Ultrafast Photoinduced Phase Change in SnSe.

Time-resolved multiterahertz (THz) spectroscopy is used to observe an ultrafast, nonthermal electronic phase change in SnSe driven by interband photoexcitation with 1.55 eV pump photons. The transient THz photoconductivity spectrum is found to be Lorentzian-like, indicating charge localization and phase segregation. The rise of photoconductivity is bimodal in nature, with both a fast and slow component due to excitation into multiple bands and subsequent intervalley scattering. The THz conductivity magnitude, dynamics, and spectra show a drastic change in character at a critical excitation fluence of approximately 6 mJ/cm^{2} due to a photoinduced phase segregation and a macroscopic collapse of the band gap.

Nanoscale force sensing of an ultrafast nonlinear optical response.

The nonlinear optical response of a material is a sensitive probe of electronic and structural dynamics under strong light fields. The induced microscopic polarizations are usually detected via their far-field light emission, thus limiting spatial resolution. Several powerful near-field techniques circumvent this limitation by employing local nanoscale scatterers; however, their signal strength scales unfavorably as the probe volume decreases. Here, we demonstrate that time-resolved atomic force microscopy is capable of temporally and spatially resolving the microscopic, electrostatic forces arising from a nonlinear optical polarization in an insulating dielectric driven by femtosecond optical fields. The measured forces can be qualitatively explained by a second-order nonlinear interaction in the sample. The force resulting from this nonlinear interaction has frequency components below the mechanical resonance frequency of the cantilever and is thus detectable by regular atomic force microscopy methods. The capability to measure a nonlinear polarization through its electrostatic force is a powerful means to revisit nonlinear optical effects at the nanoscale, without the need for emitted photons or electrons from the surface.

Coherent charge-phonon correlations and exciton dynamics in orthorhombic CH3NH3PbI3 measured by ultrafast multi-THz spectroscopy.

We use time-resolved multi-terahertz spectroscopy for the range 4-40 meV to probe coherent and incoherent ultrafast charge carrier and exciton dynamics in the low temperature orthorhombic phase of the hybrid metal halide perovskite CH3NH3PbI3. Time- and energy-resolved terahertz reflectivity maps reveal strongly damped but coherent oscillations in the 2-4 THz reststrahlen band, indicating charge coupling to a distribution of low energy phonon modes centered at 0.9 THz (3.7 meV or 30 cm-1). First-principles calculations reveal that these modes are entirely of mixed organic/inorganic sublattice character, with the power spectrum of the coherent oscillations showing a high frequency cutoff just at the onset of organic cation-only vibrations. Two anomalous reflectivity signatures are observed which are not phonon related, which we assign to a free exciton at 12 meV appearing on a 0.5 ps time scale and a defect bound exciton at 29-32 meV appearing on slower 1 ps time scale. Our measurements reveal the coherent coupling of charges to low energy vibrations of mixed sublattice character and the presence of two distinct populations of free and bound excitons at low temperatures.

Ultrafast correlated charge and lattice motion in a hybrid metal halide perovskite.

Hybrid organic-inorganic halide perovskites have shown remarkable optoelectronic properties, exhibiting an impressive tolerance to defects believed to originate from correlated motion of charge carriers and the polar lattice forming large polarons. Few experimental techniques are capable of directly probing these correlations, requiring simultaneous sub-millielectron volt energy and femtosecond temporal resolution after absorption of a photon. Here, we use time-resolved multi-THz spectroscopy, sensitive to the internal excitations of the polaron, to temporally and energetically resolve the coherent coupling of charges to longitudinal optical phonons in single-crystal CH3NH3PbI3 (MAPI). We observe room temperature intraband quantum beats arising from the coherent displacement of charge from the coupled phonon cloud. Our measurements provide strong evidence for the existence of polarons in MAPI at room temperature, suggesting that electron/hole-phonon coupling is a defining aspect of the hybrid metal-halide perovskites contributing to the protection from scattering and enhanced carrier lifetimes that define their usefulness in devices.

How optical excitation controls the structure and properties of vanadium dioxide.

We combine ultrafast electron diffraction and time-resolved terahertz spectroscopy measurements to link structure and electronic transport properties during the photoinduced insulator-metal transitions in vanadium dioxide. We determine the structure of the metastable monoclinic metal phase, which exhibits antiferroelectric charge order arising from a thermally activated, orbital-selective phase transition in the electron system. The relative contribution of the photoinduced monoclinic and rutile metals to the time-dependent and pump-fluence-dependent multiphase character of the film is established, as is the respective impact of these two distinct phase transitions on the observed changes in terahertz conductivity. Our results represent an important example of how light can control the properties of strongly correlated materials and demonstrate that multimodal experiments are essential when seeking a detailed connection between ultrafast changes in optical-electronic properties and lattice structure.

