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  1. Free, publicly-accessible full text available August 1, 2024
  2. Photon upconversion in systems incorporating inorganic quantum dots (QDs) is of great interest for applications in solar energy conversion, bioimaging, and photodynamic therapy. Achieving high up-conversion efficiency requires not only high-quality inorganic nanoparticles, but also precise control of their surface functional groups. Gas-phase surface functionalization provides a new pathway towards controlling the surface of small inorganic nanoparticles. In this contribution, we utilize a one-step low-temperature plasma technique for the synthesis and in-flight partial functionalization of silicon QDs with alkyl chains. The partially functionalized surface is then modified further with 9-vinylanthracene via thermal hydrosilylation resulting in the grafting of 9-ethylanthracene (9EA) groups. We have found that the minimum alkyl ligand density necessary for quantum dot solubility also gives the maximum upconversion quantum yield, reaching 17% for silicon QDs with Si-dodecyl chains and an average of 3 9EA molecules per particle. 
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  3. Titanium nitride (TiN) is presented as an alternative plasmonic nanomaterial to the commonly used gold (Au) for its potential use in laser rewarming of cryopreserved biomaterials. The rewarming of vitrified, glass like state, cryopreserved biomaterials is a delicate process as potential ice formation leads to mechanical stress and cracking on a macroscale, and damage to cell walls and DNA on a microscale, ultimately leading to the destruction of the biomaterial. The use of plasmonic nanomaterials dispersed in cryoprotective agent solutions to rapidly convert optical radiation into heat, generally supplied by a focused laser beam, proposes a novel approach to overcome this difficulty. This study focuses on the performance of TiN nanoparticles (NPs), since they present high thermal stability and are inexpensive compared to Au. To uniformly warm up the nanomaterial solutions, a beam splitting laser system was developed to heat samples from multiple sides with equal beam energy distribution. In addition, uniform laser warming requires equal distribution of absorption and scattering properties in the nanomaterials. Preliminary results demonstrated higher absorption but less scattering in TiN NPs than Au nanorods (GNRs). This led to the development of TiN clusters, synthetized by nanoparticle agglomeration, to increase the scattering cross-section of the material. Overall, this study analyzed the heating rate, thermal efficiency, and heating uniformity of TiN NPs and clusters in comparison to GNRs at different solution concentrations. TiN NPs and clusters demonstrated higher heating rates and solution temperatures, while only clusters led to a significantly improved uniformity in heating. These results highlight a promising alternative plasmonic nanomaterial to rewarm cryopreserved biological systems in the future.

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  4. Abstract The use of silicon nanoparticles for lithium-ion batteries requires a precise control over both their average size and their size distribution. Particles larger than the generally accepted critical size of 150 nm fail during lithiation because of excessive swelling, while very small particles (<10 nm) inevitably lead to a poor first cycle coulombic efficiency because of their excessive specific surface area. Both mechanisms induce irreversible capacity losses and are detrimental to the anode functionality. In this manuscript we describe a novel approach for enhanced growth of nanoparticles to ∼20 nm using low-temperature flow-through plasma reactors via pulsing. Pulsing of the RF power leads to a significant increase in the average particle size, all while maintaining the particles well below the critical size for stable operation in a lithium-ion battery anode. A zero-dimensional aerosol plasma model is developed to provide insights into the dynamics of particle agglomeration and growth in the pulsed plasma reactor. The accelerated growth correlates with the shape of the particle size distribution in the afterglow, which is in turn controlled by parameters such as metastable density, gas and electron temperature. The accelerated agglomeration in each afterglow phase is followed by rapid sintering of the agglomerates into single-crystal particles in the following plasma-on phase. This study highlights the potential of non-thermal plasma reactors for the synthesis of functional nanomaterials, while also underscoring the need for better characterization of their fundamental parameters in transient regimes. 
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  5. null (Ed.)
    Silicon has received a considerable amount of attention in the last few years because of its large lithiation capacity. Its widespread utilization in real-life lithium-ion batteries has so far been prevented by the plethora of challenges presented by this material. This review discusses the most promising technologies that have been put forward to address these issues. While silicon is now much closer to being compatible with commercial-grade storage devices, some critical barriers still deserve further attention. Most importantly, device performance is strongly dependent on particle size and size distribution, with these parameters strongly controlled by the particle synthesis technique. Moreover, the nanoparticle synthesis technique ultimately controls the material manufacturing cost and compatibility with large-scale utilization. These issues are discussed in detail, and recommendations to the community are provided. 
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  6. Abstract

