No abstract

Tunable two-color ultrafast pump−probe experiments are performed on colloidal metal nanospheres in water and ethanol, and the results are interpreted through a model including thermal dynamics in both the nanoparticle and its environment. Transient optical signals measured for gold nanoparticles in ethanol display a complex temporal response strongly dependent on the wavelength of the probe beam. We demonstrate that its origin is related to a large contribution of liquid environment transient heating to the optical response, in contrast to the usual assumption that optical transmission changes reflect the evolution of nanoparticle temperature only. Accounting for this contribution enables an accurate measurement of thermal conductances at gold− ethanol and gold−water interfaces. Moreover, the thermal dynamics of the solvent can be selectively probed through a specific choice of probe wavelength.

Acoustic vibrations of small nanoparticles are still ruled by continuum mechanics laws down to diameters of a few nanometers. The elastic behavior at lower sizes (<1–2 nm), where nanoparticles become molecular clusters made by few tens to few atoms, is still little explored. The question remains to which extent the transition from small continuous-mass solids to discrete-atom molecular clusters affects their specific low-frequency vibrational modes, whose period is classically expected to linearly scale with diameter. Here, we investigate experimentally by ultrafast time-resolved optical spectroscopy the acoustic response of atomically defined ligand-protected metal clusters Au n (SR) m with a number n of atoms ranging from 10 to 102 (0.5–1.5 nm diameter range). Two periods, corresponding to fundamental breathing- and quadrupolar-like acoustic modes, are detected, with the latter scaling linearly with cluster diameters and the former taking a constant value. Theoretical calculations based on density functional theory (DFT) predict in the case of bare clusters vibrational periods scaling with size down to diatomic molecules. For ligand-protected clusters, they show a pronounced effect of the ligand molecules on the breathing-like mode vibrational period at the origin of its constant value. This deviation from classical elasticity predictions results from mechanical mass-loading effects due to the protecting layer. This study shows that clusters characteristic vibrational frequencies are compatible with extrapolation of continuum mechanics model down to few atoms, which is in agreement with DFT computations.

Superatom state-resolved dynamics of the Au25(SC8H9)18(-) monolayer-protected cluster (MPC) were examined using femtosecond two-dimensional electronic spectroscopy (2DES). The electronic ground state of the Au25(SC8H9)18(-) MPC is described by an eight-electron P-like superatom orbital. Hot electron relaxation (200 ± 15 fs) within the superatom D manifold of lowest-unoccupied molecular orbitals was resolved from hot hole relaxation (290 ± 20 fs) in the superatom P states by using 2DES in a partially collinear pump-probe geometry. Electronic relaxation dynamics mediated by specific superatom states were distinguished by examining the time-dependent cross-peak amplitudes for specific excitation and detection photon energy combinations. Quantification of the time-dependent amplitudes and energy positions of cross peaks in the 2.21/1.85 eV (excitation/detection) region confirmed that an apparent energetic blue shift observed for transient bleach signals results from rapid hot electron relaxation in the superatom D states. The combination of structurally precise MPCs and state-resolved 2DES can be used to examine directly the influence of nanoscale structural modifications on electronic carrier dynamics, which are critical for developing nanocluster-based photonic devices.

We report on the broadband transient optical response of anisotropic, amorphous silicon nanobricks that exhibit Mie-type resonances. A quantitative model is developed to identify and disentangle the three physical processes that govern the ultrafast changes of the nanobrick optical properties, namely, two-photon absorption, free-carrier relaxation, and lattice heating. We reveal a set of operating windows where ultrafast all-optical modulation of transmission is achieved with full return to zero in 20 ps. This is made possible because of the distinct dispersive features exhibited by the competing nonlinear processes in transmission and despite the slow (nanosecond) internal lattice dynamics. The observed ultrafast switching behavior can be independently engineered for both orthogonal polarizations using the large anisotropy of nanobricks, thus allowing ultrafast anisotropy control. Our results categorically ascertain the potential of all-dielectric resonant nanophotonics as a platform for ultrafast optical devices and reveal the possibility for ultrafast polarization-multiplexed displays and polarization rotators

Time-resolved thermoplasmonics is emerging as the go-to technique for nanoscale thermal metrology. In this context, connecting the ultrafast optical response of nanoobjects to the correct thermal pathways is of paramount importance. We developed full thermo-optical models relating transient spectroscopy measurements, performed on metal nanoobjects in dielectric environments, to the overall system thermal dynamics. The models are applicable to small spherical nanoparticles embedded in a homogeneous matrix, following an analytical approach, and are expanded to include the cases of arbitrarily complex geometries and sizes relying on the finite-element method. These approaches are then exploited to rationalize several observations made in the context of previous time-resolved thermo-optical studies at the nanoscale. The present tools open the path for accurate retrieval of thermal parameters, notably the Kapitza resistance and the local environment thermal conductivity, from experiments. They also allow identifying the optimal parameters for selectively probing thermal dynamics of either a nanoobject or its nanoscale environment.

Investigations of the ultrafast acoustic response of metal nanosystems yield important information on the validity of continuous elastic mechanics at the nanoscale and also provide an optical way to probe nanoobject morphologies. In this context, we used femtosecond time-resolved pump–probe spectroscopy to study two classes of bimetallic nanoparticles: chemically synthesized AuAg nanospheres in water in the 20–45 nm size range, both with alloyed and segregated core–shell morphologies, and mass-selected glass-embedded PtAu core–shell nanospheres in the very small size range (2.3–2.5 nm), synthesized by physical methods. The analysis of the corresponding breathing mode periods demonstrates validity of the predictions of the continuous elastic model for bimetallic nanoobjects with the investigated sizes, morphologies and composition. Moreover, discrimination of nanoparticles internal structure (alloy or core–shell) by measurement of their acoustic response is also demonstrated.

We use two-dimensional electronic spectroscopy (2DES) to disentangle the separate electron and hole relaxation pathways and dynamics of CdTe nanorods on a sub-100 fs time scale. By simultaneously exciting and probing the first three excitonic transitions (S1, S2, and S3) and exploiting the unique combination of high temporal and spectral resolution of 2DES, we derive a complete picture for the state-selective carrier relaxation. We find that hot holes relax from the 1Σ3/2 to the 1Σ1/2 state (S2 → S1) with 30 ± 10 fs time constant, and the hot electrons relax from the Σ′ to the Σ state (S3 → S1) with 50 ± 10 fs time constant. This observation would not have been possible with conventional transient absorption spectroscopy due to the spectral congestion of the transitions and the very fast relaxation time scales.