Achieving Low Voltage Plasma Discharge in Aqueous Solution Using Lithographically Defined Electrodes and Metal/Dielectric Nanoparticles.

Because of the high dielectric strength of water, it is extremely difficult to discharge plasma in a controllable way in the aqueous phase. By using lithographically defined electrodes and metal/dielectric nanoparticles, we create electric field enhancement that enables plasma discharge in liquid electrolytes at significantly reduced applied voltages. Here, we use high voltage (10-30 kV) nanosecond pulse (20 ns) discharges to generate a transient plasma in the aqueous phase. An electrode geometry with a radius of curvature of approximately 10 µm, a gap distance of 300 µm, and an estimated field strength of 5 × 106 V/cm resulted in a reduction in the plasma discharge threshold from 28 to 23 kV. A second structure had a radius of curvature of around 5 µm and a gap distance of 100 µm had an estimated field strength of 9 × 106 V/cm but did not perform as well as the larger gap electrodes. Adding gold nanoparticles (20 nm diameter) in solution further reduced the threshold for plasma discharge to 17 kV due to the electric field enhancement at the water/gold interface, with an estimated E-field enhancement of 4×. Adding alumina nanoparticles decorated with Pt reduced the plasma discharge threshold to 14 kV. In this scenario, the emergence of a triple point at the juncture of alumina, Pt, and water results in the coexistence of three distinct dielectric constants at a singular location. This leads to a notable concentration of electric field, effectively aiding in the initiation of plasma discharge at a reduced voltage. To gain a more comprehensive and detailed understanding of the electric field enhancement mechanism, we performed rigorous numerical simulations. These simulations provide valuable insights into the intricate interplay between the lithographically defined electrodes, the nanoparticles, and the resulting electric field distribution, enabling us to extract crucial information and optimize the design parameters for enhanced performance.

Voltage-Induced Inversion of Band Bending and Photovoltages at Semiconductor/Liquid Interfaces.

At semiconductor/liquid interfaces, the surface potential and photovoltages are produced by a combination of band bending and quasi-Fermi-level splitting at the semiconductor surface, which are usually treated in a qualitative fashion. As such, it is important to develop quantitative metrics for the band energies and photovoltaics at these interfaces. Here, we present a spectroscopic method for monitoring the photovoltages produced at semiconductor/liquid junctions. The surface reporter molecule mercaptobenzonitrile (MBN) is functionalized on the photoelectrode surface (p-type silicon) and is measured using in situ surface-enhanced Raman scattering (SERS) spectroscopy with a water immersion lens under electrochemical working conditions. In particular, the vibrational frequency of the C≡N stretch mode (ωCN) around 2225 cm-1 is sensitive to the local electric field in solution at the electrode/electrolyte interface via the vibrational Stark effect. Over the applied potential range from -0.8 to 0.6 V vs Ag/AgCl, we observe ωCN to increase from 2220 to 2229 cm-1 (at low laser power). As the incident laser power is increased from 83.5 µW to 13.3 mW, we observe additional shifts of ΔωCN = ±1 cm-1, corresponding to photovoltages produced at the semiconductor/liquid interface ΔV = ±0.2 V. Based on Mott-Schottky measurements, the flat band potential (FBP) occurs at -0.39 V vs Ag/AgCl. For applied potentials above the FBP, we observe ΔωCN > 0 (i.e., blue-shifts ∼1 cm-1) corresponding to positive photovoltages, whereas for applied potentials below the flat band potential, we observe ΔωCN < 0 (i.e., red-shifts ∼1 cm-1) corresponding to negative photovoltages. These spectroscopic observations reveal voltage-induced changes in the band bending at the semiconductor/liquid junction that, thus far, have been difficult to measure.

Photoexcited Hot Electron Catalysis in Plasmon-Resonant Grating Structures with Platinum, Nickel, and Ruthenium Coatings.

