Ultrafast Imaging of Carrier Cooling in Metal Halide Perovskite Thin Films.

Understanding carrier relaxation in lead halide perovskites at the nanoscale is critical for advancing their device physics. Here, we directly image carrier cooling in polycrystalline CH3NH3PbI3 films with nanometer spatial resolution. We observe that upon photon absorption, highly energetic carriers rapidly thermalize with the lattice at different rates across the film. The initial carrier temperatures vary by many multiples of the lattice temperature across hundreds of nanometers, a factor that cannot be accounted for by excess photon energy above the bandgap alone or in variations of the initial carrier density. Electron microscopy suggests that morphology plays a critical role in determining the initial carrier temperature and that carriers in small crystal domains decay slower than those in large crystal domains. Our results demonstrate that local disorder dominates the observed carrier behavior, highlighting the importance of making local rather than averaged measurements in these materials.

Stable and high-power few cycle supercontinuum for 2D ultrabroadband electronic spectroscopy.

Broadband supercontinuum (SC) pulses in the few cycle regime are a promising source for spectroscopic and imaging applications. However, SC sources are plagued by poor stability, greatly limiting their utility in phase-resolved nonlinear experiments such as 2D photon echo spectroscopy (2D PES). Here, we generated SC by two-stage filamentation in argon and air starting from 100 fs input pulses, which are sufficiently high-power and stable to record time-resolved 2D PE spectra in a single laser shot. We obtain a total power of 400 µJ/pulse in the visible spectral range of 500-850 nm and, after compression, yield pulses with duration of 6 fs according to transient-grating frequency-resolved optical gating (TG-FROG) measurements. We demonstrate the method on the laser dye, Cresyl Violet, and observe coherent oscillations indicative of nuclear wavepacket dynamics.

Metal-free inorganic ligands for colloidal nanocrystals: S2-, HS-, Se2-, HSe-, Te2-, HTe-, TeS3(2-), OH-, and NH2- as surface ligands.

All-inorganic colloidal nanocrystals were synthesized by replacing organic capping ligands on chemically synthesized nanocrystals with metal-free inorganic ions such as S(2-), HS(-), Se(2-), HSe(-), Te(2-), HTe(-), TeS(3)(2-), OH(-) and NH(2)(-). These simple ligands adhered to the NC surface and provided colloidal stability in polar solvents. The versatility of such ligand exchange has been demonstrated for various semiconductor and metal nanocrystals of different size and shape. We showed that the key aspects of Pearson's hard and soft acids and bases (HSAB) principle, originally developed for metal coordination compounds, can be applied to the bonding of molecular species to the nanocrystal surface. The use of small inorganic ligands instead of traditional ligands with long hydrocarbon tails facilitated the charge transport between individual nanocrystals and opened up interesting opportunities for device integration of colloidal nanostructures.

Semiconductor nanocrystals functionalized with antimony telluride zintl ions for nanostructured thermoelectrics.

The energy efficiency of heat engines could be improved by the partial recovery of waste heat using thermoelectric (TE) generators. We show the possibility of designing nanostructured TE materials using colloidal inorganic nanocrystals functionalized with molecular antimony telluride complexes belonging to the family of Zintl ions. The unique advantage of using Zintl ions as the nanocrystal surface ligands is the possibility to convert them into crystalline metal chalcogenides, thus linking individual nanobuilding blocks into a macroscopic assembly of electronically coupled functional modules. This approach allows preserving the benefits of nanostructuring and quantum confinement while enabling facile charge transport through the interparticle boundaries. A developed methodology was applied for solution-based fabrication of nanostructured n- and p-type Bi(2-x)Sb(x)Te(3) alloys with tunable composition and PbTe-Sb(2)Te(3) nanocomposites with controlled grain size. Characterization of the TE properties of these materials showed that their Seebeck coefficients, electrical and thermal conductivities, and ZT values compared favorably with those of previously reported solution-processed TE materials.

Effect of Spectral Diffusion on the Coherence Properties of a Single Quantum Emitter in Hexagonal Boron Nitride.

Quantum emitters capable of producing single photons on-demand with high color purity are the building blocks of emerging schemes in secure quantum communications, quantum computing, and quantum metrology. Such solid-state systems, however, are usually prone to effects of spectral diffusion (SD), i.e., fast modulation of the emission wavelength due to the presence of localized, fluctuating electric fields. Two-dimensional materials are especially vulnerable to SD by virtue of the proximity of the emitters to the outside environment. In this study we report measurements of SD in a single hexagonal boron nitride (hBN) quantum emitter on the nanosecond to second time scales using photon correlation Fourier spectroscopy. We demonstrate that the spectral diffusion dynamics can be modeled by a two-component Gaussian random jump model, suggesting multiple sources of local fluctuations. We provide a lower limit of ∼0.13 for the ratio of the emitter's coherence time (T2) to twice its radiative lifetime (2T1) when it is measured on submicrosecond time scales. These results suggest that attaining transform-limited line widths could be achieved with moderate enhancement of the radiative rate. Moreover, the complex SD dynamics identified in our work inspires further exploration of the dephasing mechanisms in hBN as a viable quantum emitter platform.

