Using Surface-Enhanced Raman Spectroscopy to Probe Surface-Localized Nonthermal Plasma Activation.

Low-temperature, nonthermal plasmas generate a complex environment even when operated in nonreactive gases. Plasma-produced species impinge on exposed surfaces, and their thermalization is highly localized at the surface. Here we present a Raman thermometry approach to quantifying the resulting degree of surface heating. A nanostructured silver substrate is used to enhance the Raman signal and make it easily distinguishable from the background radiation from the plasma. Phenyl phosphonic acid is used as a molecular probe. Even under moderate plasma power and density, we measure a significant degree of vibrational excitation for the phenyl group, corresponding to an increase in surface temperature of ∼80 °C at a plasma density of 2 × 1010 cm-3. This work confirms that surface-localized thermal effects can be quantified in low-temperature plasma processes. Their characterization is needed to improve our understanding of the plasma-induced activation of surface reactions, which is highly relevant for a broad range of plasma-driven processes.

Enhancing the Combustion of Magnesium Nanoparticles via Low-Temperature Plasma-Induced Hydrogenation.

The hydrogenation of metal nanoparticles provides a pathway toward tuning their combustion characteristics. Metal hydrides have been employed as solid-fuel additives for rocket propellants, pyrotechnics, and explosives. Gas generation during combustion is beneficial to prevent aggregation and sintering of particles, enabling a more complete fuel utilization. Here, we discuss a novel approach for the synthesis of magnesium hydride nanoparticles based on a two-step aerosol process. Mg particles are first nucleated and grown via thermal evaporation, followed immediately by in-flight exposure to a hydrogen-rich low-temperature plasma. During the second step, atomic hydrogen generated by the plasma rapidly diffuses into the Mg lattice, forming particles with a significant fraction of MgH2. We find that hydrogenated Mg nanoparticles have an ignition temperature that is reduced by ∼200 °C when combusted with potassium perchlorate as an oxidizer, compared to the non-hydrogenated Mg material. This is due to the release of hydrogen from the fuel, jumpstarting its combustion. In addition, characterization of the plasma processes suggests that a careful balance between the dissociation of molecular hydrogen and heating of the nanoparticles must be achieved to avoid hydrogen desorption during production and achieve a significant degree of hydrogenation.

Efficient photon upconversion enabled by strong coupling between silicon quantum dots and anthracene.

Hybrid structures formed between organic molecules and inorganic quantum dots can accomplish unique photophysical transformations by taking advantage of their disparate properties. The electronic coupling between these materials is typically weak, leading photoexcited charge carriers to spatially localize to the dot or to a molecule at its surface. However, we show that by converting a chemical linker that covalently binds anthracene molecules to silicon quantum dots from a carbon-carbon single bond to a double bond, we access a strong coupling regime where excited carriers spatially delocalize across both anthracene and silicon. By pushing the system to delocalize, we design a photon upconversion system with a higher efficiency (17.2%) and lower threshold intensity (0.5 W cm-2) than that of a corresponding weakly coupled system. Our results show that strong coupling between molecules and nanostructures achieved through targeted linking chemistry provides a complementary route for tailoring properties in materials for light-driven applications.

Gas-phase grafting for the multifunctional surface modification of silicon quantum dots.

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.

Photothermal heating of titanium nitride nanomaterials for fast and uniform laser warming of cryopreserved biomaterials.

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.

Nanocrystalline Yttria-Stabilized Zirconia Ceramics for Cranial Window Applications.

