Sub-10-fs observation of bound exciton formation in organic optoelectronic devices.

Fundamental mechanisms underlying exciton formation in organic semiconductors are complex and elusive as it occurs on ultrashort sub-100-fs timescales. Some fundamental aspects of this process, such as the evolution of exciton binding energy, have not been resolved in time experimentally. Here, we apply a combination of sub-10-fs Pump-Push-Photocurrent, Pump-Push-Photoluminescence, and Pump-Probe spectroscopies to polyfluorene devices to track the ultrafast formation of excitons. While Pump-Probe is sensitive to the total concentration of excited states, Pump-Push-Photocurrent and Pump-Push-Photoluminescence are sensitive to bound states only, providing access to exciton binding dynamics. We find that excitons created by near-absorption-edge photons are intrinsically bound states, or become such within 10 fs after excitation. Meanwhile, excitons with a modest >0.3 eV excess energy can dissociate spontaneously within 50 fs before acquiring bound character. These conclusions are supported by excited-state molecular dynamics simulations and a global kinetic model which quantitatively reproduce experimental data.

Multipulse Terahertz Spectroscopy Unveils Hot Polaron Photoconductivity Dynamics in Metal-Halide Perovskites.

Hot carriers in metal-halide perovskites (MHPs) present a foundation for understanding carrier-phonon coupling in the materials as well as the prospective development of high-performance hot carrier photovoltaics. While the carrier population dynamics during cooling have been scrutinized, the evolution of the hot carrier properties, namely mobility, remains largely unexplored. Here we introduce novel ultrafast visible pump-infrared push-terahertz probe spectroscopy to monitor the real-time conductivity dynamics of cooling carriers in methylammonium lead iodide. We find a decrease in mobility upon optically re-exciting the carriers, as expected for band transport. Surprisingly, the conductivity recovery is incommensurate with the hot carrier population dynamics measured by infrared probe and exhibits a negligible dependence on the hot carrier density. Our results reveal the importance of localized lattice heating toward the hot carrier mobility. This collective polaron-lattice phenomenon may contribute to the unusual photophysics of MHPs and should be accounted for in hot carrier devices.

Two-photon conversion of a bacterial phytochrome.

In nature, sensory photoreceptors underlie diverse spatiotemporally precise and generally reversible biological responses to light. Photoreceptors also serve as genetically encoded agents in optogenetics to control by light organismal state and behavior. Phytochromes represent a superfamily of photoreceptors that transition between states absorbing red light (Pr) and far-red light (Pfr), thus expanding the spectral range of optogenetics to the near-infrared range. Although light of these colors exhibits superior penetration of soft tissue, the transmission through bone and skull is poor. To overcome this fundamental challenge, we explore the activation of a bacterial phytochrome by a femtosecond laser emitting in the 1 µm wavelength range. Quantum chemical calculations predict that bacterial phytochromes possess substantial two-photon absorption cross sections. In line with this notion, we demonstrate that the photoreversible Pr ↔ Pfr conversion is driven by two-photon absorption at wavelengths between 1170 and 1450 nm. The Pfr yield was highest for wavelengths between 1170 and 1280 nm and rapidly plummeted beyond 1300 nm. By combining two-photon activation with bacterial phytochromes, we lay the foundation for enhanced spatial resolution in optogenetics and unprecedented penetration through bone, skull, and soft tissue.

Kinetic modelling of intraband carrier relaxation in bulk and nanocrystalline lead-halide perovskites.

The relaxation of high-energy "hot" carriers in semiconductors is known to involve the redistribution of energy between hot and cold carriers, as well as the transfer of energy from hot carriers to phonons. Over the past few years, these two processes have been identified in lead-halide perovskites (LHPs) using ultrafast pump-probe experiments, but their interplay is not fully understood. Here we present a practical and intuitive kinetic model that accounts for the effects of both hot and cold carriers on carrier relaxation in LHPs. We apply this model to describe the dynamics of hot carriers in bulk and nanocrystalline CsPbBr3 as observed by multi-pulse "pump-push-probe" spectroscopy. The model captures the slowing of the relaxation dynamics in the materials as the number of hot carriers increases, which has previously been explained by a "hot-phonon bottleneck" mechanism. The model also correctly predicts an acceleration of the relaxation kinetics as the number of cold carriers in the samples is increased. Using a series of natural approximations, we reduce our model to a simple form containing terms for the carrier-carrier and carrier-phonon interactions. The model can be instrumental for evaluating the details of carrier relaxation and carrier-phonon couplings in LHPs and other soft optoelectronic materials.