Coherent single-photon emission from colloidal lead halide perovskite quantum dots.

Chemically made colloidal semiconductor quantum dots have long been proposed as scalable and color-tunable single emitters in quantum optics, but they have typically suffered from prohibitively incoherent emission. We now demonstrate that individual colloidal lead halide perovskite quantum dots (PQDs) display highly efficient single-photon emission with optical coherence times as long as 80 picoseconds, an appreciable fraction of their 210-picosecond radiative lifetimes. These measurements suggest that PQDs should be explored as building blocks in sources of indistinguishable single photons and entangled photon pairs. Our results present a starting point for the rational design of lead halide perovskite-based quantum emitters that have fast emission, wide spectral tunability, and scalable production and that benefit from the hybrid integration with nanophotonic components that has been demonstrated for colloidal materials.

Single Nanocrystal Spectroscopy of Shortwave Infrared Emitters.

Short-wave infrared (SWIR) emitters are at the center of ground-breaking applications in biomedical imaging, next-generation optoelectronic devices, and optical communications. Colloidal nanocrystals based on indium arsenide are some of the most promising SWIR emitters to date. However, the lack of single-particle spectroscopic methods accessible in the SWIR has prevented advances in both nanocrystal synthesis and fundamental characterization of emitters. Here, we demonstrate an implementation of a solution photon correlation Fourier spectroscopy (s-PCFS) experiment utilizing the SWIR sensitivity and time resolution of superconducting nanowire single-photon detectors to extract single-particle emission linewidths from colloidal indium arsenide/cadmium selenide (InAs/CdSe) core/shell nanocrystals emissive from 1.2 to 1.6 µm. We show that the average single InAs/CdSe nanocrystal fluorescence linewidth is, remarkably, as narrow as 52 meV, similar to what has been observed in some of the most narrowband nanostructured emitters in the visible region. Additionally, the single nanocrystal fluorescence linewidth increases with increasing shell thickness, suggesting exciton-phonon coupling as the dominant emission line-broadening mechanism in this system. The development of the SWIR s-PCFS technique has enabled measurements of spectral linewidths of colloidal SWIR-emissive NCs in solution and provides a platform to study the single NC spectral characteristics of SWIR emitters.

Mapping multidimensional electronic structure and ultrafast dynamics with single-element detection and compressive sensing.

Compressive sensing allows signals to be efficiently captured by exploiting their inherent sparsity. Here we implement sparse sampling to capture the electronic structure and ultrafast dynamics of molecular systems using phase-resolved 2D coherent spectroscopy. Until now, 2D spectroscopy has been hampered by its reliance on array detectors that operate in limited spectral regions. Combining spatial encoding of the nonlinear optical response and rapid signal modulation allows retrieval of state-resolved correlation maps in a photosynthetic protein and carbocyanine dye. We report complete Hadamard reconstruction of the signals and compression factors as high as 10, in good agreement with array-detected spectra. Single-point array reconstruction by spatial encoding (SPARSE) Spectroscopy reduces acquisition times by about an order of magnitude, with further speed improvements enabled by fast scanning of a digital micromirror device. We envision unprecedented applications for coherent spectroscopy using frequency combs and super-continua in diverse spectral regions.

Enhanced-Resolution Single-Shot 2DFT Spectroscopy by Spatial Spectral Interferometry.

We demonstrate use of spatial interference for the complete electric field reconstruction of two-dimensional (2D) coherent spectroscopic signals generated through four-wave mixing (4WM) in a single laser shot. Until now, the amplitude and phase characterization of 4WM signals has relied primarily on Fourier transform spectral interferometry (FTSI), which limits the measurement's sensitivity and resolution. We show that spatial spectral interferometry (SSI) is a generalized approach to 4WM signal detection that eliminates these inherent limitations of FTSI without introducing additional experimental complexity. SSI is used to measure the 2D photon echo spectra of two systems with dramatically different line widths, the coupled D line transitions in rubidium vapor and the energy-transfer dynamics in the light-harvesting protein LH2.

Mapping the Vibronic Structure of a Molecule by Few-Cycle Continuum Two-Dimensional Spectroscopy in a Single Pulse.

Accurate mapping of the electronic and vibrational structure of a molecular system is a basic goal of chemistry as it underpins reactivity and function. Experimentally, the challenge is to uncover the intramolecular interactions and ensuing dynamics that define this structure. Multidimensional coherent spectroscopy can map such interactions analogous to the way in which nuclear magnetic resonance provides access to the nuclear spin structure. Here we present two-dimensional coherent spectra measured using few-cycle continuum light. Critically, our approach instantaneously maps the energy landscape of a complex molecular system in a single laser pulse across 350 nm of bandwidth, thereby making it suitable for rapid molecular fingerprinting. We envision few-cycle supercontinuum spectroscopy based on the nonlinear optical response as a powerful tool to examine molecules in the condensed phase at the extremes of time, space, and energy.