Transparent yttria-stabilized zirconia (YSZ) ceramics are promising for cranial window applications because of their good mechanical and optical properties as well as biocompatibility. YSZ discs with different yttria concentrations were either processed via current-activated pressure-assisted densification (CAPAD) using commercial nanoparticles or densified via spark plasma sintering (SPS) using pyrolysis-synthesized nanoparticles in-house. This study provided critical results to screen composition, processing, microstructure, and cytocompatibility of transparent YSZ discs for cranial window applications. CAPAD-processed YSZ discs with 6 or 8 mol % yttria (6YSZ and 8YSZ) and SPS-densified YSZ discs with 4 mol % yttria (4YSZ_P) showed 200-350 nm polycrystalline grains containing 20-30 nm crystallite domains. SPS-densified YSZ discs with 8 mol % yttria (8YSZ_P) showed larger polycrystalline grains of 819 ± 155 nm with 29 ± 5 nm crystallite domains. CAPAD-processed YSZ discs with 3 mol % yttria (3YSZ) showed 39 ± 9 nm grains. Bone-marrow-derived stem cells (BMSCs) on the polished YSZ discs showed statistically higher spreading areas than those on the unpolished YSZ discs of the same compositions. Generally, polished 8YSZ, 4YSZ_P, and 8YSZ_P discs and unpolished 8YSZ_R, 4YSZ_PR, and 8YSZ_PR discs had lower average cell adhesion densities than other YSZ discs under direct contact conditions. Under indirect contact conditions, all the YSZ disc groups showed similar average cell adhesion densities to the Cell-only control. The groups of polished 4YSZ_P and 8YSZ_P discs, unpolished 4YSZ_PR and 8YSZ_PR discs, and particle control of 8YSZ_Pnp showed higher Y3+ ion concentrations than other groups. No mineral deposition was detected on the polished YSZ discs after cell culture. Considering multiple factors such as cytocompatibility, cell adhesion density, Y3+ ion release, mineral deposition, and optical transparency collectively, 8YSZ may be the best candidate for the cranial window applications. Further studies are needed to evaluate the long-term transparency and biocompatibility of YSZ discs.

Laser-induced cavitation in plasmonic nanoparticle solutions: A comparative study between gold and titanium nitride.

In this work, we present an extensive comparative study between novel titanium nitride nanoparticles (TiN NPs) and commercial gold nanorods (GNR), both dispersed in water and exposed to a pulsed laser-induced cavitation process. The optical density, shockwave emission, and bubble formation of these solutions were investigated using shadowgraphy, spatial transmittance modulation, and acoustic measurements. TiN nanoparticle solutions exhibited high stability undser a periodic nanosecond pulsed-laser irradiation, making these nanomaterials promising agents for high-power applications. In addition, they demonstrated a stronger nonlinear absorption compared to the GNR solutions, and plasma formation at lower laser energies. This study advances our understanding of the optical properties of TiN and discusses significant differences compared to gold, with important implications for future applications of this material in water treatment, nonlinear signal converting, and laser-induced cavitation for medical implementations, among others.

Efficient facemask decontamination via forced ozone convection.

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 using Escherichia coli (E. coli) and Vesicular 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.

Bidirectional triplet exciton transfer between silicon nanocrystals and perylene.

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.

Silicon Nanoparticles for the Reactivity and Energetic Density Enhancement of Energetic-Biocidal Mesoparticle Composites.

Biocidal nanothermite composites show great potential in combating biological warfare threats because of their high-energy-release rates and rapid biocidal agent release. Despite their high reactivity and combustion performance, these composites suffer from low-energy density because of the voids formed due to inefficient packing of fuel and oxidizer particles. In this study, we explore the potential of plasma-synthesized ultrafine Si nanoparticles (nSi, ∼5 nm) as an energetic filler fuel to increase the energy density of Al/Ca(IO3)2 energetic-biocidal composites by filling in the voids in the microstructure. Microscopic and elemental analyses show the partial filling of mesoparticle voids by nSi, resulting in an estimated energy density enhancement of ∼21%. In addition, constant-volume combustion cell results show that nSi addition leads to a ∼2-3-fold increase in reactivity and combustion performance, as compared to Al/Ca(IO3)2 mesoparticles. Oxidation timescale analyses suggest that nSi addition can promote initiation due to faster oxygen transport through the oxide shell of Si nanoparticles. At nSi loadings higher than ∼8%, however, slower burning characteristics of nSi and sintering effects lead to an overall degradation of combustion behavior of the composites.

Harnessing Plasma Environments for Ammonia Catalysis: Mechanistic Insights from Experiments and Large-Scale Ab Initio Molecular Dynamics.

