Exciton-photocarrier interference in mixed lead-halide-perovskite nanocrystals.

The use of semiconductor nanocrystals in scalable quantum technologies requires characterization of the exciton coherence dynamics in an ensemble of electronically isolated crystals in which system-bath interactions are nevertheless strong. In this communication, we identify signatures of Fano-like interference between excitons and photocarriers in the coherent two-dimensional photoluminescence excitation spectral lineshapes of mixed lead-halide perovskite nanocrystals in dilute solution. Specifically, by tuning the femtosecond-pulse spectrum, we show such interference in an intermediate coupling regime, which is evident in the coherent lineshape when simultaneously exciting the exciton and the free-carrier band at higher energy. We conclude that this interference is an intrinsic effect that will be consequential in the quantum dynamics of the system and will thus dictate decoherence dynamics, with consequences in their application in quantum technologies.

Near Infrared Light-Emitting Diodes Based on Colloidal InAs/ZnSe Core/Thick-Shell Quantum Dots.

Heavy-metal-free III-V colloidal quantum dots (QDs) exhibit promising attributes for application in optoelectronics. Among them, InAs QDs are demonstrating excellent optical performance with respect to absorption and emission in the near-infrared spectral domain. Recently, InAs QDs attained a substantial improvement in photoluminescence quantum yield, achieving 70% at a wavelength of 900 nm through the strategic overgrowth of a thick ZnSe shell atop the InAs core. In the present study, light-emitting diodes (LEDs) based on this type of InAs/ZnSe QDs are fabricated, reaching an external quantum efficiency (EQE) of 13.3%, a turn-on voltage of 1.5V, and a maximum radiance of 12 Wsr-1m-2. Importantly, the LEDs exhibit an extensive emission dynamic range, characterized by a nearly linear correlation between emission intensity and current density, which can be attributed to the efficient passivation provided by the thick ZnSe shell. The obtained results are comparable to state-of-the-art PbS QD LEDs. Furthermore, it should be stressed not only that the fabricated LEDs are fully RoHS-compliant but also that the emitting InAs QDs are prepared via a synthetic route based on a non-pyrophoric, cheap, and commercially available as precursor, namely tris(dimethylamino)-arsine.

High-Efficiency and Stable Colloidal One-Dimensional Core/Shell Nanorod Light-Emitting Diodes.

Anisotropic nanocrystals such as nanorods (NRs) display unique linearly polarized emission, which is expected to break the external quantum efficiency (EQE) limit of quantum dot-based light-emitting diodes (LEDs). However, the progress in achieving a higher EQE using NRs encounters several challenges, primarily involving a low photoluminescence quantum yield (PLQY) of NRs and imbalanced charge injection in NR-LEDs. In this work, we investigated NR-LEDs based on CdSe/CdZnS/ZnS rod-in-rod NRs with a high PLQY and higher linear polarization compared to those of dot-in-rod NRs. The balanced charge injection is achieved using ZnMgO nanoparticles as the electron transport layer and poly-TPD {poly[N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine]} as the hole transport layer. Therefore, the NR-LEDs exhibit a maximum EQE of 21.5% and a maximum luminance of >120 000 cd/m2 owing to the high level of in-plane transitions with a dipole moment of 90%. The NR-LEDs also have greatly inhibited droop in EQE under a high current density as well as outstanding operation lifetime and cycle stability.

A Robust Anti-Thermal-Quenching Phosphor Based on Zero-Dimensional Metal Halide Rb3InCl6:xSb3.

High-power phosphor-converted white light-emitting diodes (hp-WLEDs) have been widely involved in modern society as outdoor lighting sources. In these devices, due to the Joule effect, the high applied currents cause high operation temperatures (>500 K). Under these conditions, most phosphors lose their emission, an effect known as thermal quenching (TQ). Here, we introduce a zero-dimensional (0D) metal halide, Rb3InCl6:xSb3+, as a suitable anti-TQ phosphor offering robust anti-TQ behavior up to 500 K. We ascribe this behavior of the metal halide to two factors: (1) a compensation process via thermally activated energy transfer from structural defects to emissive centers and (2) an intrinsic structural rigidity of the isolated octahedra in the 0D structure. The anti-TQ phosphor-based WLEDs can stably work at a current of 2000 mA. The low synthesis cost and nontoxic composition reported here can herald a new generation of anti-TQ phosphors for hp-WLED.

