Spectral fingerprints of individual Mn2+ impurities and Mn2+ pairs in magic-sized nanoclusters

The chemical synthesis of (CdSe)(13) magic-sized clusters (MSCs) allows the replacement of host atoms by individual transition metals such as Mn. By analyzing the spectral fingerprints of the Mn2+ photoluminescence (PL) in MSCs with different dopant concentrations, we are able to distinguish between single Mn2+ ions and coupled Mn2+ pairs. In case of Mn2+ pair emission, temperature-dependent studies show a pronounced red shift, followed by a distinct blue shift of the PL energy upon heating. This is related to a spin ladder formation of the ground and excited states due to Mn2+-Mn2+ exchange interaction at cryogenic temperatures, which is assumed to vanish at higher temperatures. In contrast, single Mn2+ ion PL exhibits a unique redshift with increasing temperature, which can be attributed to a particularly strong coupling to vibronic modes due to the ultimate small size of the MSCs.Y

Magic-Sized Stoichiometric II-VI Nanoclusters

Metal chalcogenide nanomaterials have gained widespread interest in the past two decades for their potential optoelectronic, energy, and catalytic applications. The colloidal growth of various forms of these materials, such as nanowires, platelets, and lamellar assemblies, proceeds through certain thermodynamically stable, ultrasmall (<2 nm) intermediates called magic-sized nanoclusters (MSCs). Due to quantum confinement and its resultant intriguing properties, isolation or direct synthesis of MSCs and their structure characterization, which is very much challenging, are current topics of fundamental and applied scientific research. By comprehensive understanding of the structure-activity relationships in MSCs, the nucleation and growth processes can be manipulated, resulting in the synthesis of novel metal chalcogenide materials for various applications. This review focuses on recent advances in the chemical synthesis, characterization, and theoretical calculations of CdSe and its related II-VI nanoclusters. It highlights the studies of photophysical and magneto-optical properties as well as heteroatom doping of MSCs followed by their chemical transformation to high-dimensional nanostructures. At the end of the review, future directions and possible ways to overcome the challenges in the research of semiconductor MSCs are also presented.

High photoluminescence from self-assembled Ag2Cl2(dppe)(2) clusters through metallophilic interactions

Ligand protected metal nanoclusters (NCs) are an emerging class of functional materials with intriguing photophysical and chemical properties. The size and molecular structure play an important role in endowing NCs with characteristic optical and electronic properties. Modulation of these properties through the chemical reactivity of NCs is largely unexplored. Here, we report on the synthesis of self-assembled Ag2Cl2(dppe)(2) clusters through the ligand-exchange-induced transformation of [Pt2Ag23Cl7(PPh3)(10)] NCs [(dppe): 1,2-bis(diphenylphosphino)ethane; (PPh3): triphenylphosphine]. The single crystal x-ray structure reveals that two Ag atoms are bridged by one dppe and two Cl ligands, forming a Ag2Cl2(dppe) cluster, which is subsequently self-assembled through dppe ligands to form [Ag2Cl2(dppe)(2)](n). Importantly, the Ag2Cl2(dppe)(2) cluster assembly exhibits high photoluminescence quantum yield: similar to 18%, which is attributed to the metallophilic interactions and rigidification of the ligand shell. We hope that this work will motivate the exploitation of the chemical reactivity of NCs as a new path to attain cluster assemblies endowed with enhanced photophysical properties. Published under an exclusive license by AIP Publishing.

Moisture proof hole transport layers based on CISe quantum dots for highly stable and large active area perovskite solar cells

© 2019 Elsevier B.V.Extensive studies have been performed to improve the environmental stability of perovskite solar cells (PSCs) with the use of inorganic charge transport layers (CTLs). However, for n-i-p structures, it is difficult to deposit p-type inorganic nanocrystals onto perovskites to form the CTLs because they are usually prepared in polar solvents. In this regard, hydrophobic nanoparticles dispersed in nonpolar solvents would be beneficial for their deposition onto the perovskites, thus leading to the formation of a hole transport layer (HTL). In this work, we report on the preparation of monodispersed CuIn1.5Se3 (CISe) quantum dots (QDs) (diameter = 4 nm) for the design of PSCs based on all-inorganic CTLs. By means of efficient hole injection and transfer process through the CISe-HTLs, impressive power conversion efficiencies (PCEs) of 13.72% and 12.19% for active areas of 0.12 cm2 and 1.0 cm2 are achieved, respectively, and the devices exhibit hysteresis-less behaviors. Furthermore, the devices show excellent PCE retentions of 89.2% and 74.9% after 30 d relative to their initial values at relative humidity of 25% and 50%, respectively. The hydrophobic QDs effectively suppress the penetration of moisture such that the device maintains its stability in humid environments11sciescopu

