Size-Dependent Optical Properties of InP Colloidal Quantum Dots.

Indium phosphide colloidal quantum dots (CQDs) are the main alternative for toxic and restricted Cd based CQDs for lighting and display applications. Here we systematically report on the size-dependent optical absorption, ensemble, and single particle photoluminescence (PL) and biexciton lifetimes of core-only InP CQDs. This systematic study is enabled by improvements in the synthesis of InP CQDs to yield a broad size series of monodisperse core-only InP CQDs with narrow absorption and PL line width and significant PL quantum yield.

Tuning the Driving Force for Charge Transfer in Perovskite-Chromophore Systems.

Understanding the interplay between the kinetics and energetics of photophysical processes in perovskite-chromophore hybrid systems is crucial for realizing their potential in optoelectronics, photocatalysis, and light-harvesting applications. By combining steady-state optical characterizations and transient absorption spectroscopy, we have investigated the mechanism of interfacial charge transfer (CT) between colloidal CsPbBr3 nanoplatelets (NPLs) and surface-anchored perylene derivatives and have explored the possibility of controlling the CT rate by tuning the driving force. The CT driving force was tuned systematically by attaching acceptors with different electron affinities and by varying the bandgap of NPLs via thickness-controlled quantum confinement. Our data show that the charge-separated state is formed by selectively exciting either the electron donors or acceptors in the same system. Upon exciting attached acceptors, hole transfer from perylene derivatives to CsPbBr3 NPLs takes place on a picosecond time scale, showing an energetic behavior in line with the Marcus normal regime. Interestingly, such energetic behavior is absent upon exciting the electron donor, suggesting that the dominant CT mechanism is energy transfer followed by ultrafast hole transfer. Our findings not only elucidate the photophysics of perovskite-molecule systems but also provide guidelines for tailoring such hybrid systems for specific applications.

Nucleation and Growth of Bipyramidal Yb:LiYF4 Nanocrystals-Growing Up in a Hot Environment.

Lanthanide-doped LiYF4 (Ln:YLF) is commonly used for a broad variety of optical applications, such as lasing, photon upconversion and optical refrigeration. When synthesized as nanocrystals (NCs), this material is also of interest for biological applications and fundamental physical studies. Until now, it was unclear how Ln:YLF NCs grow from their ionic precursors into tetragonal NCs with a well-defined, bipyramidal shape and uniform dopant distribution. Here, we study the nucleation and growth of ytterbium-doped LiYF4 (Yb:YLF), as a template for general Ln:YLF NC syntheses. We show that the formation of bipyramidal Yb:YLF NCs is a multistep process starting with the formation of amorphous Yb:YLF spheres. Over time, these spheres grow via Ostwald ripening and crystallize, resulting in bipyramidal Yb:YLF NCs. We further show that prolonged heating of the NCs results in the degradation of the NCs, observed by the presence of large LiF cubes and small, irregular Yb:YLF NCs. Due to the similarity in chemical nature of all lanthanide ions our work sheds light on the formation stages of Ln:YLF NCs in general.

Cryo-EM structure of gas vesicles for buoyancy-controlled motility.

Gas vesicles are gas-filled nanocompartments that allow a diverse group of bacteria and archaea to control their buoyancy. The molecular basis of their properties and assembly remains unclear. Here, we report the 3.2 Å cryo-EM structure of the gas vesicle shell made from the structural protein GvpA that self-assembles into hollow helical cylinders closed off by cone-shaped tips. Two helical half shells connect through a characteristic arrangement of GvpA monomers, suggesting a mechanism of gas vesicle biogenesis. The fold of GvpA features a corrugated wall structure typical for force-bearing thin-walled cylinders. Small pores enable gas molecules to diffuse across the shell, while the exceptionally hydrophobic interior surface effectively repels water. Comparative structural analysis confirms the evolutionary conservation of gas vesicle assemblies and demonstrates molecular features of shell reinforcement by GvpC. Our findings will further research into gas vesicle biology and facilitate molecular engineering of gas vesicles for ultrasound imaging.

Multivalent interactions facilitate motor-dependent protein accumulation at growing microtubule plus-ends.