Partial Ligand Stripping from CsPbBr3 Nanocrystals Improves Their Performance in Light-Emitting Diodes.

Halide perovskite nanocrystals (NCs), specifically CsPbBr3, have attracted considerable interest due to their remarkable optical properties for optoelectronic devices. To achieve high-efficiency light-emitting diodes (LEDs) based on CsPbBr3 nanocrystals (NCs), it is crucial to optimize both their photoluminescence quantum yield (PLQY) and carrier transport properties when they are deposited to form films on substrates. While the exchange of native ligands with didodecyl dimethylammonium bromide (DDAB) ligand pairs has been successful in boosting their PLQY, dense DDAB coverage on the surface of NCs should impede carrier transport and limit device efficiency. Following our previous work, here, we use oleyl phosphonic acid (OLPA) as a selective stripping agent to remove a fraction of DDAB from the NC surface and demonstrate that such stripping enhances carrier transport while maintaining a high PLQY. Through systematic optimization of OLPA dosage, we significantly improve the performance of CsPbBr3 LEDs, achieving a maximum external quantum efficiency (EQE) of 15.1% at 516 nm and a maximum brightness of 5931 cd m-2. These findings underscore the potential of controlled ligand stripping to enhance the performance of CsPbBr3 NC-based optoelectronic devices.

Stainless Steel Activation for Efficient Alkaline Oxygen Evolution in Advanced Electrolyzers.

Designing robust and cost-effective electrocatalysts for efficient alkaline oxygen evolution reaction (OER) is of great significance in the field of water electrolysis. In this study, an electrochemical strategy to activate stainless steel (SS) electrodes for efficient OER is introduced. By cycling the SS electrode within a potential window that encompasses the Fe(II)↔Fe(III) process, its OER activity can be enhanced to a great extent compared to using a potential window that excludes this redox reaction, decreasing the overpotential at current density of 100 mA cm-2 by 40 mV. Electrochemical characterization, Inductively Coupled Plasma - Optical Emission Spectroscopy, and operando Raman measurements demonstrate that the Fe leaching at the SS surface can be accelerated through a Fe → γ-Fe2O3 → Fe3O4 or FeO → Fe2+ (aq.) conversion process, leading to the sustained exposure of Cr and Ni species. While Cr leaching occurs during its oxidation process, Ni species display higher resistance to leaching and gradually accumulate on the SS surface in the form of OER-active Fe-incorporated NiOOH species. Furthermore, a potential-pulse strategy is also introduced to regenerate the OER-activity of 316-type SS for stable OER, both in the three-electrode configuration (without performance decay after 300 h at 350 mA cm-2) and in an alkaline water electrolyzer (≈30 mV cell voltage increase after accelerated stress test-AST). The AST-stabilized cell can still reach 1000 and 4000 mA cm-2 at cell voltages of 1.69 and 2.1 V, which makes it competitive with state-of-the-art electrolyzers based on ion-exchange membrane using Ir-based anodes.

Near-Infrared Light Emitting Metal Halides: Materials, Mechanisms, and Applications.

Near-Infrared (NIR) light emitting metal halides are emerging as a new generation of optical materials owing to their appealing features, which include low-cost synthesis, solution processability, and adjustable optical properties. NIR-emitting perovskite-based light-emitting diodes (LEDs) have reached an external quantum efficiency (EQE) of over 20% and a device stability of over 10,000 h. Such results have sparked an interest in exploring new NIR metal halide emitters. In this review, several different types of NIR-emitting metal halides, including lead/tin bromide/iodide perovskites, lanthanide ions doped/based metal halides, double perovskites, low dimensional hybrid and Bi3+/Sb3+/Cr3+ doped metal halides, are summarized, and their recent advancement is assessed. The characteristics and mechanisms of narrow-band or broadband NIR luminescence in all these materials are discussed in detail. Also, the various applications of NIR-emitting metal halides are highlighted and an outlook for the field is provided.

Halide Perovskite Artificial Solids as a New Platform to Simulate Collective Phenomena in Doped Mott Insulators.

