Electronic Structure and Excited State Dynamics of Cadmium Chalcogenide Nanorods.

The cylindrical quasi-one-dimensional shape of colloidal semiconductor nanorods (NRs) gives them unique electronic structure and optical properties. In addition to the band gap tunability common to nanocrystals, NRs have polarized light absorption and emission and high molar absorptivities. NR-shaped heterostructures feature control of electron and hole locations as well as light emission energy and efficiency. We comprehensively review the electronic structure and optical properties of Cd-chalcogenide NRs and NR heterostructures (e.g., CdSe/CdS dot-in-rods, CdSe/ZnS rod-in-rods), which have been widely investigated over the last two decades due in part to promising optoelectronic applications. We start by describing methods for synthesizing these colloidal NRs. We then detail the electronic structure of single-component and heterostructure NRs and follow with a discussion of light absorption and emission in these materials. Next, we describe the excited state dynamics of these NRs, including carrier cooling, carrier and exciton migration, radiative and nonradiative recombination, multiexciton generation and dynamics, and processes that involve trapped carriers. Finally, we describe charge transfer from photoexcited NRs and connect the dynamics of these processes with light-driven chemistry. We end with an outlook that highlights some of the outstanding questions about the excited state properties of Cd-chalcogenide NRs.

Exciton and biexciton transient absorption spectra of CdSe quantum dots with varying diameters.

Transient absorption (TA) spectroscopy of semiconductor nanocrystals (NCs) is often used for excited state population analysis, but recent results suggest that TA bleach signals associated with multiexcitons in NCs do not scale linearly with exciton multiplicity. In this manuscript, we probe the factors that determine the intensities and spectral positions of exciton and biexciton components in the TA spectra of CdSe quantum dots (QDs) of five diameters. We find that, in all cases, the peak intensity of the biexciton TA spectrum is less than 1.5 times that of the single exciton TA spectrum, in stark contrast to a commonly made assumption that this ratio is 2. The relative intensities of the biexciton and exciton TA signals at each wavelength are determined by at least two factors: the TA spectral intensity and the spectral offset between the two signals. We do not observe correlations between either of these factors and the particle diameter, but we find that both are strongly impacted by replacing the native organic surface-capping ligands with a hole-trapping ligand. These results suggest that surface trapping plays an important role in determining the absolute intensities of TA features for CdSe QDs and not just their decay kinetics. Our work highlights the role of spectral offsets and the importance of surface trapping in governing absolute TA intensities. It also conclusively demonstrates that the biexciton TA spectra of CdSe QDs at the band gap energy are less than twice as intense as those of the exciton.

Resolving the Triexciton Recombination Pathway in CdSe/CdS Nanocrystals through State-Specific Correlation Measurements.

As luminescence applications of colloidal semiconductor nanocrystals push toward higher excitation flux conditions, there is an increased need to both understand and potentially control emission from multiexciton states. We develop a spectrally resolved correlation method to study the triply excited state that enables direct measurements of the recombination pathway for the triexciton, rather than relying on indirect extraction of rates. We demonstrate that, for core-shell CdSe-CdS nanocrystals, triexciton emission arises exclusively from the band-edge S-like state. Time-dependent density functional theory and extended particle-in-a-sphere calculations demonstrate that reduced carrier overlap induced by the core-shell heterostructure can account for the lack of emission observed from the P-like state. These results provide a potential avenue for the control of nanocrystal luminescence, where core-shell heterostructures can be leveraged to control carrier separation and therefore maintain emission color purity over a broader range of excitation fluxes.

Light Management in Organic Photovoltaics Processed in Ambient Conditions Using ZnO Nanowire and Antireflection Layer with Nanocone Array.

Low carrier mobility and lifetime in semiconductor polymers are some of the main challenges facing the field of organic photovoltaics (OPV) in the quest for efficient devices with high current density. Finding novel strategies such as device structure engineering is a key pathway toward addressing this issue. In this work, the light absorption and carrier collection of OPV devices are improved by employment of ZnO nanowire (NW) arrays with an optimum NW length (50 nm) and antireflection (AR) film with nanocone structure. The optical characterization results show that ZnO NW increases the transmittance of the electron transporting layer as well as the absorption of the polymer blend. Moreover, the as-deposited polymer blend on the ZnO NW array shows better charge transfer as compared to the planar sample. By employing PC70BM:PV2000 as a promising air-stable active-layer, power conversion efficiencies of 9.8% and 10.1% are achieved for NW devices without and with an AR film, indicating 22.5% and 26.2% enhancement in PCE as compared to that of planar device. Moreover, it is shown that the AR film enhances the water-repellent ability of the OPV device.