Magic‐Sized Stoichiometric II–VI Nanoclusters

Metal chalcogenide nanomaterials have gained widespread interest in the past two decades for their potential optoelectronic, energy, and catalytic applications. The colloidal growth of various forms of these materials, such as nanowires, platelets, and lamellar assemblies, proceeds through certain thermodynamically stable, ultrasmall (<2 nm) intermediates called magic-sized nanoclusters (MSCs). Due to quantum confinement and its resultant intriguing properties, isolation or direct synthesis of MSCs and their structure characterization, which is very much challenging, are current topics of fundamental and applied scientific research. By comprehensive understanding of the structure-activity relationships in MSCs, the nucleation and growth processes can be manipulated, resulting in the synthesis of novel metal chalcogenide materials for various applications. This review focuses on recent advances in the chemical synthesis, characterization, and theoretical calculations of CdSe and its related II-VI nanoclusters. It highlights the studies of photophysical and magneto-optical properties as well as heteroatom doping of MSCs followed by their chemical transformation to high-dimensional nanostructures. At the end of the review, future directions and possible ways to overcome the challenges in the research of semiconductor MSCs are also presented.11Nsciescopu

Digital Doping in Magic-Sized CdSe Clusters

Magic-sized semiconductor clusters represent an exciting class of materials located at the boundary between quantum dots and molecules. It is expected that replacing single atoms of the host crystal with individual dopants in a one-by-one fashion can lead to unique modifications of the material properties. Here, we demonstrate the dependence of the magneto-optical response of (CdSe)13 clusters on the discrete number of Mn2+ ion dopants. Using time-of-flight mass spectrometry, we are able to distinguish undoped, monodoped, and bidoped cluster species, allowing for an extraction of the relative amount of each species for a specific average doping concentration. A giant magneto-optical response is observed up to room temperature with clear evidence that exclusively monodoped clusters are magneto-optically active, whereas the Mn2+ ions in bidoped clusters couple antiferromagnetically and are magneto-optically passive. Mn2+-doped clusters therefore represent a system where magneto-optical functionality is caused by solitary dopants, which might be beneficial for future solotronic applications. © 2016 American Chemical Society116151sciescopu

Highly luminescent and catalytically active suprastructures of magic-sized semiconductor nanoclusters

Metal chalcogenide magic-sized nanoclusters have shown intriguing photophysical and chemical properties, yet ambient instability has hampered their extensive applications. Here we explore the periodic assembly of these nanoscale building blocks through organic linkers to overcome such limitations and further boost their properties. We designed a diamine-based heat-up self-assembly process to assemble Mn2+:(CdSe)(13) and Mn2+:(ZnSe)(13) magic-sized nanoclusters into three- and two-dimensional suprastructures, respectively, obtaining enhanced stability and solid-state photoluminescence quantum yields (from <1% for monoamine-based systems to similar to 72% for diamine-based suprastructures). We also exploited the atomic-level miscibility of Cd and Zn to synthesize Mn2+:(Cd1-xZnxSe)(13) alloy suprastructures with tunable metal synergy: Mn2+:(Cd0.5Zn0.5Se)(13) suprastructures demonstrated high catalytic activity (turnover number, 17,964 per cluster in 6 h; turnover frequency, 2,994 per cluster per hour) for converting CO2 to organic cyclic carbonates under mild reaction conditions. The enhanced stability, photoluminescence and catalytic activity through combined cluster-assembly and metal synergy advance the usability of inorganic semiconductor nanoclusters.

Recent Advances and Prospects in Colloidal Nanomaterials

Colloidal nanomaterials of metals, metal oxides, and metal chalcogenides have attracted great attention in the past decade owing to their potential applications in optoelectronics, catalysis, and energy conversion. Introduction of various synthetic routes has resulted in diverse colloidal nanostructured materials with wellcontrolled size, shape, and composition, enabling the systematic study of their intriguing physicochemical, optoelectronic, and chemical properties. Furthermore, developments in the instrumentation have offered valuable insights into the nucleation and growth mechanism of these nanomaterials, which are crucial in designing prospective materials with desired properties. In this perspective, recent advances in the colloidal synthesis and mechanism studies of nanomaterials of metal chalcogenides, metals, and metal oxides are discussed. In addition, challenges in the characterization and future direction of the colloidal nanomaterials are provided.11Nothe

Scalable Neural Architecture Search for 3D Medical Image Segmentation

In this paper, a neural architecture search (NAS) framework is proposed for 3D medical image segmentation, to automatically optimize a neural architecture from a large design space. Our NAS framework searches the structure of each layer including neural connectivities and operation types in both of the encoder and decoder. Since optimizing over a large discrete architecture space is difficult due to high-resolution 3D medical images, a novel stochastic sampling algorithm based on a continuous relaxation is also proposed for scalable gradient based optimization. On the 3D medical image segmentation tasks with a benchmark dataset, an automatically designed architecture by the proposed NAS framework outperforms the human-designed 3D U-Net, and moreover this optimized architecture is well suited to be transferred for different tasks