The development of quantum simulators, artificial platforms where the predictions of many-body theories of correlated quantum materials can be tested in a controllable and tunable way, is one of the main challenges of condensed matter physics. Here we introduce artificial lattices made of lead halide perovskite nanocubes as a new platform to simulate and investigate the physics of correlated quantum materials. We demonstrate that optical injection of quantum confined excitons in this system realizes the two main features that ubiquitously pervade the phase diagram of many quantum materials: collective phenomena, in which long-range orders emerge from incoherent fluctuations, and the excitonic Mott transition, which has one-to-one correspondence with the insulator-to-metal transition described by the repulsive Hubbard model in a magnetic field. Our results demonstrate that time-resolved experiments provide a quantum simulator that is able to span a parameter range relevant for a broad class of phenomena, such as superconductivity and charge-density waves.

The Bright and Enlightening Science of Quantum Dots.

The 2023 Nobel Prize in Chemistry was awarded to Alexei Ekimov, Louis Brus, and Moungi Bawendi for the discovery and development of quantum dots, an area of research ripe with exciting results in terms of both fundamental science and present and forthcoming applications. Quantum dots, with their colors and their intriguing properties, have fascinated and engaged generations of scientists over the last 40 years, including myself. I present here a brief historical perspective of the field, from my personal standpoint and with insights from my own career, along with an outlook on what I believe will be the most interesting future developments in the field.

Facet-Defect Tolerant Bi-Doped Cs2AgxNa1-xInCl6 Nanoplatelets with a Near-Unity Photoluminescence Quantum Yield.

We report the colloidal synthesis of Bi-doped Cs2AgxNa1-xInCl6 double perovskite nanoplatelets (NPLs) exhibiting a near-unity photoluminescence quantum yield (PLQY), a record emission efficiency for nanoscale lead-free metal halides. A combination of optical spectroscopies revealed that nonradiative decay processes in the NPL were suppressed, indicating a well-passivated surface. By comparison, nanocubes with the same composition and surface ligands as the NPLs had a PLQY of only 40%. According to our calculations, the type of trap states arising from the presence of surface defects depends on their specific location: defects located on the facets of nanocubes generate only shallow traps, while those at the edges result in deep traps. In NPLs, due to their extended basal facets, most of the surface defects are facet defects. This so-called facet-defect tolerant behavior of double perovskites explains the more efficient optical emission of NPLs compared to that of nanocubes.

CsPbCl3 → CsPbI3 Exchange in Perovskite Nanocrystals Proceeds through a Jump-the-Gap Reaction Mechanism.

Halide exchange is a popular strategy to tune the properties of CsPbX3 nanocrystals after synthesis. However, while Cl → Br and Br → I exchanges proceed through the formation of stable mixed-halide nanocrystals, the Cl ⇌ I exchange is more elusive. Indeed, the large size difference between chloride and iodide ions causes a miscibility gap in the CsPbCl3-CsPbI3 system, preventing the isolation of stable CsPb(ClxI1-x)3 nanocrystals. Yet, previous works have claimed that a full CsPbCl3 → CsPbI3 exchange can be achieved. Even more interestingly, interrupting the exchange prematurely yields a mixture of CsPbCl3 and CsPbI3 nanocrystals that coexist without undergoing further transformation. Here, we investigate the reaction mechanism of CsPbCl3 → CsPbI3 exchange in nanocrystals. We show that the reaction proceeds through the early formation of iodide-doped CsPbCl3 nanocrystals covered by a monolayer shell of CsI. These nanocrystals then leap over the miscibility gap between CsPbCl3 and CsPbI3 by briefly transitioning to short-lived and nonrecoverable CsPb(ClxI1-x)3 nanocrystals, which quickly expel the excess chloride and turn into the chloride-doped CsPbI3 nanocrystals found in the final product.

Ru-Cu Nanoheterostructures for Efficient Hydrogen Evolution Reaction in Alkaline Water Electrolyzers.

Combining multiple species working in tandem for different hydrogen evolution reaction (HER) steps is an effective strategy to design HER electrocatalysts. Here, we engineered a hierarchical electrode for the HER composed of amorphous-TiO2/Cu nanorods (NRs) decorated with cost-effective Ru-Cu nanoheterostructures (Ru mass loading = 52 µg/cm2). Such an electrode exhibits a stable, over 250 h, low overpotential of 74 mV at -200 mA/cm2 for the HER in 1 M NaOH. The high activity of the electrode is attributed, by structural analysis, operando X-ray absorption spectroscopy, and first-principles simulations, to synergistic functionalities: (1) mechanically robust, vertically aligned Cu NRs with high electrical conductivity and porosity provide fast charge and gas transfer channels; (2) the Ru electronic structure, regulated by the size of Cu clusters at the surface, facilitates the water dissociation (Volmer step); (3) the Cu clusters grown atop Ru exhibit a close-to-zero Gibbs free energy of the hydrogen adsorption, promoting fast Heyrovsky/Tafel steps. An alkaline electrolyzer (AEL) coupling the proposed cathode and a stainless-steel anode can stably operate in both continuous (1 A/cm2 for over 200 h) and intermittent modes (accelerated stress tests). A techno-economic analysis predicts the minimal overall hydrogen production cost of US$2.12/kg in a 1 MW AEL plant of 30 year lifetime based on our AEL single cell, hitting the worldwide targets (US$2-2.5/kgH2).

