Cavity-mediated thermal control of metal-to-insulator transition in 1T-TaS2.

Placing quantum materials into optical cavities provides a unique platform for controlling quantum cooperative properties of matter, by both weak and strong light-matter coupling1,2. Here we report experimental evidence of reversible cavity control of a metal-to-insulator phase transition in a correlated solid-state material. We embed the charge density wave material 1T-TaS2 into cryogenic tunable terahertz cavities3 and show that a switch between conductive and insulating behaviours, associated with a large change in the sample temperature, is obtained by mechanically tuning the distance between the cavity mirrors and their alignment. The large thermal modification observed is indicative of a Purcell-like scenario in which the spectral profile of the cavity modifies the energy exchange between the material and the external electromagnetic field. Our findings provide opportunities for controlling the thermodynamics and macroscopic transport properties of quantum materials by engineering their electromagnetic environment.

Manipulation of Charge Delocalization in a Bulk Heterojunction Material Using a Mid-Infrared Push Pulse.

In organic bulk heterojunction materials, charge delocalization has been proposed to play a vital role in the generation of free carriers by effectively reducing the Coulomb attraction via an interfacial charge transfer exciton (CTX). Pump-push-probe (PPP) experiments produced evidence that the excess energy given by a push pulse enhances delocalization, thereby increasing photocurrent. However, previous studies have employed near-infrared push pulses in the range ∼0.4-0.6 eV, which is larger than the binding energy of a typical CTX. This raises the doubt that the push pulse may directly promote dissociation without involving delocalized states. Here, we perform PPP experiments with mid-infrared push pulses at energies that are well below the binding energy of a CTX state (0.12-0.25 eV). We identify three types of CTXs: delocalized, localized, and trapped. The excitation resides over multiple polymer chains in delocalized CTXs, while it is restricted to a single chain (albeit maintaining a degree of intrachain delocalization) in localized CTXs. Trapped CTXs are instead completely localized. The pump pulse generates a "hot" delocalized CTX, which promptly relaxes to a localized CTX and eventually to trapped states. We find that photo-exciting localized CTXs with push pulses resonant to the mid-infrared charge transfer absorption can promote delocalization and, in turn, contribute to the formation of long-lived charge separated states. On the other hand, we found that trapped CTXs are non-responsive to the push pulses. We hypothesize that delocalized states identified in prior studies are only accessible in systems where there is significant interchain electronic coupling or regioregularity that supports either inter- or intrachain polaron delocalization. This, in turn, emphasizes the importance of engineering the micromorphology and energetics of the donor-acceptor interface to exploit the full potential of a material for photovoltaic applications.

Anomalous non-equilibrium response in black phosphorus to sub-gap mid-infrared excitation.

The competition between the electron-hole Coulomb attraction and the 3D dielectric screening dictates the optical properties of layered semiconductors. In low-dimensional materials, the equilibrium dielectric environment can be significantly altered by the ultrafast excitation of photo-carriers, leading to renormalized band gap and exciton binding energies. Recently, black phosphorus emerged as a 2D material with strongly layer-dependent electronic properties. Here, we resolve the response of bulk black phosphorus to mid-infrared pulses tuned across the band gap. We find that, while above-gap excitation leads to a broadband light-induced transparency, sub-gap pulses drive an anomalous response, peaked at the single-layer exciton resonance. With the support of DFT calculations, we tentatively ascribe this experimental evidence to a non-adiabatic modification of the screening environment. Our work heralds the non-adiabatic optical manipulation of the electronic properties of 2D materials, which is of great relevance for the engineering of versatile van der Waals materials.

Tunable cryogenic terahertz cavity for strong light-matter coupling in complex materials.

We report here the realization and commissioning of an experiment dedicated to the study of the optical properties of light-matter hybrids constituted of crystalline samples embedded in an optical cavity. The experimental assembly developed offers the unique opportunity to study the weak and strong coupling regimes between a tunable optical cavity in cryogenic environment and low energy degrees of freedom, such as phonons, magnons, or charge fluctuations. We describe here the setup developed that allows for the positioning of crystalline samples in an optical cavity of different quality factors, the tuning of the cavity length at cryogenic temperatures, and its optical characterization with a broadband time domain THz spectrometer (0.2-6 THz). We demonstrate the versatility of the setup by studying the vibrational strong coupling in CuGeO3 single crystal at cryogenic temperatures.

