Search for: All records

Uniform-size, non-native oxide-passivated metallic aluminum nanoparticles (Al NPs) have desirable properties for fuel applications, battery components, plasmonics, and hydrogen catalysis. Nonthermal plasma-assisted synthesis of Al NPs was previously achieved with an inductively coupled plasma (ICP) reactor, but the low production rate and limited tunability of particle size were key barriers to the applications of this material. This work focuses on the application of capacitively coupled plasma (CCP) to achieve improved control over Al NP size and a ten-fold increase in yield. In contrast with many other materials, where NP size is controlled via the gas residence time in the reactor, the Al NP size appeared to depend on the power input to the CCP system. The results indicate that the CCP reactor assembly, with a hydrogen-rich argon/hydrogen plasma, was able to produce Al NPs with diameters that were tunable between 8 and 21 nm at a rate up ∼ 100 mg h⁻¹. X-ray diffraction indicates that a hydrogen-rich environment results in crystalline metal Al particles. The improved synthesis control of the CCP system compared to the ICP system is interpreted in terms of the CCP’s lower plasma density, as determined by double Langmuir probe measurements, leading to reduced NP heating in the CCP that is more amenable to NP nucleation and growth.

 

Abstract Silver nanoparticles (NPs) are extensively used in electronic components, chemical sensors, and disinfection applications, in which many of their properties depend on particle size. However, control over silver NP size and morphology still remains a challenge for many synthesis techniques. In this work, we demonstrate the surfactant-free synthesis of silver NPs using a low-pressure inductively coupled nonthermal argon plasma. Continuously forming droplets of silver nitrate (AgNO 3 ) precursor dissolved in glycerol are exposed to the plasma, with the droplet residence time being determined by the precursor flow rate. Glycerol has rarely been studied in plasma-liquid interactions but shows favorable properties for controlled NP synthesis at low pressure. We show that the droplet residence time and plasma power have strong influence on NP properties, and that improved size control and particle monodispersity can be achieved by pulsed power operation. Silver NPs had mean diameters of 20 nm with geometric standard deviations of 1.6 under continuous wave operation, which decreased to 6 nm mean and 1.3 geometric standard deviation for pulsed power operation at 100 Hz and 20% duty cycle. We propose that solvated electrons from the plasma and vacuum ultraviolet (VUV) radiation induced electrons produced in glycerol are the main reducing agents of Ag + , the precursor for NPs, while no significant change of chemical composition of the glycerol solvent was detected. 

Low-temperature plasmas have seen increasing use for synthesizing high-quality, mono-disperse nanoparticles (NPs). Recent work has highlighted that an important process in NP growth in plasmas is particle trapping—small, negatively charged nanoparticles become trapped by the positive electrostatic potential in the plasma, even if only momentarily charged. In this article, results are discussed from a computational investigation into how pulsing the power applied to an inductively coupled plasma (ICP) reactor may be used for controlling the size of NPs synthesized in the plasma. The model system is an ICP at 1 Torr to grow silicon NPs from an Ar/SiH 4 gas mixture. This system was simulated using a two-dimensional plasma hydrodynamics model coupled to a three-dimensional kinetic NP growth and trajectory tracking model. The effects of pulse frequency and pulse duty cycle are discussed. We identified separate regimes of pulsing where particles become trapped for one pulsed cycle, a few cycles, and many cycles—each having noticeable effects on particle size distributions. For the same average power, pulsing can produce a stronger trapping potential for particles when compared to continuous wave power, potentially increasing particle mono-dispersity. Pulsing may also offer a larger degree of control over particle size for the same average power. Experimental confirmation of predicted trends is discussed. 

Abstract Thin-film deposition from chemically reactive multi-component plasmas is complex, and the lack of electron collision cross-sections for even the most common metalorganic precursors and their fragments complicates their modeling based on fundamental plasma physics. This study focuses on understanding the plasma physics and chemistry in argon (Ar) plasmas containing lithium bis (trimethylsilyl) amide used to deposit Li x Si y thin films. These films are emerging as potential solid electrolytes for lithium-ion batteries, and the Li-to-Si ratio is a crucial parameter to enhance their ionic conductivity. We deposited Li x Si y films in an axial flow-through plasma reactor and studied the factors that determine the variation of the Li-to-Si ratio in films deposited at various points on a substrate spanning the entire reactor axis. While the Li-to-Si ratio is 1:2 in the precursor, the Li-to-Si ratio is as high as 3:1 in films deposited near the plasma entrance and decreases to 1:1 for films deposited downstream. Optical emission from the plasma is dominated by Li emission near the entrance, but Li emission disappears downstream, which we attribute to the complete consumption of the precursor. We hypothesized that the axially decreasing precursor concentration affects the electron energy distribution function in a way that causes different dissociation efficiencies for the production of Li and Si. We used Li line intensities to estimate the local precursor concentration and Ar line ratios to estimate the local reduced electric field to test this hypothesis. This analysis suggests that the mean electron energy increases along the reactor axis with decreasing precursor concentration. The decreasing Li-to-Si ratio with axially decreasing precursor concentration may be explained by Li release from the precursor having lower threshold energy than Si release. 

