Rafael Quintero-Bermudez

Transient grating spectroscopy has become a mainstay among metal and semiconductor characterization techniques. Here, we extend the technique toward the shortest achievable time scales by using tabletop high-harmonic generation of attosecond extreme ultraviolet (XUV) pulses that diffract from transient gratings generated with sub-5 fs near-infrared (NIR) pulses. We demonstrate the power of attosecond transient grating spectroscopy (ATGS) by investigating the ultrafast photoexcited dynamics in an Sb semimetal thin film. ATGS provides an element-specific, background-free signal unfettered by spectral congestion, in contrast to transient absorption spectroscopy. With ATGS measurements in Sb polycrystalline thin films, we observe the generation of coherent phonons and investigate the lattice and carrier dynamics. Among the latter processes, we extract carrier thermalization, hot carrier cooling, and electron-hole recombination, which are on the order of 20 fs, 50 fs, and 2 ps time scales, respectively. Furthermore, the simultaneous collection of transient absorption and transient grating data allows us to extract the total complex dielectric constant in the sample dynamics with a single measurement, including the real-valued refractive index, from which we are also able to investigate carrier-phonon interactions and longer-lived phonon dynamics. The outlined experimental technique expands the capabilities of transient grating spectroscopy and attosecond spectroscopies by providing a wealth of information concerning carrier and lattice dynamics with an element-selective technique at the shortest achievable time scales.

In the past, laser propagation in a fluid with heat transfer has been modeled using simplistic conduction and convection conditions yielding inaccurate predictions. Here we present a detailed numerical study describing the thermal profile of the fluid and its interaction with the laser. Furthermore, we evaluate the diffraction field in the far field produced by a pump beam impinging in the fluid and the interferometric pattern obtained normal to the propagation direction to test our model. Direct comparison between experimental results and numerical simulation allows for a complete understanding of the energy transfer from the laser to the liquid and the subsequent effect on the laser propagation. Spatial self-phase modulation and propagation control from small-phase diffraction to aberration-controlled diffraction and up to diffraction oscillation are observed and explained with our modeling.

The use of LiF as a thin interlayer between the electron transport layer and cathode has played a pivotal role in remarkable advances in perovskite LEDs (PLEDs); however, the mechanism behind the effect of LiF remains to be fully understood. Here we report a combined experimental and computational study from which we ascribe the benefits of a LiF interlayer to the migration of dissociated Li into the cathode and dissociated F into the anode. Electronic device simulations reveal that the former improves electron injection by lowering the Schottky barrier height, while the latter reduces the barrier width. These reduce turn-on voltage and improve current density and charge balance in LEDs. We fabricate PLEDs with and without the LiF interlayer and link these materials and electronic phenomena to the device light-current-voltage characteristics. X-ray photoelectron spectroscopy obtained in sputter profiling of PLEDs corroborates the dissociation of LiF.

Metal halide perovskites are being increasingly explored for use in light emitting diodes (LEDs), with achievements in efficiency and brightness charted across the spectrum. One path to further boosting the fraction of useful photons generated by injected electrical charges will be to tailor the emission patterns of devices. Here we investigate directional emission from layered metal halide perovskites. We quantify the proportion of in-plane versus out-of-plane transition dipole components for a suite of layered perovskites. We find that certain perovskite single crystals have highly anisotropic emissions and up to 90% of their transition dipole in-plane. For thin films, emission anisotropy increases as the nominal layer thickness decreases and is generally greater with butylammonium cations than with phenethylammonium cations. Numerical simulations reveal that anisotropic emission from layered perovskites in thin film LEDs may lead to external quantum efficiencies of 45%—an absolute gain of 13% over equivalent films with isotropic emitters.

Metal halide perovskites show promise for light-emitting diodes (LEDs) owing to their facile manufacture and excellent optoelectronic performance, including high color purity and spectral stability, especially in the green region. However, for blue perovskite LEDs, the emission spectrum line width is broadened to over 25 nm by the coexistence of multiple reduced-dimensional perovskite domains, and the spectral stability is poor, with an undesirable shift (over 7 nm) toward longer wavelengths under operating conditions, degradation that occurs due to phase separation when mixed halides are employed. Here we demonstrate chloride insertion-immobilization, a strategy that enables blue perovskite LEDs, the first to exhibit narrowband (line width of 18 nm) and spectrally stable (no wavelength shift) performance. We prepare bromide-based perovskites and then employ organic chlorides for dynamic treatment, inserting and in situ immobilizing chlorides to blue-shift and stabilize the emission. We achieve sky-blue LEDs with a record luminance over 5100 cd/m² at 489 nm, and an operating half-life of 51 min at 1500 cd/m². By device structure optimization, we further realize an improved EQE of 5.2% at 479 nm and an operating half-life of 90 min at 100 cd/m².

Perovskite nanocrystals exhibit high photoluminescence quantum yields (PLQYs) and tunable bandgaps from ultraviolet to infrared. However, blue perovskite light‐emitting diodes (LEDs) suffer from color instability under applied bias. Developing narrow‐bandwidth deep‐blue emitters will maximize the color gamut of display technologies. Mixed anion approaches suffer from halide segregation that leads to their spectral instability. Here instead, a mixed cation strategy is employed whereby Rb⁺ is directly incorporated during synthesis into CsPbBr₃ nanocrystals. Blue‐emitting perovskite quantum dots (QDs) with stable photoluminescence, PLQYs greater than 60%, tunable emission from 460 to 500 nm, and narrow emission linewidths (−2 at an EQE of 0.75%, the best reported to date of perovskite QD LEDs.

The deployment of perovskite solar cells will rely on further progress in the operating and ambient stability of active layers and interfaces within these materials. Low-dimensional perovskites, also known as perovskite quantum wells (PQWs), utilize organic ligands to protect the perovskite lattice from degradation and offer to improve device stability; combining 2D and 3D perovskites in heterostructures has been shown to take advantage of the high efficiency of the majority 3D active layers and combine it with the improved stability of a thin 2D top layer. Prior PQWs have relied on relatively weak interwell van der Waals bonding between hydrophobic organic moieties of the ligands. Here we instead use the ligand 4-vinylbenzylammonium to form well-ordered PQWs atop a 3D perovskite layer. The ligand’s vinyl group is activated using UV light which photochemically forms new covalent bonds among PQWs. UV-cross-linked 2D/3D devices show improved operational stability as well as improved long-term dark stability in air: they retain 90% of their initial efficiency after 2300 h of dark aging compared to a retention of 20% of performance in the case of 3D films. The UV-cross-linked PQWs and 2D/3D interfaces reduce device hysteresis and improve the open-circuit voltages to values up to 1.20 V, resulting in more efficient devices (PCE of up to 20.4%). This work highlights the exploitation of the chemical reactivity of PQW ligands to tailor the molecular properties of PQW interfaces for improved stability and performance in 2D/3D perovskite photovoltaics.