Growing microtubule ends organize end-tracking proteins into comets of mixed composition. Here using a reconstituted fission yeast system consisting of end-binding protein Mal3, kinesin Tea2 and cargo Tip1, we found that these proteins can be driven into liquid-phase droplets both in solution and at microtubule ends under crowding conditions. In the absence of crowding agents, cryo-electron tomography revealed that motor-dependent comets consist of disordered networks where multivalent interactions may facilitate non-stoichiometric accumulation of cargo Tip1. We found that two disordered protein regions in Mal3 are required for the formation of droplets and motor-dependent accumulation of Tip1, while autonomous Mal3 comet formation requires only one of them. Using theoretical modelling, we explore possible mechanisms by which motor activity and multivalent interactions may lead to the observed enrichment of Tip1 at microtubule ends. We conclude that microtubule ends may act as platforms where multivalent interactions condense microtubule-associated proteins into large multi-protein complexes.

Zero-Threshold Optical Gain in Electrochemically Doped Nanoplatelets and the Physics Behind It.

Colloidal nanoplatelets (NPLs) are promising materials for lasing applications. The properties are usually discussed in the framework of 2D materials, where strong excitonic effects dominate the optical properties near the band edge. At the same time, NPLs have finite lateral dimensions such that NPLs are not true extended 2D structures. Here we study the photophysics and gain properties of CdSe/CdS/ZnS core-shell-shell NPLs upon electrochemical n doping and optical excitation. Steady-state absorption and PL spectroscopy show that excitonic effects are weaker in core-shell-shell nanoplatelets due to the decreased exciton binding energy. Transient absorption studies reveal a gain threshold of only one excitation per nanoplatelet. Using electrochemical n doping, we observe the complete bleaching of the band edge exciton transitions. Combining electrochemical doping with transient absorption spectroscopy, we demonstrate that the gain threshold is fully removed over a broad spectral range and gain coefficients of several thousand cm-1 are obtained. These doped NPLs are the best performing colloidal nanomaterial gain medium reported to date, with the lowest gain threshold and broadest gain spectrum and gain coefficients that are 4 times higher than in n-doped colloidal quantum dots. The low exciton binding energy due to the CdS and ZnS shells, in combination with the relatively small lateral size of the NPLs, results in excited states that are effectively delocalized over the entire platelet. Core-shell NPLs are thus on the border between strong confinement in QDs and dominant Coulombic effects in 2D materials. We demonstrate that this limit is in effect ideal for optical gain and that it results in an optimal lateral size of the platelets where the gain threshold per nm2 is minimal.

Nanofluidic chips for cryo-EM structure determination from picoliter sample volumes.

Cryogenic electron microscopy has become an essential tool for structure determination of biological macromolecules. In practice, the difficulty to reliably prepare samples with uniform ice thickness still represents a barrier for routine high-resolution imaging and limits the current throughput of the technique. We show that a nanofluidic sample support with well-defined geometry can be used to prepare cryo-EM specimens with reproducible ice thickness from picoliter sample volumes. The sample solution is contained in electron-transparent nanochannels that provide uniform thickness gradients without further optimisation and eliminate the potentially destructive air-water interface. We demonstrate the possibility to perform high-resolution structure determination with three standard protein specimens. Nanofabricated sample supports bear potential to automate the cryo-EM workflow, and to explore new frontiers for cryo-EM applications such as time-resolved imaging and high-throughput screening.

The Fine-Structure Constant as a Ruler for the Band-Edge Light Absorption Strength of Bulk and Quantum-Confined Semiconductors.

Low-dimensional semiconductors have found numerous applications in optoelectronics. However, a quantitative comparison of the absorption strength of low-dimensional versus bulk semiconductors has remained elusive. Here, we report generality in the band-edge light absorptance of semiconductors, independent of their dimensions. First, we provide atomistic tight-binding calculations that show that the absorptance of semiconductor quantum wells equals mπα (m = 1 or 2 with α as the fine-structure constant), in agreement with reported experimental results. Then, we show experimentally that a monolayer (superlattice) of quantum dots has similar absorptance, suggesting an absorptance quantum of mπα per (confined) exciton diameter. Extending this idea to bulk semiconductors, we experimentally demonstrate that an absorptance quantum equal to mπα per exciton Bohr diameter explains their widely varying absorption coefficients. We thus provided compelling evidence that the absorptance quantum πα per exciton diameter rules the band-edge absorption of all direct semiconductors, regardless of their dimension.

Quantitative Electrochemical Control over Optical Gain in Quantum-Dot Solids.

