H2 Plasma Research Articles

Controlling synthesis of defect state lignin-derived carbon and application for U(VI) removal from aqueous solution: Effects of oxygen-defect and grain-size

Lignin has deemed to be the main polluting component of paper industry wastewater. But developing a potential strategy for utilization of lignin is a challenges problem. Lignin derived materials present potential performance for heavy metal wastewater treatment due to their unique physicochemical properties, and were found to be promising candidate materials in U(VI) removal. However, it is still lacking of a comprehensive understanding that the influences of surface oxygen-defect and grain-size on U(VI) removal processes. Here, using lignin as the raw material, combining plasma treatment technology to prepare defect states Lignin Derived Carbon (LDC), and exploring the influences of surface oxygen-defect and grain-size on their removal U(VI) process. The results indicated that with the reducing of LDC particle size (from ∼4 to ∼ 1 μm), the removal performance of U(VI) was improved. And the U(VI) removal performance of LDC was further improved by introducing of oxygen defect via H2 plasma etch. The characterization analysis of defect states LDC before and after reaction with U(VI) shown that the U(VI) removal mechanism was dominated by defects site complexation. These finding provide deep insight into the recycling of industrial solid wastes lignin and improving of U(VI) removal performance via defect controlling technology.

Boosting Dry Reforming of Methane Over NiCo/CeO2 Catalysts Treated by Hydrogen Plasma

ABSTRACTNickel (Ni)‐based catalysts are prospective materials for dry reforming of methane (DRM) reaction, but suffer from coke formation and limited activity for CO2 conversion. To improve the reactivity of Ni‐based catalysts, a promising strategy is introducing cobalt (Co) metal. Here, we construct highly efficient NiCo sites on CeO2 support by H2 plasma, which enables the catalyst to obtain a remarkable increase in DRM reaction than the samples treated by conventional H2 reduction. H2 plasma treatment results in the formation of highly dispersed NiCo alloy nanoparticles and high‐concentration oxygen vacancy. These features create large numbers of highly active sites to boost the activation of CH4 and especially CO2 and their catalytic reactions, resulting in strong coke resistance in the DRM reaction.

Direct Hydrogen Production Promoted by Laser-Induced Water Plasma.

Hydrogen, as a clean energy carrier, plays an important role in addressing the current energy and environmental crisis. However, conventional hydrogen production technologies require extreme reaction conditions, such as high temperature, high pressure, and catalysts. Herein, we study the microscopic mechanism of laser-induced water plasma and subsequent H2 production with real-time time-dependent density functional theory simulations and ab initio molecular dynamics simulations. The results demonstrate that intense laser excites liquid water to generate nonequilibrium plasma in a warm-dense state, which constitutes a superior reaction environment. Subsequent annealing leads to the recombination of energetic reactive particles to generate H2, O2, and H2O2 molecules. Annealing rate and laser wavelength are shown to modulate the product ratio, and the energy conversion efficiency can reach ∼9.2% with an annealing rate of 1.0 K/fs. This work reveals the nonequilibrium atomistic mechanisms of hydrogen production from laser-induced water plasma and shows far-reaching implications for the design of optically controllable hydrogen technology.

Effect of Al precursor’s properties on interactions with self-assembled monolayers for area selective deposition

Area selective deposition (ASD) is a high-precision atomic-level manufacturing technology that enables the development of bottom-up manufacturing methods in the future semiconductor field. The area selective deposition behavior of Al precursors on 1-octadecylthiol (ODT) passivated Cu/SiO2 surfaces was studied through experimental and theoretical analysis. The relationship between precursor steric hindrance, symmetry, penetration depth in ODT, and adsorption energy was elucidated. The loss of selectivity caused by different penetration depths of the precursor in ODT can be post-treated with acids or H2 plasma to remove the physisorption of precursor molecules between ODT chains, thereby improving the selectivity. Reliable ASD technology has been successfully applied to Cu/SiO2 patterns. Dimethylaluminum isopropoxide can selectively deposit about 10 nm of Al2O3 on SiO2 without detectable defects on the Cu area. This provides important insights into the choice of precursors in the ASD process and can extend its application to a wider range of device manufacturing schemes.

Nonhalogen Dry Etching of Metal Carbide TiAlC by Low-Pressure N2/H2 Plasma at Room Temperature.

