Chemically prepared 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 ps, an appreciable fraction of their 210 ps 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 with fast emission, wide spectral-tunability, scalable production, and which benefit from the hybrid-integration with nano-photonic components that has been demonstrated for colloidal materials. Tisdale.

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.

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.

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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 CHNHPbI 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.

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 (T 2) to twice its radiative lifetime (2T 1) 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.

Metal halide perovskites are promising solar energy materials, but their mechanism of action remains poorly understood. It has been conjectured that energetically stabilized states such as those corresponding to polarons, quasiparticles in which the carriers are dressed with phonons, are responsible for their remarkable photophysical properties. Yet, no direct evidence of polarons or other low-energy states have been reported despite extensive efforts. Such states should manifest as below bandgap features in transient absorption and photoluminescence measurements. Here, we use single-particle transient absorption microscopy on MAPbI (MA = methylammonium) to unambiguously identify spectrally narrow sub-bandgap states directly; we demonstrate that such signals are completely averaged away in ensemble measurements. Carrier temperature-dependent studies suggest that hot carriers are directed toward transient low-energy states which are immune from permanent defects and traps, thereby giving rise to low carrier recombination rates and ultimately high power conversion efficiency in devices. The utilization of short-lived sub-bandgap states may be a key design principle that propels widespread use of highly heterogeneous materials in optoelectronic applications.

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.