Solution-processed quantum dot (QD) lasers are one of the holy grails of nanoscience. They are not yet commercialized because the lasing threshold is too high: one needs >1 exciton per QD, which is difficult to achieve because of fast nonradiative Auger recombination. The threshold can, however, be reduced by electronic doping of the QDs, which decreases the absorption near the band-edge, such that the stimulated emission (SE) can easily outcompete absorption. Here, we show that by electrochemically doping films of CdSe/CdS/ZnS QDs, we achieve quantitative control over the gain threshold. We obtain stable and reversible doping of more than two electrons per QD. We quantify the gain threshold and the charge carrier dynamics using ultrafast spectroelectrochemistry and achieve quantitative agreement between experiments and theory, including a vanishingly low gain threshold for doubly doped QDs. Over a range of wavelengths with appreciable gain coefficients, the gain thresholds reach record-low values of ∼1 × 10-5 excitons per QD. These results demonstrate a high level of control over the gain threshold in doped QD solids, opening a new route for the creation of cheap, solution-processable, low-threshold QD lasers.

On the Stability of Permanent Electrochemical Doping of Quantum Dot, Fullerene, and Conductive Polymer Films in Frozen Electrolytes for Use in Semiconductor Devices.

Semiconductor films that allow facile ion transport can be electronically doped via electrochemistry, where the amount of injected charge can be controlled by the potential applied. To apply electrochemical doping to the design of semiconductor devices, the injected charge has to be stabilized to avoid unintentional relaxation back to the intrinsic state. Here, we investigate methods to increase the stability of electrochemically injected charges in thin films of a wide variety of semiconductor materials, namely inorganic semiconductors (ZnO NCs, CdSe NCs, and CdSe/CdS core/shell NCs) and organic semiconductors (P3DT, PCBM, and C60). We show that by charging the semiconductors at elevated temperatures in solvents with melting points above room temperature, the charge stability at room temperature increases greatly, from seconds to days. At reduced temperature (-75 °C when using succinonitrile as electrolyte solvent) the injected charge becomes entirely stable on the time scale of our experiments (up to several days). Other high melting point solvents such as dimethyl sulfone, ethylene carbonate, and poly(ethylene glycol) (PEG) also offer increased charge stability at room temperature. Especially the use of PEG increases the room temperature charge stability by several orders of magnitude compared to using acetonitrile. We discuss how this improvement of the charge stability is related to the immobilization of electrolyte ions and impurities. While the electrolyte ions are immobilized, conductivity measurements show that electrons in the semiconductor films remain mobile. These results highlight the potential of using solidified electrolytes to stabilize injected charges, which is a promising step toward making semiconductor devices based on electrochemically doped semiconductor thin films.

Tuning and Probing the Distribution of Cu+ and Cu2+ Trap States Responsible for Broad-Band Photoluminescence in CuInS2 Nanocrystals.

The processes that govern radiative recombination in ternary CuInS2 (CIS) nanocrystals (NCs) have been heavily debated, but recently, several research groups have come to the same conclusion that a photoexcited electron recombines with a localized hole on a Cu-related trap state. Furthermore, it has been observed that single CIS NCs display narrower photoluminescence (PL) line widths than the ensemble, which led to the conclusion that within the ensemble there is a distribution of Cu-related trap states responsible for PL. In this work, we probe this trap-state distribution with in situ photoluminescence spectroelectrochemistry. We find that Cu2+ states result in individual "dark" nanocrystals, whereas Cu+ states result in "bright" NCs. Furthermore, we show that we can tune the PL position, intensity, and line width in a cyclic fashion by injecting or removing electrons from the trap-state distribution, thereby converting a subset of "dark" Cu2+ containing NCs into "bright" Cu+ containing NCs and vice versa. The electrochemical injection of electrons results in brightening, broadening, and a red shift of the PL, in line with the activation of a broad distribution of "dark" NCs (Cu2+ states) into "bright" NCs (Cu+ states) and a rise of the Fermi level within the ensemble trap-state distribution. The opposite trend is observed for electrochemical oxidation of Cu+ states into Cu2+. Our work shows that there is a direct correlation between the line width of the ensemble Cu+/Cu2+ trap-state distribution and the characteristic broad-band PL feature of CIS NCs and between Cu2+ cations in the photoexcited state (bright) and in the electrochemically oxidized ground state (dark).

