Localization-limited exciton oscillator strength in colloidal CdSe nanoplatelets revealed by the optically induced stark effect.

2D materials are considered for applications that require strong light-matter interaction because of the apparently giant oscillator strength of the exciton transitions in the absorbance spectrum. Nevertheless, the effective oscillator strengths of these transitions have been scarcely reported, nor is there a consistent interpretation of the obtained values. Here, we analyse the transition dipole moment and the ensuing oscillator strength of the exciton transition in 2D CdSe nanoplatelets by means of the optically induced Stark effect (OSE). Intriguingly, we find that the exciton absorption line reacts to a high intensity optical field as a transition with an oscillator strength FStark that is 50 times smaller than expected based on the linear absorption coefficient. We propose that the pronounced exciton absorption line should be seen as the sum of multiple, low oscillator strength transitions, rather than a single high oscillator strength one, a feat we assign to strong exciton center-of-mass localization. Within the quantum mechanical description of excitons, this 50-fold difference between both oscillator strengths corresponds to the ratio between the coherence area of the exciton's center of mass and the total area, which yields a coherence area of a mere 6.1 nm2. Since we find that the coherence area increases with reducing temperature, we conclude that thermal effects, related to lattice vibrations, contribute to exciton localization. In further support of this localization model, we show that FStark is independent of the nanoplatelet area, correctly predicts the radiative lifetime, and lines up for strongly confined quantum dot systems.

Extended Nucleation and Superfocusing in Colloidal Semiconductor Nanocrystal Synthesis.

Hot-injection synthesis is renowned for producing semiconductor nanocolloids with superb size dispersions. Burst nucleation and diffusion-controlled size focusing during growth have been invoked to rationalize this characteristic yet experimental evidence supporting the pertinence of these concepts is scant. By monitoring a CdSe synthesis in-situ with X-ray scattering, we find that nucleation is an extended event that coincides with growth during 15-20% of the reaction time. Moreover, we show that size focusing outpaces predictions of diffusion-limited growth. This observation indicates that nanocrystal growth is dictated by the surface reactivity, which drops sharply for larger nanocrystals. Kinetic reaction simulations confirm that this so-called superfocusing can lengthen the nucleation period and promote size focusing. The finding that narrow size dispersions can emerge from the counteracting effects of extended nucleation and reaction-limited size focusing ushers in an evidence-based perspective that turns hot injection into a rational scheme to produce monodisperse semiconductor nanocolloids.

Phonon-Mediated and Weakly Size-Dependent Electron and Hole Cooling in CsPbBr3 Nanocrystals Revealed by Atomistic Simulations and Ultrafast Spectroscopy.

We combine state-of-the-art ultrafast photoluminescence and absorption spectroscopy and nonadiabatic molecular dynamics simulations to investigate charge-carrier cooling in CsPbBr3 nanocrystals over a very broad size regime, from 0.8 to 12 nm. Contrary to the prevailing notion that polaron formation slows down charge-carrier cooling in lead-halide perovskites, no suppression of carrier cooling is observed in CsPbBr3 nanocrystals except for a slow cooling (over ∼10 ps) of "warm" electrons in the vicinity (within ∼0.1 eV) of the conduction band edge. At higher excess energies, electrons and holes cool with similar rates, on the order of 1 eV ps-1 carrier-1, increasing weakly with size. Our ab initio simulations suggest that cooling proceeds via fast phonon-mediated intraband transitions driven by strong and size-dependent electron-phonon coupling. The presented experimental and computational methods yield the spectrum of involved phonons and may guide the development of devices utilizing hot charge carriers.

Integration of Colloidal PbS/CdS Quantum Dots with Plasmonic Antennas and Superconducting Detectors on a Silicon Nitride Photonic Platform.

Single-photon sources and detectors are indispensable building blocks for integrated quantum photonics, a research field that is seeing ever increasing interest for numerous applications. In this work, we implemented essential components for a quantum key distribution transceiver on a single photonic chip. Plasmonic antennas on top of silicon nitride waveguides provide Purcell enhancement with a concurrent increase of the count rate, speeding up the microsecond radiative lifetime of IR-emitting colloidal PbS/CdS quantum dots (QDs). The use of low-fluorescence silicon nitride, with a waveguide loss smaller than 1 dB/cm, made it possible to implement high extinction ratio optical filters and low insertion loss spectrometers. Waveguide-coupled superconducting nanowire single-photon detectors allow for low time-jitter single-photon detection. To showcase the performance of the components, we demonstrate on-chip lifetime spectroscopy of PbS/CdS QDs. The method developed in this paper is predicted to scale down to single QDs, and newly developed emitters can be readily integrated on the chip-based platform.