Ternary metal carbide TiAlC has been proposed as a metal gate material in logic semiconductor devices. It is a hard-to-etch material due to the low volatility of the etch byproducts. Here, a simple, highly controllable, and dry etching method for TiAlC has been first presented using nonhalogen N2/H2 plasmas at low pressure (several Pa) and 20 °C. A capacitively coupled plasma etcher was used to generate N2/H2 plasmas containing active species, such as N, NH, and H to modify the metal carbide surface. The etch rate of TiAlC was obtained at 3 nm/min by using the N2/H2 plasma, whereas no etching occurred with pure N2 plasma or pure H2 plasma under the same conditions. The surface roughness of the TiAlC film etched by N2/H2 plasma was controlled at the atomic level. A smooth etched surface was achieved with a root-mean-square roughness of 0.40 nm, comparable to the initial roughness of 0.44 nm. The plasma properties of the N2/H2 plasmas were diagnosed by using a high-resolution optical emission spectrometer, detecting the NH molecular line at 336 nm. The etching behavior and plasma-surface reaction between N2/H2 plasma and TiAlC were investigated by using in situ spectroscopic ellipsometry, in situ attenuated total reflectance-Fourier transform infrared spectrometry, and X-ray photoelectron spectroscopy. The findings indicate that the N-H, C-N, and Ti(Al)-N bonds form on the TiAlC surface etched by the N2/H2 plasmas. The mechanism for etching of TiAlC involving transformation reactions between inorganic materials (metal carbides) and inorganic etchants (N2/H2 plasma) to form volatile organic compounds such as methylated, methyl-aminated, and aminated metals is proposed. Nonhalogen or nonorganic compound etchants were used during the etching process. The study provides useful insights into microfabrication for large-scale integrated circuits.

Suppression of Threshold Voltage Variation by H₂ Plasma Improved KrF Photoresist Profile

Suppression of Threshold Voltage Variation by H₂ Plasma Improved KrF Photoresist Profile

Improvement of memory storage capacity and prolongation of endurance/retention through H2 plasma treatment of IGZO/HZO structure

Improvement of memory storage capacity and prolongation of endurance/retention through H2 plasma treatment of IGZO/HZO structure

Measurements of atomic hydrogen recombination coefficients and the reduction of Al2O3 using a heat flux sensor

The knowledge of atomic hydrogen recombination coefficient (γ) is essential for plasma simulations to calculate accurate atomic hydrogen fluxes. However, γ is a complex material property, and it is affected by the experimental conditions under which it is measured. Therefore, values of γ can differ even by a few orders of magnitude for the same material. In this paper, we demonstrate measurements of hydrogen recombination coefficients at room temperature using an in-house-built catalytic sensor for two selected materials: aluminum Al-5083 (alimex) and stainless steel 316 l, under the load of low-temperature H2 plasma with an admixture of H2O or N2 gases. The plasma settings were carefully chosen to mimic properties of the so-called extreme ultraviolet-generated plasma.1 The measured γ values agree well with literature data obtained for similar plasma conditions and show a correlation with ion energy. Additionally, we show a novel application of the sensor for indirect measurements of the reduction of oxidized surfaces as a function of ion dose. In these experiments, a correlation between reduction time and background water pressure is observed.

Interfacial improvement of diamond through epitaxial lateral overgrowth with periodic Ir/SiO2/Ir stripe mask

Epitaxial lateral overgrowth (ELO) of diamond film with SiO2 stripe mask has been carried out through microwave plasma chemical vapor deposition systems. To solve the peel-off of SiO2, this study evaluates different kinds of metal buffer layers and chooses Ir as the optimal metal. The effects of the interface feature of two types of stripe masks (Ir/SiO2 and Ir/SiO2/Ir stripes) on the internal stress status and the fluorescence properties are characterized. The optical image confirms that the diamond emerges in the interval of stripes at the initial growth stage and then forms a continuous film with smooth surface and step-flow mode after 37 h lateral overgrowth. Photoluminescence (PL) mapping demonstrates that the SiO2 mask is etched by H2 plasma and results in a high SiV− intensity, especially above the mask. The Ir cap layer on the Ir/SiO2 mask surface is effective in preventing the SiO2 from being etched in the plasma atmosphere, greatly alleviating the PL intensity of the SiV− color center compared with that of the Ir/SiO2 mask. In addition, the Ir cap layer can suppress the stress in the epitaxial layer. The findings of this study can advance the existing research on ELO technology and be potentially applied to vacancy-related color centers.