Multiexciton Lifetimes Reveal Triexciton Emission Pathway in CdSe Nanocrystals.

Multiexcitons in emerging semiconducting nanomaterials play a critical role in potential optoelectronic and quantum computational devices. We describe photon resolved single molecule methods to directly probe the dynamics of biexcitons and triexcitons in colloidal CdSe quantum dots. We confirm that biexcitons emit from a spin-correlated state, consistent with statistical scaling. Contrary to current understanding, we find that triexciton emission is dominated by band-edge 1Se1S3/2 recombination rather than the higher energy 1Pe1P3/2 recombination.

Probing Linewidths and Biexciton Quantum Yields of Single Cesium Lead Halide Nanocrystals in Solution.

Cesium lead halide (CsPbX3, X = Cl, Br, I) perovskite nanocrystals (PNCs) have recently become a promising material for optoelectronic applications due to their high emission quantum yields and facile band gap tunability via both halide composition and size. The spectroscopy of single PNCs enhances our understanding of the effect of confinement on excitations in PNCs in the absence of obfuscating ensemble averaging and can also inform synthetic efforts. However, single PNC studies have been hampered by poor PNC photostability under confocal excitation, precluding interrogation of all but the most stable PNCs, and leading to a lack of understanding of PNCs in the regime of high confinement. Here, we report the first comprehensive spectroscopic investigation of single PNC properties using solution-phase photon-correlation methods, including both highly confined and blue-emitting PNCs, previously inaccessible to single NC techniques. With minimally perturbative solution-phase photon-correlation Fourier spectroscopy (s-PCFS), we establish that the ensemble emission linewidth of PNCs of all sizes and compositions is predominantly determined by the intrinsic single PNC linewidth (homogeneous broadening). The single PNC linewidth, in turn, dramatically increases with increasing confinement, consistent with what has been found for II-VI semiconductor nanocrystals. With solution-phase photon antibunching measurements, we survey the biexciton-to-exciton quantum yield ratio (BX/X QY) in the absence of user-selection bias or photodegradation. Remarkably, the BX/X QY ratio depends both on the PNC size and halide composition, with values between ∼2% for highly confined bromide PNCs and ∼50% for intermediately confined iodide PNCs. Our results suggest a wide range of underlying Auger rates, likely due to transitory charge carrier separation in PNCs with relaxed confinement.

News in Nanocrystals Seminar: Self-Assembly of Early Career Researchers toward Globally Accessible Nanoscience.

In 2020, many in-person scientific events were canceled due to the COVID-19 pandemic, creating a vacuum in networking and knowledge exchange between scientists. To fill this void in scientific communication, a group of early career nanocrystal enthusiasts launched the virtual seminar series, News in Nanocrystals, in the summer of 2020. By the end of the year, the series had attracted over 850 participants from 46 countries. In this Nano Focus, we describe the process of organizing the News in Nanocrystals seminar series; discuss its growth, emphasizing what the organizers have learned in terms of diversity and accessibility; and provide an outlook for the next steps and future opportunities. This summary and analysis of experiences and learned lessons are intended to inform the broader scientific community, especially those who are looking for avenues to continue fostering discussion and scientific engagement virtually, both during the pandemic and after.

The Motion of Trapped Holes on Nanocrystal Surfaces.

This Perspective discusses the phenomenon of trapped-hole diffusion in colloidal semiconductor nanocrystals. Surface charge-carrier traps are ubiquitous in nanocrystals and often dictate the fate of photoexcited carriers. New measurements and calculations are unveiling the nature of the nanocrystal surface, but many challenges to understanding the dynamics of trapped carriers remain. In contrast to the view that trapped holes are stationary, we have put forward a series of reports demonstrating that trapped holes on the surfaces of CdS and CdSe nanocrystals are mobile and move between traps in a sequence of hops. We summarize how these findings advance the understanding of carrier dynamics in colloidal nanocrystals and how they may impact a broad set of excited-state behaviors in these materials.

Setting an Upper Bound to the Biexciton Binding Energy in CsPbBr3 Perovskite Nanocrystals.

Cesium lead halide perovskite nanocrystals are promising emissive materials for a variety of optoelectronic applications. To fully realize the potential of these materials, we must understand the energetics and dynamics of multiexciton states which are populated under device relevant excitation conditions. We utilized time-resolved and spectrally-resolved photoluminescence studies to investigate the biexciton binding energy as well as a red-shifted emission feature previously reported under high-flux excitation conditions. We determine that this red-shifted emission feature can be ascribed to sample sintering induced by air-exposure and high-flux irradiation. Furthermore, we determine that the biexciton binding energy at room temperature is at most ±20 meV, providing a key insight toward understanding many-body interactions in the lead halide perovskite lattice.

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.