Colloidal InAs Tetrapods: Impact of Surfactants on the Shape Control.

We have approached the synthesis of colloidal InAs nanocrystals (NCs) using amino-As and ligands that are different from the commonly employed oleylamine (OA). We found that carboxylic and phosphonic acids led only to oxides, whereas tri-n-octylphosphine, dioctylamine, or trioctylamine (TOA), when employed as the sole ligands, yielded InAs NCs with irregular sizes and a broad size distribution. Instead, various combinations of TOA and OA delivered InAs NCs with good control over the size distribution, and the TOA:OA volume ratio of 4:1 generated InAs tetrapods with arm length of 5-6 nm. Contrary to tetrapods of II-VI materials, which have a zinc-blende core and wurtzite arms, these NCs are entirely zinc-blende, with arms growing along the ⟨111⟩ directions. They feature a narrow excitonic peak at ∼950 nm in absorption and a weak photoluminescence emission at 1050 nm. Our calculations indicated that the bandgap of the InAs tetrapods is mainly governed by the size of their core and not by their arm lengths when these are longer than ∼3 nm. Nuclear magnetic resonance analyses revealed that InAs tetrapods are mostly passivated by OA with only a minor fraction of TOA. Molecular dynamics simulations showed that OA strongly binds to the (111) facets whereas TOA weakly binds to the edges and corners of the NCs and their combined use (at high TOA:OA volume ratios) promotes growth along the ⟨111⟩ directions, eventually forming tetrapods. Our work highlights the use of mixtures of ligands as a means of improving control over InAs NCs size and size distribution.

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.

High-performance alkaline water electrolyzers based on Ru-perturbed Cu nanoplatelets cathode.

Alkaline electrolyzers generally produce hydrogen at current densities below 0.5 A/cm2. Here, we design a cost-effective and robust cathode, consisting of electrodeposited Ru nanoparticles (mass loading ~ 53 µg/cm2) on vertically oriented Cu nanoplatelet arrays grown on metallic meshes. Such cathode is coupled with an anode based on stacked stainless steel meshes, which outperform NiFe hydroxide catalysts. Our electrolyzers exhibit current densities as high as 1 A/cm2 at 1.69 V and 3.6 A/cm2 at 2 V, reaching the performances of proton-exchange membrane electrolyzers. Also, our electrolyzers stably operate in continuous (1 A/cm2 for over 300 h) and intermittent modes. A total production cost of US$2.09/kgH2 is foreseen for a 1 MW plant (30-year lifetime) based on the proposed electrode technology, meeting the worldwide targets (US$2-2.5/kgH2). Hence, the use of a small amount of Ru in cathodes (~0.04 gRu per kW) is a promising strategy to solve the dichotomy between the capital and operational expenditures of conventional alkaline electrolyzers for high-throughput operation, while facing the scarcity issues of Pt-group metals.

Ultrastable and High-Efficiency Deep Red QLEDs through Giant Continuously Graded Colloidal Quantum Dots with Shell Engineering.

Quantum dot (QD) based light-emitting diodes (QLEDs) hold great promise for next-generation lighting and displays. In order to reach a wide color gamut, deep red QLEDs emitting at wavelengths beyond 630 nm are highly desirable but have rarely been reported. Here, we synthesized deep red emitting ZnCdSe/ZnSeS QDs (diameter ∼16 nm) with a continuous gradient bialloyed core-shell structure. These QDs exhibit high quantum yield, excellent stability, and a reduced hole injection barrier. The QLEDs based on ZnCdSe/ZnSeS QDs have an external quantum efficiency above 20% in the luminance range of 200-90000 cd m-2 and a record T95 operation lifetime (time for the luminance to decrease to 95% of its initial value) of more than 20000 h at a luminance of 1000 cd m-2. Furthermore, the ZnCdSe/ZnSeS QLEDs have outstanding shelf stability (>100 days) and cycle stability (>10 cycles). The reported QLEDs with excellent stability and durability can accelerate the pace of QLED applications.