Effects of surface treatments for the adhesion improvement between Cu and SiCN in BEOL interconnect

This study focuses on the enhancement of interfacial reliability between Cu interconnects and silicon carbon nitride (SiCN) capping layers in semiconductor packaging structures through pre-deposition surface treatments. We compare three distinct treatments combined with H2 plasma, NH3 plasma, and SiH4 gas inflow, evaluating their effectiveness through quantitative measurement of interfacial adhesion energy using a double cantilever beam (DCB) fracture mechanics test. The results exhibit a remarkable adhesion energy improvement of over 1150 % with the addition of SiH4 gas treatment. Thorough investigations reveal that the mechanism of the exceptional adhesion enhancement is attributed to unique chemical bonding and fracture behavior. In other words, Si atoms in the SiH4 gas treatment incorporate onto Cu surfaces with specific crystallographic orientations, resulting in significantly stronger Cu–Si bonding in selective regions compared to other bondings. Moreover, the crystallographic-orientation-dependent bonding characteristic induces crack kinking at grain boundaries, dissipating the crack propagation energy. This work will provide crucial insight into enhancing the interfacial reliability and manufacturing yield of semiconductor devices.

The effect of impurity seeding on edge toroidal rotation in the ADITYA-U tokamak

Intrinsic toroidal rotation velocity (Vφ ) has been measured from the Doppler shift of C5+ carbon spectral lines (at 529.05 nm) in the edge region of the ADITYA-U tokamak without any auxiliary torque input in an ohmically heated pure hydrogen (H2) plasma as well as in H2 plasmas seeded with medium-Z (neon and argon) impurities . The toroidal rotation in the edge region is observed to reverse its direction from the counter-current to the co-current direction with an increase in plasma current beyond I p ∼ 145–150 kA. Furthermore, a systematic decrease in the co-current Vφ has been observed with the edge density, which tends to decrease to almost zero velocity with an increase in the edge density. The injection of medium-Z (neon and argon) impurities is observed to influence the edge toroidal rotation significantly. In low I p discharges, argon injection leads to a reversal of edge intrinsic rotation from the counter-current to the co-current direction. In high I p discharges, both neon and argon seeding enhance the co-current rotation by about ∼5–10 km s−1, at a constant I p compared to pure H2 discharges. Simultaneous measurements of the edge radial electric field, E r, shows that the E r × Bθ flow seems to be driving the edge toroidal rotation in ADITYA-U. With impurity injection, the E r also gets modified, leading to an observed increase in the edge toroidal rotation.

Mechanism study of H2-plasma assisted Si3N4 layered etch

The cyclic two-step process, comprised of energetic H2 plasma followed by HF wet clean or in situ NF3 plasma, demonstrates Si3N4 layer-by-layer removal capability exceeding 10 nm per cycle, surpassing typical atomic layer etch methods by an order of magnitude. In this paper, we investigated the surface reaction mechanisms via first principle density functional theory simulations and surface analysis. The results unveiled that energetic H2 plasma, in the first step, selectively removes nitrogen (N) in preference to silicon (Si), generating ammonia (NHx) and transforming Si3N4 into SiON upon exposure to air, which becomes removable by HF wet clean in the second step. For the second step employing in situ NF3 plasma, it further leverages H-passivated surfaces to enhance NF3 dissociation and provide alternative reaction pathways to yield volatile byproducts such as SiHF3 and SiFx, thereby significantly improving nitride removal efficiency.

Optical and electrical evaluation methods of plasma-induced damage in InP substrates

Indium phosphide (InP) has been focused on as one of the emerging materials that can be implemented in advanced semiconductor devices. We proposed optical and electrical characterization methods to evaluate plasma-induced physical damage (PPD)—ion bombardment damage—to InP substrates. By introducing a native oxide phase in an interfacial layer, we proposed an optical model of the damaged structure applicable for in-line monitoring by spectroscopic ellipsometry. Gas species dependence was obtained, which suggested that the H2 plasma exposure formed a thicker damaged layer than Ar. Impedance spectroscopy (IS) under various biases (V b) was implemented to reveal the nature of damaged structures. Capacitive and conductive components assigned by the IS were confirmed to depend on incident species from plasma, indicating the difference in the energy profile of created defects. The presented methods are useful to characterize and control PPD in designing future high-performance InP-based devices.

