Surface Reaction Mechanism Research Articles

Pt‐Mo₂N Catalyst Formed by Inverse Sintering for the Reverse Water‐Gas Shift Reaction

AbstractThe reverse water‐gas shift (RWGS) reaction is significant for the resource utilization of CO2. However, this reaction requires high temperatures and metal catalysts are prone to agglomeration, leading to loss of activity. In this work, a Pt catalyst supported on Mo₂N formed via phase transition and metal reverse sintering under a high‐temperature NH₃ atmosphere is developed. This catalyst exhibits excellent RWGS activity, achieving a CO production rate of 294.8 mmolgcat−1 h−1 at 623 K, with CO selectivity maintained at 93%. Moreover, under continuous testing conditions for 100 h, the catalyst's activity shows no significant decline. Notably, further investigation reveals that the surface reaction mechanism at 623 K differs from the previously reported associative mechanism, instead following a redox mechanism in the presence of H₂. This research not only provides a deeper theoretical understanding of the mechanism of CO2 hydrogenation but also offers valuable insights for developing novel and efficient metal catalyst regeneration technologies.

Zinc separation from brass dust by the Fenton process

AbstractBrass polishing facilities generate waste dust rich in zinc and copper, presenting both an economic opportunity for resource recovery and an environmental challenge. The Fenton process, a promising hydrometallurgical solution, offers a way to separate zinc from this waste dust. Researchers employed an experimental design method to identify optimal parameters for zinc dissolution, including pH, ferrous iron (Fe2+) content, stirring speed, and hydrogen peroxide (H2O2) concentration. Kinetic modeling identified the optimal parameters for zinc dissolution: pH 1, 0.1 M Fe2+, 60 rpm stirring speed, 1.0% H2O2 concentration (flow rate 1 mL min−1), and a reaction time of 2 h. The kinetic data suggested a first‐order kinetic model, indicating a chemically controlled surface reaction mechanism. These findings demonstrate the Fenton process's effectiveness in zinc dissolution from brass dust. This paves the way for further research on zinc recovery methods, such as electrolysis for metallic zinc production or integration into chemical manufacturing processes.

Growth mechanism of HfO2 film on H-terminated Si (100) surface from atomic layer deposition process using tetrakis(ethylmethylamino)hafnium

The deposition of HfO2 on H-terminated Si (100) surfaces presents both interest and challenges due to the complexity of the surface reaction mechanisms. Previous experimental studies reported conflicting results regarding the formation of interfacial layers and the presence of incubation periods during the initial cycles of the HfO2 atomic layer deposition (ALD) process. In this study, we provide a detailed analysis of the surface reaction mechanism of HfO2 ALD on H-terminated Si (100) surfaces using tetrakis(ethylmethylamino)hafnium (TEMAH) and water. Our findings demonstrate that TEMAH chemisorbs onto the H-terminated Si (100) surface through the formation of two N-Si interfacial bonds. Additionally, the remaining ligands of the adsorbed Hf precursor are efficiently removed through hydroxylation during the water pulse, with low energy barriers of +25.9 to +30.0 kJ/mol. Furthermore, the N-Si interfacial bonds can be broken, allowing for the formation of Hf-O-Si interfacial bonds during either the water pulse or post-deposition processes. This work provides valuable insights into the surface reactions of HfO2 ALD and explains the varied interfacial bonding and incubation periods observed in prior studies.

Exploring effects of reactant’s chemical environments on adsorption and reaction mechanism by global optimization and IR spectrum calculation, using NO oxidation as a case