Hot Carrier Dynamics in Perovskite Nanocrystal Solids: Role of the Cold Carriers, Nanoconfinement, and the Surface.

Carrier cooling is of widespread interest in the field of semiconductor science. It is linked to carrier-carrier and carrier-phonon coupling and has profound implications for the photovoltaic performance of materials. Recent transient optical studies have shown that a high carrier density in lead-halide perovskites (LHPs) can reduce the cooling rate through a "phonon bottleneck". However, the role of carrier-carrier interactions, and the material properties that control cooling in LHPs, is still disputed. To address these factors, we utilize ultrafast "pump-push-probe" spectroscopy on LHP nanocrystal (NC) films. We find that the addition of cold carriers to LHP NCs increases the cooling rate, competing with the phonon bottleneck. By comparing different NCs and bulk samples, we deduce that the cooling behavior is intrinsic to the LHP composition and independent of the NC size or surface. This can be contrasted with other colloidal nanomaterials, where confinement and trapping considerably influence the cooling dynamics.

Resolution and contrast in terahertz pulse time-domain holographic reconstruction.

Here, we present a comprehensive study of the reconstruction quality in terahertz (THz) pulse time-domain holography. We look into single wavelength reconstructions, as well as broadband recovery enabled by the ultrabroadband nature of radiation and coherent detection enabled by electro-optic or photoconductive sensing. We demonstrate the transverse resolution dependence for amplitude and phase objects on the solid angle of the inline recorded time-domain THz hologram, and then turn to the contrast of reconstructed binary amplitude objects, and further to longitudinal resolution of phase objects. We show that transverse resolution can reach values comparable to the wavelength of the radiation used, and longitudinally, phase objects can be resolved with even greater precision. We compare the obtained resolution with theoretical estimates and show that THz pulse time-domain holography is a powerful non-contact imaging tool.

Effect of object thickness on ultrashort pulse diffraction.

When calculated in the spectral domain, the propagation of an ultrashort optical pulse may suffer from inaccuracy due to the finite thickness of the object it diffracts on. Unlike monochromatic radiation, ultrashort pulse interaction with an object in the time domain depends on the pulse longitudinal coordinate. Here, we propose an algorithm to study the effect of the object thickness on ultrashort pulse diffraction on amplitude, phase, and three-dimensional highly scattering objects. The algorithm comprises a stepwise approach to simulating the diffraction of ultrashort pulses on apertures or scatterers having a finite thickness. We confirm the applicability of the approach and convergence of the result upon reducing the simulation step. We compare the simulation results obtained with traditionally calculated wavefields and the updated results obtained with the proposed approach. We reveal a discrepancy of about 7% for pulsed radiation with λ=800nm on a 1 mm thick object. Then, we demonstrate the dependence of this mismatch on the object thickness and show that for non-Gaussian vortex beams, this effect is even more pronounced. We reveal that spatiotemporal coupling effects depend on the pulse-object interaction simulation approach as well. The obtained results demonstrate that applicability of the single-layer representation of the simulated object strongly depends on its specific features, and inaccuracy of such an approach strongly depends on individual characteristics of the object.

Spatio-temporal and spatiospectral metrology of terahertz broadband uniformly topologically charged vortex beams.

A comprehensive characterization of the diffraction properties of terahertz (THz) pulsed broadband vortex beams consisting of several electromagnetic field oscillations requires state-of-the-art techniques for studying the evolution of a wavefront as it propagates. For this purpose, we have applied the capabilities offered by THz pulse time domain holography. Accurate metrological study of pulsed single-period THz field propagation allowed us to reveal the spatio-temporal and spatiospectral couplings in broadband uniformly topologically charged vortex beams. Here, we reveal dynamics of such beam propagation in a free space as well as in the experiment with edge diffraction with 50% blocking of the beam focal waist. In this study, we compare the dynamics of freely propagating and edge-diffracted THz vortex. Despite the fact that in the amplitude representation one can observe the emergence of strong asymmetry, analysis of the spectral trajectory of the singular point at some distance from the obstacle and the visualization of phase distribution for individual spectral components testify to the conservation of transverse energy circulation. Similar to the edge diffraction of monochromatic optical vortices, it can be interpreted as self-reconstruction of vortex properties. The given term has not previously been used for the case of pulsed broadband THz beams, to the best of our knowledge.