Comparison оf Secondary Nucleation Processes during Diamond Synthesis in Microwave Plasma in H2–CH4–N2 and H2–CH4–NH3 Gas Mixtures

Comparison оf Secondary Nucleation Processes during Diamond Synthesis in Microwave Plasma in H2–CH4–N2 and H2–CH4–NH3 Gas Mixtures

Enhanced Hydrogen Generation through Low-Temperature Plasma Treatment of Waste Aluminum for Hydrolysis Reaction.

This study investigates the low-temperature hydrogen plasma treatment approach for the improvement of hydrogen generation through waste aluminum (Al) reactions with water and electricity generation via proton-exchange membrane fuel cell (PEM FC). Waste Al scraps were subjected to ball milling and treated using two different low-temperature plasma regimes: Diode and magnetron-initiated plasma treatment. Hydrolysis experiments were conducted using powders with different treatments, varying molarities, and reaction temperatures to assess hydrogen generation, reaction kinetics, and activation energy. The results indicate that magnetron-initiated plasma treatment significantly enhances the hydrolysis reaction kinetics compared to untreated powders or those treated with diode-generated plasma. Analysis of chemical bonds revealed that magnetron-initiated hydrogen plasma treatment takes advantage by promoting a dual procedure: Surface cleaning and Al nanocluster deposition on top of Al powders. Moreover, it was modeled that such H2 plasma could penetrate up to 150 Å depth. Meanwhile, electricity generation tests demonstrate that only 0.2 g of treated Al powder can generate approximately 1 V for over 300 s under a constant 2.5 Ω load and 1.5 V for 2700 s with a spinning fan.

Plasma Engineering toward Improving the Microwave-Absorbing/Shielding Feature of a Biomass-Derived Material.

During the past decade, ever-increasing electromagnetic pollution has excited a global concern. A sustainable resource, facile experimental scenario, fascinating reflection loss (RL), and broad efficient bandwidth are the substantial factors that intrigue researchers. This research led to the achievement of a brilliant microwave-absorbing material by treating pampas as biomass. The carbon-based microfibers attained by biowaste were treated by plasma under diverse environments to amplify their microwave-absorbing features. Moreover, a pyrolysis scenario was performed to compare the results. The reductive processes were performed by H2 plasma and carbonization. However, the CO2 plasma was performed to regulate the heteroatoms and defects. Interestingly, polystyrene (PS) was applied as a microwave-absorbing matrix. The aromatic rings existing in the absorbing medium establish electrostatic interactions, elevating interfacial polarization, and physical characteristics of PS augment the practical applications of the final product. The manipulated biomasses were characterized by Raman, X-ray diffraction, energy-dispersive spectroscopy, field emission scanning electron microscopy, and diffuse reflection spectroscopy analyses. Eventually, the microwave-absorbing features were estimated by a vector network analyzer. The plasma-treated pampas under H2/Ar blended with PS gained a maximum RL of -90.65 dB at 8.79 GHz and an efficient bandwidth (RL ≤ -10 dB) of 4.24 GHz with a thickness of 3.20 mm; meanwhile, plasma treatment under CO2 led to a maximum RL of 97.99 dB at 14.92 GHz and an efficient bandwidth of 7.74 GHz with a 2.05 mm thickness. Particularly, the biomass plasmolyzed under Ar covered the entire X and Ku bands with a thickness of 2.10 mm. Notably, total shielding efficiencies of the treated bioinspired materials were up to ≈99%, desirable for practical applications.

