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Nonlinear optical phenomena are at the heart of various technological domains such as high-speed data transfer, optical logic applications, and emerging fields such as non-reciprocal optics and photonic time crystal design. However, conventional nonlinear materials exhibit inherent limitations in the post-fabrication tailoring of their nonlinear optical properties. Achieving real-time control over optical nonlinearities remains a challenge. In this work, we demonstrate a method to switch third harmonic generation (THG), a commonly occurring nonlinear optical response. Third harmonic generation enhancements up to 50 times are demonstrated in zinc oxide films via the photoexcited state generation and tunable electric field enhancement. More interestingly, the enhanced third harmonic generation follows a quadratic scaling with incident power, as opposed to the conventional cubic scaling, which demonstrates a previously unreported mechanism of third harmonic generation. The THG can also be suppressed by modulating the optical losses in the film. This work shows that the photoexcitation of states can not only enhance nonlinearities, but can create new processes for third harmonic generation. Importantly, the proposed method enables real-time manipulation of the nonlinear response of a medium. The process is switchable and reversible, with the modulations occurring at picosecond timescale. Our study paves the way to boost or suppress the nonlinearities of solid-state media, enabling robust, switchable sources for nonlinear optical applications.

Lead halide perovskite nanocrystals demonstrate efficient up-conversion, although the precise mechanism remains a subject of active research. This study utilizes steady-state and time-resolved spectroscopy methods to unravel the mechanism driving the up-conversion process in CsPbBr3 nanocrystals. Employing above- and below-gap photoluminescence measurements, we extract a distinct phonon mode with an energy of ~7 meV and identify the Pb-Br-Pb bending mode as the phonon involved in the up-conversion process. This result was corroborated by Raman spectroscopy. We confirm an up-conversion efficiency reaching up to 75%. Transient absorption measurements under conditions of sub-gap excitation also unexpectedly reveal coherent phonons for the subset of nanocrystals undergoing up-conversion. This coherence implies that the up-conversion and subsequent relaxation is accompanied by a synchronized and phased lattice motion. This study reveals that efficient up-conversion in CsPbBr3 nanocrystals is powered by a unique interplay between the soft lattice structure, phonons, and excited states dynamics., Comment: Main text has 6 figures, supporting information has 7 figures. total number of pages 39

Lead-halide perovskite nanocrystals such as CsPbBr$_3$, exhibit efficient photoluminescence (PL) up-conversion, also referred to as anti-Stokes photoluminescence (ASPL). This is a phenomenon where irradiating nanocrystals up to 100 meV below gap results in higher energy band edge emission. Most surprising is that ASPL efficiencies approach unity and involve single photon interactions with multiple phonons. This is unexpected given the statistically disfavored nature of multiple-phonon absorption. Here, we report and rationalize near-unity anti-Stokes photoluminescence efficiencies in CsPbBr$_3$ nanocrystals and attribute it to resonant multiple-phonon absorption by polarons. The theory explains paradoxically large efficiencies for intrinsically disfavored, multiple-phonon-assisted ASPL in nanocrystals. Moreover, the developed microscopic mechanism has immediate and important implications for applications of ASPL towards condensed phase optical refrigeration.

Fluorophores emitting in the NIR-IIb wavelength range (1.5 micron - 1.7 micron) show great potential for bioimaging due to their large tissue penetration. However, current fluorophores suffer from poor emission with quantum yields ~2% in aqueous solvents. In this work, we report the synthesis of HgSe/CdSe core/shell quantum dots emitting at 1.7 microns through the interband transition. Growth of a thick shell led to a drastic increase in the photoluminescence quantum yield, with a value of 55% in nonpolar solvents. The quantum yields of our QDs and other reported QDs are explained well by a model of Forster resonance energy transfer to ligands and solvent molecules. The model predicts a quantum yield >6% when these HgSe/CdSe QDs are solubilized in water. Our work demonstrates the importance of a thick type-I shell to obtain bright emission in the NIR-IIb region, Comment: Main text: 9 pages, 4 figures. Supplementary Information: 31 pages, 21 figures