    The COVID-19 crisis has taken a significant toll on human life and the global economy since its start in early 2020. Healthcare professionals have been particularly vulnerable because of the unprecedented shortage of Facepiece Respirators (FPRs), which act as fundamental tools to protect the medical staff treating the coronavirus patients. In addition, many FPRs are designed to be disposable single-use devices, creating an issue related to the generation of large quantities of non-biodegradable waste. In this contribution, we describe a plasma-based decontamination technique designed to circumvent the shortages of FPRs and alleviate the environmental problems posed by waste generation. The system utilizes a Dielectric Barrier Discharge (DBD) to generate ozone and feed it through the fibers of the FPRs. The flow-through configuration is different than canonical ozone-based sterilization methods, in which the equipment is placed in a sealed ozone-containing enclosure without any flow through the mask polymer fibers. We demonstrate the rapid decontamination of surgical masks usingEscherichia coli(E. coli) andVesicular Stomatitis Virus(VSV) as model pathogens, with the flow-through configuration providing a drastic reduction in sterilization time compared to the canonical approach. We also demonstrate that there is no deterioration in mask structure or filtration efficiency resulting from sterilization. Finally, we show that this decontamination approach can be implemented using readily available tools, such as a plastic box, a glass tube, few 3D printed components, and the high-voltage power supply from a plasma globe toy. The prototype assembled for this study is portable and affordable, with effectiveness comparable to that of larger and more expensive equipment.

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  7. null (Ed.)
    Hybrid materials comprised of inorganic quantum dots functionalized with small-molecule organic chromophores have emerged as promising materials for reshaping light's energy content. Quantum dots in these structures can serve as light harvesting antennas that absorb photons and pass their energy to molecules bound to their surface in the form of spin-triplet excitons. Energy passed in this manner can fuel upconversion schemes that use triplet fusion to convert infrared light into visible emission. Likewise, triplet excitons passed in the opposite direction, from molecules to quantum dots, can enable solar cells that use singlet fission to circumvent the Shockley–Queisser limit. Silicon QDs represent a key target for these hybrid materials due to silicon's biocompatibility and preeminence within the solar energy market. However, while triplet transfer from silicon QDs to molecules has been observed, no reports to date have shown evidence of energy moving in the reverse direction. Here, we address this gap by creating silicon QDs functionalized with perylene chromophores that exhibit bidirectional triplet exciton transfer. Using transient absorption, we find triplet transfer from silicon to perylene takes place over 4.2 μs while energy transfer in the reverse direction occurs two orders of magnitude faster, on a 22 ns timescale. To demonstrate this system's utility, we use it to create a photon upconversion system that generates blue emission at 475 nm using photons with wavelengths as long as 730 nm. Our work shows formation of covalent linkages between silicon and organic molecules can provide sufficient electronic coupling to allow efficient bidirectional triplet exchange, enabling new technologies for photon conversion. 
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  8. null (Ed.)
    The photophysics of silicon quantum dots (QDs) is not well understood despite their potential for many optoelectronic applications. One of the barriers to the study and widespread adoption of Si QDs is the difficulty in functionalizing their surface, to make, for example, a solution-processable electronically-active colloid. While thermal hydrosilylation of Si QDs is widely used, the high temperature typically needed may trigger undesirable side-effects, like uncontrolled polymerization of the terminal alkene. In this contribution, we show that this high-temperature method for installing aromatic and aliphatic ligands on non-thermal plasma-synthesized Si QDs can be replaced with a low-temperature, radical-initiated hydrosilylation method. Materials prepared via this low-temperature route perform similarly to those created via high-temperature thermal hydrosilylation when used in triplet fusion photon upconversion systems, suggesting the utility of low-temperature, radical-initiated methods for creating Si QDs with a range of functional behavior. 
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  9. Abstract

    Titanium nitride nanoparticles have become a research interest due to their distinguished optical and photothermal properties. Furthermore, the search for nanoparticle solutions with tunable nonlinear optical properties for laser‐based applications is critical. More specifically, third order optical nonlinearities such as reverse saturable absorption, optical liming, and self‐focusing are important in the biomedical and electronics fields. The optical nonlinearities of titanium nitride plasmonic nanoparticles are investigated as a function of material concentration in water solutions. Furthermore, the effect of nanoparticle clustering on optical nonlinearities is investigated by fabricating micrometer‐sized clusters of ≈50 nm titanium nitride particles. These studies demonstrate that the nonlinear absorption coefficient increases linearly with concentration. However, clusters require higher concentrations compared to the freestanding nanoparticles to exhibit similar nonlinear absorption coefficient and optical density. Similarly, the optical limiting threshold for titanium nitride nanoparticles appears to be lower compared to the cluster solutions, which is impacted by the collective scattering of nanoparticles and high reverse saturable absorption. In addition, self‐focusing is observed in the continuous resonant regime. This study provides an in‐depth analysis of the nonlinear optical properties of titanium nitride, with relevant consequences for applications such as sensor protection and photothermal therapy.

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  10. null (Ed.)