Active phase control of terahertz pulses using a dynamic waveguide.

Control over the spectral phase of a light pulse is a fundamental step toward arbitrary signal generation in a spectral band. For the terahertz spectral regime, pulse shaping holds the key for applications ranging from ultra-high speed wireless data transmission to quantum control with shaped fields. In this work, we demonstrate a technique for all-optical and reconfigurable control of the spectral phase of a light pulse in the important terahertz (THz) band. The technique is based on interaction of a guided THz pulse with patterned photoexcited regions within a uniform silicon-filled parallel-plate waveguide. We use this platform to demonstrate broadband and tunable positive and negative chirp of a THz pulse, as well as control of the pulse carrier envelope phase.

Piezoelectric scattering limited mobility of hybrid organic-inorganic perovskites CH3NH3PbI3.

Carrier mobility is one of the most important parameters for semiconducting materials and their use in optoelectronic devices. Here we report a systematic first principles analysis of the acoustic phonon scattering mechanism that limits the mobility of CH3NH3PbI3 (MAPbI3) perovskites. Due to the unique hybrid organic-inorganic structure, the mechanical, electronic and transport properties are dominated by the same factor, i.e. the weak interatomic bond and the easy rotation of methylammonium (MA) molecules under strain. Both factors make MAPbI3 soft. Rotation of MA molecule induces a transverse shift between Pb and I atoms, resulting in a very low deformation potential and a strong piezoelectricity in MAPbI3. Hence the carrier mobility of pristine MAPbI3 is limited by the piezoelectric scattering, which is consistent to the form of its temperature dependence. Our calculations suggest that in the pristine limit, a high mobility of about several thousand cm2 V-1 S-1 is expected for MAPbI3.

Dynamic creation of a light-induced terahertz guided-wave resonator.

We demonstrate a dynamic light-induced resonator for terahertz (THz) frequency light created on ultrashort time scales inside a planar waveguide. The resonator is created by patterned femtosecond photoexcitation of a one-dimensional array of photoconductive regions inside a silicon-filled parallel plate waveguide. The metal-dielectric photonic crystal is created on a 2 ps time scale, ten times faster than the 20 ps transit time of the THz light through the array. The resonance reveals itself through narrowband THz transmission enhancement with accompanying phase modulation producing an induced group delay of up to 10.8 ps near resonance.

Optically induced mode coupling and interference in a terahertz parallel plate waveguide.

We demonstrate all-optical control of terahertz (THz) wavemode coupling in a silicon-filled parallel plate waveguide. Using an asymmetric photoexcitation of charge carriers on the surface of the silicon slab within the waveguide, the symmetry is broken, and THz light is partially coupled from TEM to higher-order TM modes. The resulting interference between these modes and the residual TEM mode leads to a strong frequency-dependent transmission modulation. This frequency-selective modulation is widely tunable by adjusting the relative modal phases by translating the excitation along the propagation direction. The experimental observations are well described by a numerical and analytic model of modal interference.

Graphene conductance uniformity mapping.

We demonstrate a combination of micro four-point probe (M4PP) and non-contact terahertz time-domain spectroscopy (THz-TDS) measurements for centimeter scale quantitative mapping of the sheet conductance of large area chemical vapor deposited graphene films. Dual configuration M4PP measurements, demonstrated on graphene for the first time, provide valuable statistical insight into the influence of microscale defects on the conductance, while THz-TDS has potential as a fast, non-contact metrology method for mapping of the spatially averaged nanoscopic conductance on wafer-scale graphene with scan times of less than a minute for a 4-in. wafer. The combination of M4PP and THz-TDS conductance measurements, supported by micro Raman spectroscopy and optical imaging, reveals that the film is electrically continuous on the nanoscopic scale with microscopic defects likely originating from the transfer process, dominating the microscale conductance of the investigated graphene film.

Simultaneous reference and differential waveform acquisition in time-resolved terahertz spectroscopy.

We present a new method for data acquisition in time-resolved terahertz spectroscopy experiments. Our approach is based on simultaneous collection of reference and differential THz scans. Both the optical THz generation beam and the pump beam are modulated at two different frequencies that are not harmonic with respect to each other. Our method allows not only twice as fast data acquisition but also minimization of noise connected to slowly varying laser power fluctuations and timing instabilities. Our use of the nonlinear crystal N-benzyl-2-methyl-4-nitroaniline (BNA) enables time-resolved THz spectroscopy to beyond 5 THz, thereby highlighting that the presented method is especially valuable at higher frequencies where phase errors in the data acquisition become increasingly important.