We report spin-polarized transient absorption for colloidal CdSe nanoplatelets as functions of thickness (2 to 6 monolayer thickness) and core/shell motif. Using electro-optical modulation of co- and cross-polarization pump-probe combinations, we sensitively observe spin-polarized transitions. Core-only nanoplatelets exhibit few-picosecond spin lifetimes that weakly increase with layer thickness. Spectral content of differenced spin-polarized signals indicate biexciton binding energies that decrease with increasing thickness and smaller values than previously reported. Shell growth of CdS with controlled thicknesses, which partially delocalize the electron from the hole, significantly increases the spin lifetime to ~49 picoseconds at room temperature. Implementation of ZnS shells, which do not alter delocalization but do alter surface termination, increased spin lifetimes up to ~100 ps, bolstering the interpretation that surface termination heavily influences spin coherence, likely due to passivation of dangling bonds. Spin precession in magnetic fields both confirms long coherence lifetime at room temperature and yields excitonic g-factor., Comment: Main text + supplementary, 18 pages total, 8 figures total

Terahertz (THz) sciences and technologies have contributed to a rapid development of a wide range of applications and expanded the frontiers in fundamental science. Spintronic terahertz emitters offer conceptual advantages since the spin orientation in the magnetic layer can be easily controlled either by the externally applied magnetic field or by the internal magnetic field distribution determined by the specific shape of the magnetic elements. Here, we report a switchable terahertz source based on micropatterned magnetic heterostructures driven by femtosecond laser pulses. We show that the precise tunability of the polarization state is facilitated by the underlying magnetization texture of the magnetic layer that is dictated by the shape of the microstructure. These results also reveal the underlying physical mechanisms of a nonuniform magnetization state on the generation of ultrafast spin currents in the magnetic heterostructures. Our findings indicate that the emission of the linearly polarized THz waves can be switched on and off by saturating the sample using a biasing magnetic field, opening fascinating perspectives for integrated on-chip THz devices with wide-ranging potential applications.

The unique properties of the emerging photonic materials - conducting nitrides and oxides - especially their tailorability, large damage thresholds, and the so-called epsilon-near-zero (ENZ) behavior, have enabled novel photonic phenomena spanning optical circuitry, tunable metasurfaces, and nonlinear optical devices. This work explores direct control of the optical properties of polycrystalline titanium nitride (TiN) and aluminum-doped zinc oxide (AZO) by tailoring the film thickness, and their potential for ENZ-enhanced photonic applications. We demonstrate that TiN-AZO bilayers act as Ferrell-Berreman metasurfaces with thickness-tailorable epsilon-near-zero resonances in the AZO films operating in the telecom wavelengths spanning from 1470 to 1750 nm. The bilayer stacks also act as strong light absorbers in the ultraviolet regime employing the radiative ENZ modes and the Fabry-Perot modes in the constituent TiN films. The studied Berreman metasurfaces exhibit optically-induced reflectance modulation of 15% with picosecond response-time. Together with the optical response tailorability of conducting oxides and nitrides, utilizing the field-enhancement near the tunable ENZ regime could enable a wide range of nonlinear optical phenomena, including all-optical switching, time refraction, and high-harmonic generation.

Radiation brightening was recently observed in a multi-fluorophore-conjugated brome mosaic virus (BMV) particle, at room temperature under pulsed excitation. Based on its nonlinear dependence on the number of fluorophores, the origins of the phenomenon were attributed to a collective relaxation. However, the mechanism remains unknown. We present ultrafast transient absorption and fluorescence spectroscopic studies which shed new light on the collective nature of the relaxation dynamics in such radiation-brightened, multi-fluorophore particles. Our findings indicate that the emission dynamics is consistent with a superradiance mechanism. The ratio between the rates of competing radiative and non-radiative relaxation pathways depends on the number of fluorophores per virus. We also discuss the evidence of coherent oscillations in the transient absorption trace from multi-fluorophore conjugated which last for $\sim100$s of picoseconds, at room temperature. The findings suggest that small icosahedral virus shells provide a unique biological scaffold for developing non-classical, deep subwavelength light sources, and may open new realms for the development of photonic probes for medical imaging applications.