Selective antimony reduction initiating the nucleation and growth of InSb quantum dots.

Indium antimonide (InSb) quantum dots (QDs) have unique and interesting photophysical properties, but widespread experimentation with InSb QDs is lacking due to the difficulty in synthesizing this material. The key experimental challenge in fabricating InSb QDs is preparing a suitable Sb-precursor in the correct oxidation state that reacts with the In-precursor in a controllable manner. Here, we review and discuss the synthetic strategies for making colloidal InSb QDs and present a new reaction scheme yielding small (∼1 nm diameter) InSb QDs. This was accomplished by employing Sb(NMe2)3 as the antimony precursor and by screening different reducing agents that can selectively reduce it to stibine in situ. The released SbH3, subsequently, reacts with In carboxylate to form small InSb clusters. The absorption features are moderately tunable (from 400 nm to 660 nm) by the amount and rate of reductant addition as well as the temperature of injection and subsequent annealing. Optical properties were probed with transient absorption spectroscopy and show complex time and spectral dependencies.

Hot-electron transfer in quantum-dot heterojunction films.

Thermalization losses limit the photon-to-power conversion of solar cells at the high-energy side of the solar spectrum, as electrons quickly lose their energy relaxing to the band edge. Hot-electron transfer could reduce these losses. Here, we demonstrate fast and efficient hot-electron transfer between lead selenide and cadmium selenide quantum dots assembled in a quantum-dot heterojunction solid. In this system, the energy structure of the absorber material and of the electron extracting material can be easily tuned via a variation of quantum-dot size, allowing us to tailor the energetics of the transfer process for device applications. The efficiency of the transfer process increases with excitation energy as a result of the more favorable competition between hot-electron transfer and electron cooling. The experimental picture is supported by time-domain density functional theory calculations, showing that electron density is transferred from lead selenide to cadmium selenide quantum dots on the sub-picosecond timescale.

The Role of Dopant Ions on Charge Injection and Transport in Electrochemically Doped Quantum Dot Films.

Control over the charge density is very important for implementation of colloidal semiconductor nanocrystals into various optoelectronic applications. A promising approach to dope nanocrystal assemblies is charge injection by electrochemistry, in which the charge compensating electrolyte ions can be regarded as external dopant ions. To gain insight into the doping mechanism and the role of the external dopant ions, we investigate charge injection in ZnO nanocrystal assemblies for a large series of charge compensating electrolyte ions with spectroelectrochemical and electrochemical transistor measurements. We show that charge injection is limited by the diffusion of cations in the nanocrystal films as their diffusion coefficient are found to be ∼7 orders of magnitude lower than those of electrons. We further show that the rate of charge injection depends strongly on the cation size and cation concentration. Strikingly, the onset of electron injection varies up to 0.4 V, depending on the size of the electrolyte cation. For the small ions Li+ and Na+ the onset is at significantly less negative potentials. For larger ions (K+, quaternary ammonium ions) the onset is always at the same, more negative potential, suggesting that intercalation may take place for Li+ and Na+. Finally, we show that the nature of the charge compensating cation does not affect the source-drain electronic conductivity and mobility, indicating that shallow donor levels from intercalating ions fully hybridize with the quantum confined energy levels and that the reorganization energy due to intercalating ions does not strongly affect electron transport in these nanocrystal assemblies.

Asymmetric Optical Transitions Determine the Onset of Carrier Multiplication in Lead Chalcogenide Quantum Confined and Bulk Crystals.

Carrier multiplication is a process in which one absorbed photon excites two or more electrons. This is of great promise to increase the efficiency of photovoltaic devices. Until now, the factors that determine the onset energy of carrier multiplication have not been convincingly explained. We show experimentally that the onset of carrier multiplication in lead chalcogenide quantum confined and bulk crystals is due to asymmetric optical transitions. In such transitions most of the photon energy in excess of the band gap is given to either the hole or the electron. The results are confirmed and explained by theoretical tight-binding calculations of the competition between impact ionization and carrier cooling. These results are a large step forward in understanding carrier multiplication and allow for a screening of materials with an onset of carrier multiplication close to twice the band gap energy. Such materials are of great interest for development of highly efficient photovoltaic devices.

Enhanced vapour sensing using silicon nanowire devices coated with Pt nanoparticle functionalized porous organic frameworks.