Transparent conductive oxides (TCOs) are widely used in optoelectronic devices such as flat-panel displays and solar cells. A significant optical property of TCOs is their band gap, which determines the spectral range of the transparency of the material. In this study, a tunable band gap range from 3.35 eV to 3.53 eV is achieved for zinc oxide (ZnO) nanocrystals (NCs) films synthesized by nonthermal plasmas through the removal of surface groups using atomic layer deposition (ALD) coating of Al2O3 and intense pulsed light (IPL) photo-doping. The Al2O3 coating is found to be necessary for band gap tuning, as it protects ZnO NCs from interactions with the ambient and prevents the formation of electron traps. With respect to the solar spectrum, the 0.18 eV band gap shift would allow ~4.1% more photons to pass through the transparent layer, for instance, into a CH3NH3PbX3 solar cell beneath. The mechanism of band gap tuning via photo-doping appears to be related to a combination of the Burstein–Moss (BM) and band gap renormalization (BGN) effects due to the significant number of electrons released from trap states after the removal of hydroxyl groups. The BM effect shifts the conduction band edge and enlarges the band gap, while the BGN effect narrows the band gap. 

Hydrogenated amorphous silicon (a-Si:H) has drawn keen interest as a thin-film semiconductor and superb passivation layer in high-efficiency silicon solar cells due to its low cost, low processing temperature, high compatibility with substrates, and scalable manufacturing. Although the impact of hydrogenation on the structural, optical, and electronic properties of a-Si:H has been extensively studied, the underlying physics of its impact on the thermal properties is still unclear. Here, we synthesize a-Si:H films with well-controlled hydrogen concentrations using plasma-enhanced chemical vapor deposition and systematically study the thermal conductivity of these a-Si:H films using time-domain thermoreflectance. We find that the reduction of thermal conductivity of a-Si:H films is attributed to the suppression of diffuson and propagon contributions as the hydrogen concentration increases. At the maximum hydrogen concentration of 25.4 atomic percentage, the contributions from diffusons and propagons to the thermal conductivity are decreased by 40% (from 1.10 to 0.67 W m −1 K −1 ) and 64% (from 0.61 to 0.22 W m −1 K −1 ), respectively. Such a significant reduction in the thermal conductivity of a-Si:H originates from the hydrogen induced material softening, the decrease in density, and phonon-defect scattering. The results of this work provide fundamental insights into the thermal transport properties of a-Si:H thin films, which is beneficial for the design and optimization of amorphous silicon-based technologies including photovoltaics, large-area electronics, and thermoelectric devices. 

Greenhouses provide a controlled environment for plant growth, which increases crop yields, reduces the use of water and fertilizers, and offers resilience to droughts and extreme weather. However, greenhouse operation is energy intensive due to their heating and cooling loads. Luminescent solar concentrators (LSCs) are promising for semitransparent greenhouse roofs that produce clean electricity, thus reducing the greenhouse energy demand, while also transmitting enough light to satisfy plant growth. Herein, we model the performance of LSC roofs designed as glass panels coated with quantum dot (QD)/polymer nanocomposite films and front‐facing surface‐mounted photovolatic cells. Five widely studied QD materials are examined to demonstrate that the proposed QD LSC roofs can have effective power conversion efficiencies exceeding 10% while also increasing the red‐light fraction, which is beneficial for plant growth. The effect of LSC integration on the greenhouse thermal energy demands is studied for the example of silicon (Si) QD LSC roofs. In warm climates, solar power generated by the Si QD LSC roofs satisfies the entire greenhouse energy demand and thus enables net‐zero energy operation. Overall, the results of the current research demonstrate the strong potential of integrating QD LSCs into greenhouses to reduce energy costs and enhance plant growth.