Preparation of palladium-based catalyst by plasma-assisted atomic layer deposition and its applications in CO2 hydrogenation reduction

Supported Pd catalyst is an important noble metal material in recent years due to its high catalytic performance in CO2 hydrogenation. A fluidized-bed plasma assisted atomic layer deposition (FP-ALD) process is reported to fabricate Pd nanoparticle catalyst over γ-Al2O3 or Fe2O3/γ-Al2O3 support, using palladium hexafluoroacetylacetonate as the Pd precursor and H2 plasma as counter-reactant. Scanning transmission electron microscopy exhibits that high-density Pd nanoparticles are uniformly dispersed over Fe2O3/γ-Al2O3 support with an average diameter of 4.4 nm. The deposited Pd-Fe2O3/γ-Al2O3 shows excellent catalytic performance for CO2 hydrogenation in a dielectric barrier discharge reactor. Under a typical condition of H2 to CO2 ratio of 4 in the feed gas, the discharge power of 19.6 W, and gas hourly space velocity of 10000 h−1, the conversion of CO2 is as high as 16.3% with CH3OH and CH4 selectivities of 26.5% and 3.9%, respectively.

Novel 2DEG System at the HfO2/STO Interface.

Multifunctional integration in a single device has always been a hot research topic, especially for contradictory phenomena, one of which is the coexistence of ferroelectricity and metallicity. The complex oxide heterostructures, as symmetric breaking systems, provide a great possibility to incorporate different properties. Moreover, finding a series of oxide heterostructures to achieve this goal remains as a challenge. Here, taking the advantage of different physical phenomena, we use H2 plasma to pretreat the SrTiO3 (STO) substrate and then fabricate HfO2/STO heterostructures with it. The novel, well-repeatable metallic two-dimensional electron gas (2DEG) is directly obtained at the heterointerfaces without any further complex procedures, while the obvious ferroelectric-like behavior and Rashba spin-orbit coupling are also observed. The understanding of the mechanism, as well as the modified facile preparation procedure, would be meaningful for further development of ferroelectric metal in complex oxide heterostructures.

Microwave-plasma surface modification of nanostructured-polyaniline:graphite composite counter electrode in dye-sensitized solar cells

This work demonstrates microwave plasma surface modifications of nanostructured polyaniline (NPES)-based counter electrodes (CE). Oxidative oxygen (O2) plasma and reductive hydrogen (H2) plasma were used in this study. Optical emission spectra confirm the presence of reactive species in both plasmas through the emissive species, such as O2+, O+, O•, H(nl), and H2 Fulcher-α. Microwave plasma treatment does not affect the surface morphology of NPES composite CE, which conserves its granule nanostructures, as revealed by SEM. The water contact angle measurements demonstrate how the O2 plasma treatment improves surface hydrophilicity, contrary to the H2 plasma treatment. Raman spectroscopy results show significant changes in the intrinsic-oxidation state and the number of semiquinonoid species (SQ) of NPES after plasma treatments, which are represented by the ratios of Raman intensity at 1368–1260 cm−1 and 1624–1583 cm−1, respectively. Generally, O2 plasma treatment increases the intrinsic-oxidation state and SQ number, opposite to the H2 plasma. The optimum condition of microwave plasma-assisted surface modification was attained in one minute of O2 plasma treatment, producing NPES with the highest intrinsic-oxidation state and SQ number. A power conversion efficiency of 3.17 % was obtained by a dye-sensitized solar cell fabricated with a modified CE using a one-minute O2 plasma treatment.

Enhancing oxygen evolution reaction via hydrogen plasma treatment: Unveiling the functionality of CN defects and the role of Fe in NiFe Prussian blue analogs

AbstractThe rational design of electronic and vacancy structures is crucial to regulating and enhancing electrocatalytic water splitting. However, creating novel vacancies and precisely controlling the number of vacancies in existing materials systems pose significant challenges. Herein, a novel approach to optimize the concentration of the CN vacancy (VCN) in the NiFe Prussian blue analog (PBA) nanocubes is designed by incorporating the H2 or O2 plasma treatment. The relationship between the VCN and catalysis is analyzed, and results show that a moderate concentration of VCN (6.5%) can enormously enhance oxygen evolution reaction (OER) activity of NiFe PBA. However, an excessive amount of VCN disrupts the crystal structure and hinders the transportation of charge carriers, consequently leading to inferior OER. Furthermore, the VCN significantly activates the activity of Fe sites, inducing preferential adsorption of OH− on Fe sites, followed by adsorption on Ni sites, thereby optimizing the reaction pathway and significantly promoting OER performance. In addition, VCN also suppresses Fe leaching, giving the catalyst excellent durability. This study reveals the feasibility of creating unconventional defects in nanomaterials and precisely controlling the number of vacancies for diverse catalytic and energy applications.