By combining experimental measurements with ab initio molecular dynamics simulations, we provide the first microscopic description of the interaction between metal surfaces and a low-temperature nitrogen-hydrogen plasma. Our study focuses on the dissociation of hydrogen and nitrogen as the main activation route. We find that ammonia forms via an Eley-Rideal mechanism where atomic nitrogen abstracts hydrogen from the catalyst surface to form ammonia on an extremely short time scale (a few picoseconds). On copper, ammonia formation occurs via the interaction between plasma-produced atomic nitrogen and the H-terminated surface. On platinum, however, we find that surface saturation with NH groups is necessary for ammonia production to occur. Regardless of the metal surface, the reaction is limited by the mass transport of atomic nitrogen, consistent with the weak dependence on catalyst material that we observe and has been reported by several other groups. This study represents a significant step toward achieving a mechanistic, microscopic-scale understanding of catalytic processes activated in low-temperature plasma environments.

Low temperature radical initiated hydrosilylation of silicon quantum dots.

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.

Critical barriers to the large scale commercialization of silicon-containing batteries.

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.

Synthesis, characterization, and cytocompatibility of yttria stabilized zirconia nanopowders for creating a window to the brain.

Transparent cranial window to the brain is highly desirable for brain therapies because such cranial implant would allow for continuous monitoring of brain disorders and long-term delivery of photodynamic therapy into the brain without repeated surgeries for opening skull. Nanostructured yttria-stabilized zirconia (YSZ) is a potential candidate for the window to the brain application because of its promising mechanical and optical properties. In this study, a new process using aerosol spray pyrolysis was established for synthesizing 6-7 nm YSZ nanopowders with precisely controlled compositions. YSZ nanopowders with 3 M ratios of yttria to zirconia, specifically 3, 6, and 8% yttria in zirconia (referred to as 3YSZ, 6YSZ, and 8YSZ, respectively) were synthesized and characterized. The size, structure, and composition of the produced YSZ nanoparticles are highly controllable and scalable. The in vitro cytocompatibility of the YSZ nanoparticles with bone marrow mesenchymal stem cells (BMSCs) was investigated using a direct exposure culture method for cranial implant applications. Nondoped ZrO2 and commercially available 8YSZ (named as C_8YSZ) served as controls for the in vitro cell studies. BMSCs exhibited normal morphology when cultured with the YSZs of 3 M ratios in the concentrations of 10 mM, 30 mM, and 60 mM, as well as ZrO2 and C_8YSZ controls. The BMSCs cultured with 3YSZ and 6YSZ showed no statistical differences in cell adhesion density when compared with the ZrO2 and C_8YSZ controls at respective concentrations of 10-60 mM. The possible release of YSZ nanoparticles from cranial window implants should be carefully considered and further studied.

Achieving spin-triplet exciton transfer between silicon and molecular acceptors for photon upconversion.

Inorganic semiconductor nanocrystals interfaced with spin-triplet exciton-accepting organic molecules have emerged as promising materials for converting incoherent long-wavelength light into the visible range. However, these materials to date have made exclusive use of nanocrystals containing toxic elements, precluding their use in biological or environmentally sensitive applications. Here, we address this challenge by chemically functionalizing non-toxic silicon nanocrystals with triplet-accepting anthracene ligands. Photoexciting these structures drives spin-triplet exciton transfer from silicon to anthracene through a single 15 ns Dexter energy transfer step with a nearly 50% yield. When paired with 9,10-diphenylanthracene emitters, these particles readily upconvert 488-640 nm photons to 425 nm violet light with efficiencies as high as 7 ± 0.9% and can be readily incorporated into aqueous micelles for biological use. Our demonstration of spin-triplet exciton transfer from silicon to molecular triplet acceptors can critically enable new technologies for solar energy conversion, quantum information and near-infrared driven photocatalysis.

Silicon-Core-Carbon-Shell Nanoparticles for Lithium-Ion Batteries: Rational Comparison between Amorphous and Graphitic Carbon Coatings.