Recently various porous organic frameworks (POFs, crystalline or amorphous materials) have been discovered, and used for a wide range of applications, including molecular separations and catalysis. Silicon nanowires (SiNWs) have been extensively studied for diverse applications, including as transistors, solar cells, lithium ion batteries and sensors. Here we demonstrate the functionalization of SiNW surfaces with POFs and explore its effect on the electrical sensing properties of SiNW-based devices. The surface modification by POFs was easily achieved by polycondensation on amine-modified SiNWs. Platinum nanoparticles were formed in these POFs by impregnation with chloroplatinic acid followed by chemical reduction. The final hybrid system showed highly enhanced sensitivity for methanol vapour detection. We envisage that the integration of SiNWs with POF selector layers, loaded with different metal nanoparticles will open up new avenues, not only in chemical and biosensing, but also in separations and catalysis.

Efficient Steplike Carrier Multiplication in Percolative Networks of Epitaxially Connected PbSe Nanocrystals.

Carrier multiplication (CM) is a process in which a single photon excites two or more electrons. CM is of interest to enhance the efficiency of a solar cell. Until now, CM in thin films and solar cells of semiconductor nanocrystals (NCs) has been found at photon energies well above the minimum required energy of twice the band gap. The high threshold of CM strongly limits the benefits for solar cell applications. We show that CM is more efficient in a percolative network of directly connected PbSe NCs. The CM threshold is at twice the band gap and increases in a steplike fashion with photon energy. A lower CM efficiency is found for a solid of weaker coupled NCs. This demonstrates that the coupling between NCs strongly affects the CM efficiency. According to device simulations, the measured CM efficiency would significantly enhance the power conversion efficiency of a solar cell.

Switching between Plasmonic and Fluorescent Copper Sulfide Nanocrystals.

Control over the doping density in copper sulfide nanocrystals is of great importance and determines its use in optoelectronic applications such as NIR optical switches and photovoltaic devices. Here, we demonstrate that we can reversibly control the hole carrier density (varying from >1022 cm-3 to intrinsic) in copper sulfide nanocrystals by electrochemical methods. We can control the type of charge injection, i.e., capacitive charging or ion intercalation, via the choice of the charge compensating cation (e.g., ammonium salts vs Li+). Further, the type of intercalating ion determines whether the charge injection is fully reversible (for Li+) or leads to permanent changes in doping density (for Cu+). Using fully reversible lithium intercalation allows us to switch between thin films of covellite CuS NCs (Eg = 2.0 eV, hole density 1022 cm-3, strong localized surface plasmon resonance) and low-chalcocite CuLiS NCs (Eg = 1.2 eV, intrinsic, no localized surface plasmon resonance), and back. Electrochemical Cu+ ion intercalation leads to a permanent phase transition to intrinsic low-chalcocite Cu2S nanocrystals that display air stable fluorescence, centered around 1050 nm (fwhm ∼145 meV, PLQY ca. 1.8%), which is the first observation of narrow near-infrared fluorescence for copper sulfide nanocrystals. The dynamic control over the hole doping density and fluorescence of copper sulfide nanocrystals presented in this work and the ability to switch between plasmonic and fluorescent semiconductor nanocrystals might lead to their successful implementation into photovoltaic devices, NIR optical switches and smart windows.

In situ study of the formation mechanism of two-dimensional superlattices from PbSe nanocrystals.

Oriented attachment of PbSe nanocubes can result in the formation of two-dimensional (2D) superstructures with long-range nanoscale and atomic order. This questions the applicability of classic models in which the superlattice grows by first forming a nucleus, followed by sequential irreversible attachment of nanocrystals, as one misaligned attachment would disrupt the 2D order beyond repair. Here, we demonstrate the formation mechanism of 2D PbSe superstructures with square geometry by using in situ grazing-incidence X-ray scattering (small angle and wide angle), ex situ electron microscopy, and Monte Carlo simulations. We observed nanocrystal adsorption at the liquid/gas interface, followed by the formation of a hexagonal nanocrystal monolayer. The hexagonal geometry transforms gradually through a pseudo-hexagonal phase into a phase with square order, driven by attractive interactions between the {100} planes perpendicular to the liquid substrate, which maximize facet-to-facet overlap. The nanocrystals then attach atomically via a necking process, resulting in 2D square superlattices.