Transient measurement of phononic states with covariance-based stochastic spectroscopy.

We present a novel approach to transient Raman spectroscopy, which combines stochastic probe pulses and a covariance-based detection to measure stimulated Raman signals in alpha-quartz. A coherent broadband pump is used to simultaneously impulsively excite a range of different phonon modes, and the phase, amplitude, and energy of each mode are independently recovered as a function of the pump-probe delay by a noisy-probe and covariance-based analysis. Our experimental results and the associated theoretical description demonstrate the feasibility of 2D-Raman experiments based on the stochastic-probe schemes, with new capabilities not available in equivalent mean-value-based 2D-Raman techniques. This work unlocks the gate for nonlinear spectroscopies to capitalize on the information hidden within the noise and overlooked by a mean-value analysis.

Visible pump-mid infrared pump-broadband probe: Development and characterization of a three-pulse setup for single-shot ultrafast spectroscopy at 50 kHz.

We report here an experimental setup to perform three-pulse pump-probe measurements over a wide wavelength and temperature range. By combining two pump pulses in the visible (650 nm-900 nm) and mid-IR (5 µm-20 µm) range, with a broadband supercontinuum white-light probe, our apparatus enables both the combined selective excitation of different material degrees of freedom and a full time-dependent reconstruction of the non-equilibrium dielectric function of the sample. We describe here the optical setup, the cryogenic sample environment, and the custom-made acquisition electronics capable of referenced single-pulse detection of broadband spectra at the maximum repetition rate of 50 kHz, achieving a sensitivity of the order of 10-4 over an integration time of 1 s. We demonstrate the performance of the setup by reporting data on a mid-IR pump, optical push, and broadband probe in a single crystal of Bi2Sr2Y0.08Ca0.92Cu2O8+δ across the superconducting and pseudogap phases.

Time-resolved multimode heterodyne detection for dissecting coherent states of matter.

Unveiling and controlling the time evolution of the momentum and position of low energy excitations such as phonons, magnons, and electronic excitation is the key to attain coherently driven new functionalities of materials. Here we report the implementation of femtosecond time- and frequency-resolved multimode heterodyne detection and show that it allows for independent measurement of the time evolution of the position and momentum of the atoms in coherent vibrational states in α-quartz. The time dependence of the probe field quadratures reveals that their amplitude is maximally changed when the atoms have maximum momentum, while their phase encodes a different information and evolves proportionally to the instantaneous atomic positon. We stress that this methodology, providing the mean to map both momentum and position in one optical observable, may be of relevance for both quantum information technologies and time-domain studies on complex materials.

Femtosecond covariance spectroscopy.

The success of nonlinear optics relies largely on pulse-to-pulse consistency. In contrast, covariance-based techniques used in photoionization electron spectroscopy and mass spectrometry have shown that a wealth of information can be extracted from noise that is lost when averaging multiple measurements. Here, we apply covariance-based detection to nonlinear optical spectroscopy, and show that noise in a femtosecond laser is not necessarily a liability to be mitigated, but can act as a unique and powerful asset. As a proof of principle we apply this approach to the process of stimulated Raman scattering in α-quartz. Our results demonstrate how nonlinear processes in the sample can encode correlations between the spectral components of ultrashort pulses with uncorrelated stochastic fluctuations. This in turn provides richer information compared with the standard nonlinear optics techniques that are based on averages over many repetitions with well-behaved laser pulses. These proof-of-principle results suggest that covariance-based nonlinear spectroscopy will improve the applicability of fs nonlinear spectroscopy in wavelength ranges where stable, transform-limited pulses are not available, such as X-ray free-electron lasers which naturally have spectrally noisy pulses ideally suited for this approach.