Silicon-core-carbon-shell nanoparticles have been widely studied as promising candidates for the replacement of graphite in commercial lithium-ion batteries. Over more than 10 years of R&D, the many groups actively working in this field have proposed a profusion of distinctive nanomaterial designs. This broad variety makes it extremely challenging to establish mechanistic insight into how fundamental material structure and properties affect battery performance. In particular, the interplay between the character of the carbon encapsulation layer and the electrochemical performance of the composite is still poorly understood. In this work, we aim to address this lack of knowledge through the development of a modified chemical vapor deposition approach that enables precise control of the degree of graphitization of the carbon coating. We provide a comparison between core-shell structures maintaining identical silicon cores with different types of carbon shells, that is, graphitic carbon and amorphous carbon. A highly graphitic carbon layer is not only characterized by higher electrical conductivity but markedly favors the transport of lithium ions into the silicon core with respect to an amorphous one. This advantageous property confers better cycling stability to the composite material. We also demonstrate that the graphitic-carbon-coated particles display excellent electrochemical performance even when used as a simple "drop-in" additive in graphite-dominant anodes for current generation Li-ion batteries. Replacement of 10% by weight of graphite in the electrode composition results in an increase of 60% in the storage capacity with a first cycle Coulombic efficiency of 91% and capacity retention over 100 cycles of 86%.

Plasmonic Core-Shell Silicon Carbide-Graphene Nanoparticles.

We demonstrate the synthesis of silicon carbide nanoparticles exhibiting monolayer to few-layer graphene coatings and characterize their optical response to confirm their plasmonic behavior. A multistep, low-temperature plasma process is used to nucleate silicon particles, carbonize them in-flight to give small silicon carbide nanocrystals, and coat them in-flight with a graphene shell. These particles show surface plasmon resonance in the infrared region. Tuning of the plasma parameters allows control over the nanoparticle size and consequently over the absorption peak position. A simplified equivalent dielectric permittivity model shows excellent agreement with the experimental data. In addition, optical characterization at high temperatures confirms the stability of their optical properties, making this material attractive for a broad range of applications.

Colloidal Synthesis of Silicon-Carbon Composite Material for Lithium-Ion Batteries.

We report colloidal routes to synthesize silicon@carbon composites for the first time. Surface-functionalized Si nanoparticles (SiNPs) dissolved in styrene and hexadecane are used as the dispersed phase in oil-in-water emulsions, from which yolk-shell and dual-shell hollow SiNPs@C composites are produced via polymerization and subsequent carbonization. As anode materials for Li-ion batteries, the SiNPs@C composites demonstrate excellent cycling stability and rate performance, which is ascribed to the uniform distribution of SiNPs within the carbon hosts. The Li-ion anodes composed of 46 wt % of dual-shell SiNPs@C, 46 wt % of graphite, 5 wt % of acetylene black, and 3 wt % of carboxymethyl cellulose with an areal loading higher than 3 mg cm-2 achieve an overall specific capacity higher than 600 mAh g-1 , which is an improvement of more than 100 % compared to the pure graphite anode. These new colloidal routes present a promising general method to produce viable Si-C composites for Li-ion batteries.

Grain-to-Grain Compositional Variations and Phase Segregation in Copper-Zinc-Tin-Sulfide Films.

We have performed a rigorous investigation of the structure and composition of individual grains in copper-zinc-tin-sulfide (CZTS) films realized by sulfurization of a sputtered metal stack. Although on average close to the ideal CZTS stoichiometry, elemental analysis shows significant grain-to-grain variations in composition. High-resolution Raman spectroscopy indicates that this is accompanied by grain-to-grain structural variations as well. The intensity from the 337 cm(-1) Raman peak, generally assigned to the kesterite phase of CZTS, remains constant over a large area of the sample. On the other hand, signals from secondary phases at 376 cm(-1) (copper-tin-sulfide) and 351 cm(-1) (zinc-sulfide) show significant variation over the same area. These results confirm the great complexity inherent to this material system. Moreover, structural and compositional variations are recognized in the literature as a factor limiting the efficiency of CZTS photovoltaic devices. This study demonstrates how a seemingly homogeneous CZTS thin film can actually have considerable structural and compositional variations at the microscale, and highlights the need for routine microscale characterization in this material system.

Low activation energy for the crystallization of amorphous silicon nanoparticles.

We have experimentally determined the crystallization rate of plasma-produced amorphous silicon powder undergoing in-flight thermal annealing, and have found a significant reduction in the activation energy for crystallization compared to amorphous silicon thin films. This finding allows us to shed light onto the mechanism leading to the formation of high quality nanocrystals in non-thermal plasmas.