Using Bulk-like Nanocrystals To Probe Intrinsic Optical Gain Characteristics of Inorganic Lead Halide Perovskites.

Following the introduction of perovskites for photovoltaic solar energy conversion, the use of these materials as a general purpose optoelectronic material for displays, lighting, and lasing has been explored. However, while reports on stimulated emission and lasing by perovskites show great promise, a comprehensive quantification of their optical gain characteristics is lacking. Here, we measure gain coefficients, clarify the gain mechanism, and explore the gain dynamics of colloidal CsPbBr3 nanocrystals by deploying a unique combination of broadband transient absorption and ultrafast fluorescence spectroscopy. Opposite from current literature, we show that optical gain in such nanocrystals is supported by stimulated emission from free carriers, and not from excitons or biexcitons. Importantly, we demonstrate that the concomitant gain coefficients and thresholds agree with literature results reported for perovksite thin films. Finally, we show that, even in the case of fully inorganic lead halide perovskites, a cooling bottleneck hampers the development of net stimulated emission at high excitation density. Based on these results, we propose that bulk-like colloidal nanocrystals in general offer a unique testbed to quantify optical gain of novel photonic materials and in particular for lead halide perovskites.

Light Absorption Coefficient of CsPbBr3 Perovskite Nanocrystals.

Inductively coupled plasma mass spectrometry (ICP-MS) was combined with UV-vis absorption spectroscopy and transmission electron microscopy to determine the size, composition, and intrinsic absorption coefficient µi of 4 to 11 nm sized colloidal CsPbBr3 nanocrystals (NCs). The ICP-MS measurements demonstrate the nonstoichiometric nature of the NCs, with a systematic excess of lead for all samples studied. Rutherford backscattering measurements indicate that this enrichment in lead concurs with a relative increase in the bromide content. At high photon energies, µi is independent of the nanocrystal size. This allows the nanocrystal concentration in CsPbBr3 nanocolloids to be readily obtained by a combination of absorption spectroscopy and the CsPbBr3 sizing curve.

Thin-Film Quantum Dot Photodiode for Monolithic Infrared Image Sensors.

Imaging in the infrared wavelength range has been fundamental in scientific, military and surveillance applications. Currently, it is a crucial enabler of new industries such as autonomous mobility (for obstacle detection), augmented reality (for eye tracking) and biometrics. Ubiquitous deployment of infrared cameras (on a scale similar to visible cameras) is however prevented by high manufacturing cost and low resolution related to the need of using image sensors based on flip-chip hybridization. One way to enable monolithic integration is by replacing expensive, small-scale III-V-based detector chips with narrow bandgap thin-films compatible with 8- and 12-inch full-wafer processing. This work describes a CMOS-compatible pixel stack based on lead sulfide quantum dots (PbS QD) with tunable absorption peak. Photodiode with a 150-nm thick absorber in an inverted architecture shows dark current of 10-6 A/cm² at -2 V reverse bias and EQE above 20% at 1440 nm wavelength. Optical modeling for top illumination architecture can improve the contact transparency to 70%. Additional cooling (193 K) can improve the sensitivity to 60 dB. This stack can be integrated on a CMOS ROIC, enabling order-of-magnitude cost reduction for infrared sensors.

Highly Dynamic Ligand Binding and Light Absorption Coefficient of Cesium Lead Bromide Perovskite Nanocrystals.

Lead halide perovskite materials have attracted significant attention in the context of photovoltaics and other optoelectronic applications, and recently, research efforts have been directed to nanostructured lead halide perovskites. Collodial nanocrystals (NCs) of cesium lead halides (CsPbX3, X = Cl, Br, I) exhibit bright photoluminescence, with emission tunable over the entire visible spectral region. However, previous studies on CsPbX3 NCs did not address key aspects of their chemistry and photophysics such as surface chemistry and quantitative light absorption. Here, we elaborate on the synthesis of CsPbBr3 NCs and their surface chemistry. In addition, the intrinsic absorption coefficient was determined experimentally by combining elemental analysis with accurate optical absorption measurements. (1)H solution nuclear magnetic resonance spectroscopy was used to characterize sample purity, elucidate the surface chemistry, and evaluate the influence of purification methods on the surface composition. We find that ligand binding to the NC surface is highly dynamic, and therefore, ligands are easily lost during the isolation and purification procedures. However, when a small amount of both oleic acid and oleylamine is added, the NCs can be purified, maintaining optical, colloidal, and material integrity. In addition, we find that a high amine content in the ligand shell increases the quantum yield due to the improved binding of the carboxylic acid.