Nonradiative processes limit optoelectronic functionality of nanocrystals and curb their device performance. Nevertheless, the dynamic structural origins of nonradiative relaxations in nanocrystals are not understood. Here, femtosecond electron diffraction measurements corroborated by atomistic simulations uncover transient lattice deformations accompanying radiationless electronic processes in semiconductor nanocrystals. Investigation of the excitation energy dependence shows that hot carriers created by a photon energy considerably larger than the bandgap induce structural distortions at nanocrystal surfaces on few picosecond timescales associated with the localization of trapped holes. On the other hand, carriers created by a photon energy close to the bandgap result in transient lattice heating that occurs on a much longer 200 ps timescale, governed by an Auger heating mechanism. Elucidation of the structural deformations associated with the surface trapping of hot holes provides atomic-scale insights into the mechanisms deteriorating optoelectronic performance and a pathway towards minimizing these losses in nanocrystal devices., Comment: 17 pages, 4 figures

The dielectric permittivity of a material encapsulates the essential physics of light-matter interaction into the material's local response to optical excitation. Dynamic, photo-induced modulation of the permittivity can enable an unprecedented level of control over the phase, amplitude, and polarization of light. Therefore, the detailed dynamic characterization of technology-relevant materials with substantially tunable optical properties and fast response times is a crucial step in the realization of tunable optical devices. This work reports on the extraordinarily large permittivity changes in zinc oxide thin films (up to -3.6 relative change in the real part of the dielectric permittivity at 1600 nm wavelength) induced by optically generated free carriers. We demonstrate broadband reflectance modulation up to 70 percent in metal-backed oxide mirrors at the telecommunication wavelengths, with picosecond-scale relaxation times. The epsilon near zero points of the films can be dynamically shifted from 8.5 microns to 1.6 microns by controlling the pump fluence. Finally, we show that the modulation can be selectively enhanced at specific wavelengths employing metal-backed ZnO disks while maintaining picosecond-scale switching times. This work provides insights into the free-carrier assisted permittivity modulation in zinc oxide and could enable the realization of novel dynamic devices for beam-steering, polarizers, and spatial light modulators.

Ultrafast spectroscopy is an important tool for studying photoinduced dynamical processes in atoms, molecules, and nanostructures. Typically, the time to perform these experiments ranges from several minutes to hours depending on the choice of spectroscopic method. It is desirable to reduce this time overhead to not only to shorten time and laboratory resources, but also to make it possible to examine fragile specimens which quickly degrade during long experiments. In this article, we motivate using compressive sensing to significantly shorten data acquisition time by reducing the total number of measurements in ultrafast spectroscopy. We apply this technique to experimental data from ultrafast transient absorption spectroscopy and ultrafast terahertz spectroscopy and show that good estimates can be obtained with as low as 15% of the total measurements, implying a 6-fold reduction in data acquisition time.

Transition metal nitrides have recently gained attention in the fields of plasmonics, plasmon-enhanced photocatalysis, photothermal applications, and nonlinear optics because of their suitable optical properties, refractory nature, and large laser damage thresholds. This work reports comparative studies of the transient response of films of titanium nitride, zirconium nitride, and Au under femtosecond excitation. Broadband transient optical characterization helps to adjudicate earlier, somewhat inconsistent reports regarding hot electron lifetimes based upon single wavelength measurements. These pump-probe experiments show sub-picosecond transient dynamics only within the epsilon-near-zero window of the refractory metals. The dynamics are dominated by photoinduced interband transitions resulting from ultrafast electron energy redistribution. The enhanced reflection modulation in the epsilon-near-zero window makes it possible to observe the ultrafast optical response of these films at low pump fluences. These results indicate that electron-phonon coupling in TiN and ZrN is 25-100 times greater than in Au. Strong electron-phonon coupling drives the sub-picosecond optical response and facilitates greater lattice heating compared to Au, making TiN and ZrN promising for photothermal applications. The spectral response and dynamics of TiN and ZrN are only weakly sensitive to pump fluence and pump excitation energy. However, the magnitude of the response is much greater at higher pump photon energies and higher fluences, reaching peak observed values of 15 % in TiN and 50 % in ZrN in the epsilon-near-zero window.

