Electronic Carrier Dynamics Research Articles

Atomic-Level Structure Determines Electron-Phonon Scattering Rates in 2-D Polar Metal Heterostructures.

The electron dynamics of atomically thin 2-D polar metal heterostructures, which consisted of a few crystalline metal atomic layers intercalated between hexagonal silicon carbide and graphene grown from the silicon carbide, were studied using nearly degenerate transient absorption spectroscopy. Optical pumping created charge carriers in both the 2-D metals and graphene components. Wavelength-dependent probing suggests that graphene-to-metal carrier transfer occurred on a sub-picosecond time scale. Following rapid (<300 fs) carrier-carrier scattering, charge carriers monitored through the metal interband transition relaxed through several consecutive cooling mechanisms that included sub-picosecond carrier-phonon scattering and dissipation to the silicon carbide substrate over tens of picoseconds. By studying 2-D In, 2-D Ga, and a Ga/In alloy, we resolved accelerated electron-phonon scattering rates upon alloy formation as well as structural influences on the excitation of in-plane phonon shear modes. More rapid cooling in alloys is attributed to increased lattice disorder, which was observed through correlative polarization-resolved second harmonic generation and electron microscopy. This connection between the electronic relaxation rates, far-field optical responses, and metal lattice disorder is made possible by the intimate relation between nonlinear optical properties and atomic-level structure in these materials. These studies provided insights into electronic carrier dynamics in 2-D crystalline elemental metals, including resolving contributions from specific components of a 2-D metal-containing heterojunction. The correlative ultrafast spectroscopy and nonlinear microscopy results suggest that the energy dissipation rates can be tuned through atomic-level structures.

Time-Resolved Electrical Scanning Probe Microscopy of Layered Perovskites Reveals Spatial Variations in Photoinduced Ionic and Electronic Carrier Motion.

We study light-induced dynamics in thin films comprising Ruddlesden-Popper phases of the layered 2D perovskite (C4H9NH3)2PbI4. We probe ionic and electronic carrier dynamics using two complementary scanning probe methods, time-resolved G-mode Kelvin probe force microscopy and fast free time-resolved electrostatic force microscopy, as a function of position, time, and illumination. We show that the average surface photovoltage sign is dominated by the band bending at the buried perovskite-substrate interface. However, the film exhibits substantial variations in the spatial and temporal response of the photovoltage. Under illumination, the photovoltage equilibrates over hundreds of microseconds, a time scale associated with ionic motion and trapped electronic carriers. Surprisingly, we observe that the surface photovoltage of the 2D grain centers evolves more rapidly in time than at the grain boundaries. We propose that the slower evolution at grain boundaries is due to a combination of ion migration occurring between PbI4 planes, as well as electronic carriers traversing grain boundary traps, thereby changing the time-dependent band unbending at grain boundaries. These results provide a model for the photoinduced dynamics in 2D perovskites and are a useful basis for interpreting photovoltage dynamics on hybrid 2D/3D structures.

Dissecting charge relaxation pathways in CdSe/CdS nanocrystals using femtosecond two-dimensional electronic spectroscopy.

Exciton relaxation dynamics of CdSe and quasi-type-II CdSe/CdS core/shell nanocrystals were examined using femtosecond two-dimensional electronic spectroscopy (2DES). The use of 2DES allowed for determination of structure-specific and state-resolved carrier dynamics for CdSe nanocrystals formed with five, or fewer, CdS passivation monolayers (ML). For CdSe and CdSe/CdS nanocrystals formed with one through three MLs of CdS, excitation using broad bandwidth femtosecond visible laser pulses generated electron-hole pairs among the |X1〉 = 2.14 eV and |X2〉 = 2.27 eV exciton states. For both excitations, the electron is promoted to the lowest energy excited (1Se) conduction-band state and the hole is in the 1S3/2 (X1) or 2S3/2 (X2) valence-band state. Therefore, the relaxation dynamics of the hot hole were isolated by monitoring the-time-dependent amplitude of 2DES cross peaks. The time constant for hot hole relaxation within the CdSe valence band was 150 ± 45 fs. Upon passivation by CdS, this hole relaxation time constant increased to 170 ± 30 fs (CdSe/CdS-3ML). This small increase was attributed to the formation of a graded, or alloyed, interfacial region that precedes the growth of a uniform CdS capping layer. The small increase in hole relaxation time reflects the larger nanocrystal volume of the CdSe/CdS system with respect to the CdSe nanocrystal core. In contrast, the dynamics of larger core/shell nanocrystals (≥4ML CdS) exhibited a picosecond buildup in 2DES cross-peak amplitude. This time-dependent response was attributed to interfacial hole transfer from CdS to CdSe valence-band states. Importantly, the 2DES data distinguish CdSe exciton relaxation from interfacial carrier transfer dynamics. In combination, isolation of structurally well-defined nanocrystals 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.

Superatom State-Resolved Dynamics of the Au25(SC8H9)18(-) Cluster from Two-Dimensional Electronic Spectroscopy.

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.

Carrier dynamics of electrons and holes in moderately doped silicon.

A time-domain spectroscopic technique, based on the generation and detection of a collimated beam of subpicosecond broadband terahertz pulses, is used to measure the absorption and dispersion of n- and p-type silicon, with resistivities of 0.1, 1, and 10 \ensuremath{\Omega} cm in the submillimeter range of 0.1--2 THz. From the transmission measurements performed at room temperature and at 80 K, the absorption and dispersion, and concomitantly the full complex conductivity, of the doped silicon could be obtained. The results provide an accurate view on the dynamics of the electrons and the holes. Although the simple Drude model, with an energy-independent relaxation time, gives a surprisingly accurate description of the observed carrier dynamics, the measurements do show that some refinements are needed. An extended model, with an energy-dependent carrier-relaxation rate, can explain most of the observed deviations from the simple Drude model.