Increasing the resolution of the reconstructed image in terahertz pulse time-domain holography.

In this paper, we present a novel numerical approach for increasing the resolution of retrieved images of objects after their diffraction patterns are recorded via terahertz pulse time-domain holography (THz PTDH). THz PTDH allows for spectrally resolved imaging with high spatial resolution and does not require the fine alignment of complex optics in the THz path. The proposed data post-processing method opens up the possibility to reconstruct holograms recorded with spatially restricted THz detectors, and overcome the diffraction limit even for the lower-frequency spectral components. The method involves an iterative procedure of backward-forward wavefront propagation to simulate the field distribution beyond the initially recorded hologram area. We show significant improvement in both the object reconstruction and contrast across the whole spectrum, with qualitative resolution enhancement at lower frequency spectral components.

Ultrafast Intraband Spectroscopy of Hot-Carrier Cooling in Lead-Halide Perovskites.

The rapid relaxation of above-band-gap "hot" carriers (HCs) imposes the key efficiency limit in lead-halide perovskite (LHP) solar cells. Recent studies have indicated that HC cooling in these systems may be sensitive to materials composition, as well as the energy and density of excited states. However, the key parameters underpinning the cooling mechanism are currently under debate. Here we use a sequence of ultrafast optical pulses (visible pump-infrared push-infrared probe) to directly compare the intraband cooling dynamics in five common LHPs: FAPbI3, FAPbBr3, MAPbI3, MAPbBr3, and CsPbBr3. We observe ∼100-900 fs cooling times, with slower cooling at higher HC densities. This effect is strongest in the all-inorganic Cs-based system, compared to the hybrid analogues with organic cations. These observations, together with band structure calculations, allow us to quantify the origin of the "hot-phonon bottleneck" in LHPs and assert the thermodynamic contribution of a symmetry-breaking organic cation toward rapid HC cooling.

Boosting Terahertz Photoconductive Antenna Performance with Optimised Plasmonic Nanostructures.

Advanced nanophotonics penetrates into other areas of science and technology, ranging from applied physics to biology, which results in many fascinating cross-disciplinary applications. It has been recently demonstrated that suitably engineered light-matter interactions at the nanoscale can overcome the limitations of today's terahertz (THz) photoconductive antennas, making them one step closer to many practical implications. Here, we push forward this concept by comprehensive numerical optimization and experimental investigation of a log-periodic THz photoconductive antenna coupled to a silver nanoantenna array. We shed light on the operation principles of the resulting hybrid THz antenna, providing an approach to boost its performance. By tailoring the size of silver nanoantennas and their arrangement, we obtain an enhancement of optical-to-THz conversion efficiency 2-fold larger compared with previously reported results for similar structures, and the strongest enhancement is around 1 THz, a frequency range barely achievable by other compact THz sources. We also propose a cost-effective fabrication procedure to realize such hybrid THz antennas with optimized plasmonic nanostructures via thermal dewetting process, which does not require any post processing and makes the proposed solution very attractive for applications.

Detection of harmful residues in honey using terahertz time-domain spectroscopy.

Terahertz time-domain spectroscopy (THz-TDS) has been applied for the detection and discrimination of harmful chemical residues in honey. Three antibiotics (sulfapyridine, sulfathiazole, and tetracycline) and two acaricides (coumaphos and amitraz) were characterized in the THz frequency regime between 0.5 THz and 6.0 THz. All chemical substances present distinct absorption peaks. THz transmission measurements of honey mixtures with antibiotics have been performed, revealing that antibiotic residues are traceable in highly absorptive food products, such as honey, at concentrations down to 1% weight percentage, thanks to their THz fingerprints. Moreover, multiple antibiotics were identified in their mixture with honey, pointing out the potential of the technique to be used in the near future as a fast, real-time technique for detecting and discriminating multi-residues strictly related to food safety issues.