Organic-inorganic hybrid perovskites such as methylammonium lead iodide (CH3NH3PbI3) are game-changing semiconductors for solar cells and light-emitting devices owing to their exceptionally long carrier lifetime and diffusion length. Determining whether the large dipole moment of the organic cation and dynamic disorder benefit the optoelectronic properties of CH3NH3PbI3 has been an outstanding challenge. Herein, via transient absorption measurements employing an infrared pump pulse tuned to a methylammonium vibration, we observe slow, nanosecond-long thermal dissipation from the selectively excited organic mode to the entire lattice. Resulting transient electronic signatures, during the period of thermal-nonequilibrium when the induced thermal motions are mostly concentrated on the organic sublattice, reveal that induced motions of the organic cations do not alter absorption or photoluminescence response of CH3NH3PbI3, beyond thermal effects. Our results suggest that the attractive optoelectronic properties of CH3NH3PbI3 mainly derive from the inorganic lead-halide framework., Comment: 18 pages, 4 figures

Ordered electronic phases are intimately related to emerging phenomena such as high Tc superconductivity and colossal magnetoresistance. The coupling of electronic charge with other degrees of freedom such as lattice and spin are of central interest in correlated systems. Their correlations have been intensively studied from femtosecond to picosecond time scales, while the dynamics of ordered electronic phases beyond nanoseconds are usually assumed to follow a trivia thermally driven recovery. Here, we report an unusual slowing down of the recovery of an electronic phase across a first-order phase transition, far beyond thermal relaxation time. Following optical excitation, the recovery time of both transient optical reflectivity and x-ray diffraction intensity from a charge-ordered superstructure in a La$_{1/3}$Sr$_{2/3}$FeO$_3$ thin film increases by orders of magnitude longer than the independently measured lattice cooling time when the sample temperature approaches the phase transition temperature. The combined experimental and theoretical investigations show that the slowing down of electronic recovery corresponds to the pseudo-critical dynamics that originates from magnetic interactions close to a weakly first-order phase transition. This extraordinary long electronic recovery time exemplifies an interplay of ordered electronic phases with magnetism beyond thermal processes in correlated systems.

Phonons are produced when an excited vacancy in cuprous oxide (Cu$_2$O) relaxes. Time resolved luminescence was used to find the excited copper vacancy (acceptor) and oxygen vacancy (donor) trap levels and lifetimes. It was also used to determine the typical energy and number of phonons in the phonon pulses emitted by vacancies. The vacancy properties of cuprous oxide are controlled by several synthesis parameters and by the temperature. We directly demonstrate the absorption of light by oxygen vacancies with transient absorption. Copper and oxygen vacancies behave differently, in part because the two kinds of traps capture carriers from different states. For example, the copper vacancy luminescence lifetime is around 25 times greater at low temperature. However, both kinds of vacancy luminescence are consistent with a Poissonian multiple phonon emission model., Comment: Corrected author metadata

The organic-inorganic hybrid lead trihalide perovskites have been emerging as the most attractive photovoltaic material. As regulated by Shockley-Queisser theory, a formidable materials science challenge for the next level improvement requires further band gap narrowing for broader absorption in solar spectrum, while retaining or even synergistically prolonging the carrier lifetime, a critical factor responsible for attaining the near-band gap photovoltage. Herein, by applying controllable hydrostatic pressure we have achieved unprecedented simultaneous enhancement in both band gap narrowing and carrier lifetime prolongation (up to 70~100% increase) under mild pressures at ~0.3 GPa. The pressure-induced modulation on pure hybrid perovskites without introducing any adverse chemical or thermal effect clearly demonstrates the importance of band edges on the photon-electron interaction and maps a pioneering route towards a further boost in their photovoltaic performance., Comment: 23 pages, 4 figures

The coupling between strain gradients and polarization, known as flexoelectricity, offers a new mechanism to control the functionality of dielectric materials. However, for the effect to be practically attractive, dynamic control of the strain gradient with magnitudes far exceeding those achievable via mechanical deformation (~10 $m^{-1}$) is needed. Strain-engineered thin films exhibit extraordinary strain gradients of $10^5-10^6 m{-1}$ arising from structural relaxation within a short space range that greatly enhances the steady-state flexoelectric effect. Here we report a giant, optically initiated dynamic enhancement of the strain gradient, also on the order of $10^5 -10^6 m^{-1}$, in ferroelectric BiFeO3 epitaxial thin films via time-dependent coherence analysis of X-ray diffractions. The finding opens the door for dynamic coupling of the flexoelectric effect with light, making optical switching of polarization, and thus application such as direct optical writing of non-volatile ferroelectric memory, possible. A combination of time-resolved X-ray scattering and optical spectroscopy shows that the enhancement of the strain gradient is due to a piezoelectric effect driven by a transient screening electric field, opening the opportunity for new ways of studying flexoelectric effect in strain engineered ferroelectric thin films., Comment: 17 pages, 5 figures in the main text; 13 pages, 6 figures in the supplementary information