Real-Time In Situ Observation of CsPbBr3 Perovskite Nanoplatelets Transforming into Nanosheets.

The manipulation of nano-objects through heating is an effective strategy for inducing structural modifications and therefore changing the optoelectronic properties of semiconducting materials. Despite its potential, the underlying mechanism of the structural transformations remains elusive, largely due to the challenges associated with their in situ observations. To address these issues, we synthesize temperature-sensitive CsPbBr3 perovskite nanoplatelets and investigate their structural evolution at the nanoscale using in situ heating transmission electron microscopy. We observe the morphological changes that start from the self-assembly of the nanoplatelets into ribbons on a substrate. We identify several paths of merging nanoplates within ribbons that ultimately lead to the formation of nanosheets dispersed randomly on the substrate. These observations are supported by molecular dynamics simulations. We correlate the various paths for merging to the random orientation of the initial ribbons along with the ligand mobility (especially from the edges of the nanoplatelets). This leads to the preferential growth of individual nanosheets and the merging of neighboring ones. These processes enable the creation of structures with tunable emission, ranging from blue to green, all from a single material. Our real-time observations of the transformation of perovskite 2D nanocrystals reveal a route to achieve large-area nanosheets by controlling the initial orientation of the self-assembled objects with potential for large-scale applications.

The Dark Side of Lead-Free Metal Halide Nanocrystals: Substituent-Modulated Photocatalytic Activity in Benzyl Bromide Reduction.

We illustrate here the high photocatalytic activity of sustainable lead-free metal halide nanocrystals (NCs), namely, Cs3Sb2Br9 NCs, in the reduction of p-substituted benzyl bromides in the absence of a cocatalyst. The electronic properties of the benzyl bromide substituents and the substrate affinity to the NC surface determine the selectivity in C-C homocoupling under visible light irradiation. This photocatalyst can be reused for at least three cycles and preserves its good performance with a turnover number of ca. 105,000.

Stable Sn-Based Hybrid Perovskite-Related Structures with Tunable Color Coordinates via Organic Cations in Low-Temperature Synthesis.

Organic-inorganic Pb-free layered perovskites are efficient broadband emitters and thus are promising materials for lighting applications. However, their synthetic protocols require a controlled atmosphere, high temperature, and long preparation time. This hinders the potential tunability of their emission through organic cations, as is instead common practice in Pb-based structures. Here, we present a set of Sn-Br layered perovskite-related structures that display different chromaticity coordinates and photoluminescence quantum yield (PLQY) up to 80%, depending on the choice of the organic monocation. We first develop a synthetic protocol that is performed under air and at 4 °C, requiring only a few steps. X-ray and 3D electron diffraction analyses show that the structures exhibit diverse octahedra connectivity (disconnected and face-sharing) and thus optical properties, while preserving the organic-inorganic layer intercalation. These results provide key insight into a previously underexplored strategy to tune the color coordinates of Pb-free layered perovskites through organic cations with complex molecular configurations.

Mixed Organic Cations Promote Ambient Light-Induced Formation of Metallic Lead in Lead Halide Perovskite Crystals.

One major concern toward the performance and stability of halide perovskite-based optoelectronic devices is the formation of metallic lead that promotes nonradiative recombination of charge carriers. The origin of metallic lead formation is being disputed whether it occurs during the perovskite synthesis or only after light, electron, or X-ray beam irradiation or thermal annealing. Here, we show that the quantity of metallic lead detected in perovskite crystals depends on the concentration and composition of the precursor solution. Through a controlled crystallization process, we grew black-colored mixed dimethylammonium (DMA)/methylammonium (MA) lead tribromide crystals. The black color is suggested to be due to the presence of small lead clusters. Despite the unexpected black coloring, the crystals show higher crystallinity and less defect density with respect to the standard yellow-colored DMA/MAPbBr3 crystals, as indicated by X-ray rocking curve and dark current measurements, respectively. While the formation of metallic lead could still be induced by external factors, the precursor solution composition and concentration can facilitate the formation of metallic lead during the crystallization process. Our results indicate that additional research is required to fully understand the perovskite precursor solution chemistry.