We report the electrochemical potential dependence of photocatalysis produced by hot electrons in plasmon-resonant grating structures. Here, corrugated metal surfaces with a period of 520 nm are illuminated with 785 nm wavelength laser light swept as a function of incident angle. At incident angles corresponding to plasmon-resonant excitation, we observe sharp peaks in the electrochemical photocurrent and dips in the photoreflectance consistent with the conditions under which there is wavevector matching between the incident light and the spacing between the lines in the grating. In addition to the bare plasmonic metal surface (i.e., Au), which is catalytically inert, we have measured grating structures with a thin layer of Pt, Ru, and Ni catalyst coatings. For the bare Au grating, we observe that the plasmon-resonant photocurrent remains relatively featureless over the applied potential range from -0.8 to +1.2 V vs NHE. For the Pt-coated grating, we observe a sharp peak around -0.3 V vs NHE, three times larger than the bare Au grating, and near complete suppression of the oxidation half-reaction, reflecting the reducing nature of Pt as a good hydrogen evolution reaction catalyst. The photocurrent associated with the Pt-coated grating is less noisy and produces higher photocurrents than the bare Au grating due to the faster kinetics (i.e., charge transfer) associated with the Pt-coated surface. The plasmon-resonant grating structures enable us to compare plasmon-resonant excitation with that of bulk metal interband absorption simply by rotating the polarization of the light while leaving all other parameters of the experiment fixed (i.e., wavelength, potential, electrochemical solution, sample surface, etc.). A 64X plasmon-resonant enhancement (i.e., p-to-s polarized photocurrent ratio) is observed for the Pt-coated grating compared to 28X for the bare grating. The nickel-coated grating shows an increase in the hot-electron photocurrent enhancement in both oxidation and reduction half-reactions. Similarly, Ru-coated gratings show an increase in hot-electron photocurrents in the oxidation half-reaction compared to the bare Au grating. Plasmon-resonant enhancement factors of 36X and 15X are observed in the p-to-s polarized photocurrent ratio for the Ni and Ru gratings, respectively.

Simultaneous Characterization of In-Plane and Cross-Plane Resistivities in Highly Anisotropic 2D Layered Heterostructures.

Understanding and characterizing the intrinsic properties of charge carrier transport across the interfaces in van der Waals heterostructures is critical to their applications in modern electronics, thermoelectrics, and optoelectronics. However, there are very few published cross-plane resistivity measurements of thin samples because these inherently 2-probe measurements must be corrected for contact and lead resistances. Here, we present a method to extract contact resistances and metal lead resistances by fitting the width dependence of the contact end voltages of top and bottom electrodes of different contact widths to a model based on current crowding. These contributions are then subtracted from the total 2-probe cross-plane resistance to obtain the cross-plane resistance of the material itself without needing multiple devices and/or etching steps. This approach was used to measure cross-plane resistivities of a (PbSe)1(VSe2)1 heterostructure containing alternating layers of PbSe and VSe2 with random in-plane rotational disorder. Several samples measured exhibited a 4 order of magnitude difference between cross-plane and in-plane resistivities over the 6-300 K temperature range. We also reported the observation of charge density wave transition in the cross-plane transport of the (PbSe)1(VSe2)1 heterostructure. The device fabrication process is fully liftoff compatible, and the method developed enables the straightforward measurement of the resistivity anisotropy of most thin film materials with nm thicknesses.

Dynamic Study of Intercalation/Deintercalation of Ionic Liquids in Multilayer Graphene Using an Alternating Current Raman Spectroscopy Technique.

We report Raman spectra and infrared (IR) imaging collected during the intercalation-deintercalation half cycles in a multilayer graphene (MLG) device (∼100 layers) operating at 0.2-10 Hz. The device consists of a MLG/alumina membrane/copper stack, in which the alumina membrane is filled with ionic liquid [DEME][TFSI], forming an electrochemical cell. Upon the application of a positive voltage, the TFSI- anions intercalate into the interstitial spaces in the MLG. The incident laser light is modulated using an optical chopper wheel that is synchronized with (and delayed with respect to) a 0.2-10 Hz alternating current (AC) voltage signal. Raman spectra taken just 200 ms apart show the emergence and disappearance of the intercalated G band mode at around 1610 cm-1. By integration of over hundreds of cycles, a significant Raman signal can be obtained. The intercalation/deintercalation is also monitored with thermal imaging via voltage-induced changes in the carrier density, complex dielectric function ε(ω), and thermal emissivity of the device.

Plasma-enhanced electrostatic precipitation of diesel exhaust particulates using nanosecond high voltage pulse discharge for mobile source emission control.

This study reports enhancement in the electrostatic precipitation (ESP) of diesel engine exhaust particulates using high voltage nanosecond pulse discharge in conjunction with a negative direct current (DC) bias voltage. The high voltage (20 kV) nanosecond pulses produce ion densities that are several orders of magnitude higher than those in the corona produced by a standard DC-only ESP. This plasma-enhanced electrostatic precipitator (PE-ESP) demonstrated 95 % remediation of PM and consumes less than 1 % of the engine power (i.e., 37 kW diesel engine at 75 % load). While the DC-only ESP remediation increases linearly with applied voltage, the plasma-enhanced ESP remains approximately constant over the applied range of negative DC biases. Numerical simulations of the PE-ESP process agree with the DC-only experimental results and enable us to verify the charge-based mechanism of enhancement provided by the nanosecond high voltage pulse plasma. Two different reactor configurations with different flow rates yielded the same remediation values despite one having half the flow rate of the other. This indicates that the reactor can be made even smaller without sacrificing performance. Here, this study finds that the plasma enhancement enables high remediation values at low DC voltages and smaller ESP reactors to be made with high remediation.