapping of the viscoelastic properties and of the density in the whole interfacial water region at hydrophilic surfaces. Our results suggest that water in the interfacial region possesses mixed properties and that the different pictures obtained up to now can be unified. Moreover, we discuss the effect of the interfacial water structure on the abnormal thermal transport properties of solid/liquid interfaces.

Gigahertz Coherent Guided Acoustic Phonons in AlN/GaN Nanowire Superlattices

The generation of guided acoustic phonons in the GHz range in GaN/AlN superlattices grown atop a GaN nanowire is presented. Combined with a femtosecond laser, ultrafast pump-probe spectroscopy allows the generation and detection of guided acoustic phonons at different frequencies in the nanowire superlattices. The capability of the nanowire superlattices to be excellent detectors of acoustic phonons at specific frequencies is then used to observe the strong dispersion, as a result of nanoconfinement, of guided acoustic phonons after their propagation in the nanowire. The generation of high frequency coherent guided acoustic phonons could be useful not only to realize an acoustic transducer with a nanolateral size but also as a source to understand the thermal behavior of nanowires.

THz acoustic phonon spectroscopy and nanoscopy by using piezoelectric semiconductor heterostructures

Thanks to ultrafast acoustics, a better understanding of acoustic dynamics on a short time scale has been obtained and new characterization methods at the nanoscale have been developed. Among the materials that were studied during the development of ultrafast acoustics, nitride based heterostructures play a particular role due to their piezoelectric properties and the possibility to generate phonons with over-THz frequency and bandwidth. Here, we review some of the work performed using this type of structure, with a focus on THz phonon spectroscopy and nanoscopy. First, we present a brief description of the theory of coherent acoustic phonon generation by piezoelectric heterostructure. Then the first experimental observation of coherent acoustic phonon generated by the absorption of ultrashort light pulses in piezoelectric heterostructures is presented. From this starting point, we then present some methods developed to realize customizable phonon generation. Finally we review some more recent applications of these structures, including imaging with a nanometer resolution, broadband attenuation measurements with a frequency up to 1THz and phononic bandgap characterization.

Selectively probing vibrations in a plasmonic supracrystal

The coupling of plasmonic resonances with the multiple phonon modes of a plasmonic supracrystal is studied. Ultrafast optical pump-probe spectroscopy with variable wavelength allows the selective detection of the breathing mode, the interparticle vibrations, and the vibration of the whole structure. Thanks to this selectivity, the characterization of the bonding strength between nanoparticles in different directions of the supracrystal is possible. The observation of these vibrations could be useful for the realization of future phonon modulated photonic and plasmonic devices.

Graphene-to-substrate energy transfer through out-of-plane longitudinal acoustic phonons.

Practically, graphene is often deposited on substrates. Given the major substrate-induced modification of properties and considerable energy transfer at the interface, the graphene-substrate interaction has been widely discussed. However, the proposed mechanisms were restricted to the two-dimensional (2D) plane and interface, while the energy conduction in the third dimension is hardly considered. Herein, we disclose the transfer of energy perpendicular to the interface of the combined system of the 2D graphene and the 3D base. More precisely, our observation of the energy dissipation of optically excited graphene via emitting out-of-plane longitudinal acoustic phonon into the substrate is presented. By applying nanoultrasonic spectroscopy with a piezoelectric nanolayer embedded in the substrate, we found that under photoexcitation by a femtosecond laser pulse graphene can emit longitudinal coherent acoustic phonons (CAPs) with frequencies over 1 THz into the substrate. In addition, the waveform of the CAP pulse infers that the photocarriers and sudden lattice heating in graphene caused modification of graphene-substrate bond and consequently generated longitudinal acoustic phonons in the substrate. The direct observation of this unexplored graphene-to-substrate vertical energy transfer channel can bring new insights into the understanding of the energy dissipation and limited transport properties of supported graphene.

Femtosecond excitation of radial breathing mode in 2-D arrayed GaN nanorods

Radial breathing oscillation of 2-D arrayed GaN nanorods was successfully excited in rods with different diameters by using femtosecond transient reflectivity measurement. Through analyzing thus measured diameter dependent oscillation frequency, we discovered that modification of the mechanical property appeared in the 2-D arrayed piezoelectric GaN nanorods, fabricated on top of a bulk substrate, when the rod diameter was on the order of or less than 50 nm. Our measurement observed a much reduced elastic stiffness constant (C11) of 193 ± 24 GPa in 35nm diameter nanorods, compared with the 365 ± 2 GPa in bulk GaN. This size-reduction induced mechanical modification would be a critical factor to be considered for future sensing and energy applications. Our study also provides a new spectroscopic method to explore the size-reduction-induced softening effect through the measurement of the radial breathing oscillations.

Interferometric detection of extensional modes of GaN nanorods array

Femtosecond pump probe spectroscopy experiments were carried out to observe extensional modes of GaN nanorods. Different orders of extensional modes were generated and observed following the absorption of femtosecond light pulses. This observation confirms that with a diameter on the order of 100 nm, no mechanical change is expected compared to bulk GaN. We propose and demonstrate that the detection of these modes is achieved through the modulation of the Fabry-Pérot cavity formed by the nanorod array. The extensional modes change the nanorods length and thus modify the reflectivity of the rod-array cavity.

Nondestructive Complete Mechanical Characterization of Zinc Blende and Wurtzite GaAs Nanowires Using Time-Resolved Pump− Probe Spectroscopy

We have developed and demonstrated an experimental method, based on the picosecond acoustics technique, to perform nondestructive complete mechanical characterization of nanowires, that is, the determination of the complete elasticity tensor. By means of femtosecond pump-probe spectroscopy, coherent acoustic phonons were generated in an ensemble of nanowires and their dynamics was resolved. Specific phonon modes were identified and the detection mechanism was addressed via wavelength dependent experiments. We calculated the exact phonon dispersion relation of the nanowires by fitting the experimentally observed frequencies, thus allowing the extraction of the complete elasticity tensor. The elasticity tensor and the nanowire diameter were determined for zinc blende GaAs nanowires and were found to be in a good agreement with literature data and independent measurements. Finally, we have applied this technique to characterize wurtzite GaAs nanowires, a metastable phase in bulk, for which no experimental values of elastic constants are currently available. Our results agree well with previous first principle calculations. The proposed approach to the complete and nondestructive mechanical characterization of nanowires will allow the efficient mechanical study of new crystal phases emerging in nanostructures, as well as size-dependent properties of nanostructured materials.

Enhanced detection sensitivity of higher-order vibrational modes of gold nanodisks on top of a GaN nanorod array through localized surface plasmons

We report a method that enables the excitation of localized surface plasmons (LSPs) in a gold nanodisk array by placing each nanodisk on top of a GaN nanorod. When the rod length was much longer than the plasmon penetration depth inside the nanorod, the plasmonic field was found to be localized, and coupling between neighboring gold nanodisks was eliminated. The interaction between LSPs and acoustic vibrations in gold nanodisks was then investigated. Owing to the strong localization of the plasmonic field, weak, higher-order vibrational modes of gold nanodisk could be optically observed. Furthermore, such an LSP-based acoustic sensor could be operated at any angle of incident light. Our study not only provides an approach to excite LSPs in high-density metallic arrays, but also opens one of the possible solutions for the development of highly sensitive sub-terahertz hypersonic sensors with high angle tolerance of incident light.