Reactant’s chemical environments derived from the type and concentration of surface species on heterogeneous catalysts do great effects on the structures of reactants and reaction pathway. Unraveling the arrangement of surface species and reaction mechanism at different reactant’s chemical environments in theory remains a substantial challenge due to the difficulty in obtaining the global stable configuration of surface species on catalysts and the lack of other theoretical evidences for the identification of surface species and reaction pathway. To solve this problem, a protocol combining the global optimization of surface species at different chemical environments with electronic structure analysis and IR spectrum calculation including frequency and intensity was proposed to unravel the arrangement of surface species and their reaction pathway in this work. Using NO adsorption and oxidation on Pt(111) and O-covered Pt(111) as a case, their stable structures were obtained by the global optimization; then the origins of the structural transformation of NO and NO2 at different environments were elucidated by electronic structure analysis; then the structures and reaction pathway were confirmed by comparing the experimental and calculated IR spectra of NO and NO2 with frequency and intensity. Utilizing this protocol, the stable structures of NO and its transformation, as well as oxidation pathway were revealed under varying chemical environments at the molecular level. It provides solid supports for identifying the stable arrangement of surface species, their transformation and reaction pathway, and can be easily extended to heterogeneous catalysis.

Deconvoluting Surface Modification Effects on Flow Battery Electrode Performance by Impedance Spectroscopy

Flow batteries have proliferated over the past decade, both in installed capacity and in the diversity of systems being developed for grid storage applications. As a long duration energy storage technology, flow batteries offer the distinct advantage of independent scaling of energy capacity through their liquid electrolytes, and of power capacity through stack design. Across flow battery systems, improving the design of reactor stacks to achieve high power densities at acceptable energy conversion efficiencies remains an important lever for lowering overall levelized costs of storage. In pursuit of this aim, understanding the reaction kinetics on the surfaces of porous carbon electrodes is key [1]. However, traditional techniques such as voltammetry, impedance spectroscopy, and cell performance must be utilised with caution to avoid convoluting observations of surface kinetics with other effects.Previous studies on vanadium flow batteries have used impedance spectroscopy to circumvent this issue, utilising the shared dependence of double layer capacitance and charge transfer conductance [2]. In recent years, DRT analysis of impedance spectra has also been used to further study electrode treatments for vanadium systems [3]. Building on these works, we use impedance spectroscopy combined with other techniques to deconvolute the effects of electrode treatments ex-situ before demonstrating the modified electrode performance in flow cells. The accompanying abstract image illustrates how different electrode modifications can manifest comparative differences in identified faradaic features in impedance spectra. As the most well studied system, we first apply our analysis to electrodes for vanadium electrolytes, validating our method and previous studies on electrode modifications. Following this, we apply our approach to capture a range of behaviours by studying redox active species with faster kinetics, such as recently developed organic species [4].The results of this work aim to improve the evaluation of reaction kinetics for different redox active species and electrode treatments. By doing so, we seek to further understand surface reaction mechanisms and how they can be harnessed to improve stack and electrolyte performance.[1] T. V. Sawant, C. S. Yim, T. J. Henry, D. M. Miller, and J. R. McKone, ‘Harnessing Interfacial Electron Transfer in Redox Flow Batteries’, Joule, vol. 5, no. 2, pp. 360–378, Feb. 2021, doi: 10.1016/j.joule.2020.11.022.[2] H. Fink, J. Friedl, and U. Stimming, ‘Composition of the Electrode Determines Which Half-Cell’s Rate Constant is Higher in a Vanadium Flow Battery’, J. Phys. Chem. C, vol. 120, no. 29, pp. 15893–15901, Jul. 2016, doi: 10.1021/acs.jpcc.5b12098.[3] K. Köble et al., ‘Revealing the Multifaceted Impacts of Electrode Modifications for Vanadium Redox Flow Battery Electrodes’, ACS Appl. Mater. Interfaces, vol. 15, no. 40, pp. 46775–46789, Oct. 2023, doi: 10.1021/acsami.3c07940.[4] J.-M. Fontmorin, S. Guiheneuf, T. Godet-Bar, D. Floner, and F. Geneste, ‘How anthraquinones can enable aqueous organic redox flow batteries to meet the needs of industrialization’, Current Opinion in Colloid & Interface Science, vol. 61, p. 101624, Oct. 2022, doi: 10.1016/j.cocis.2022.101624. Figure 1

Surface reaction mechanisms research of Cun and Pdn (n=1–3) clusters modified MoSTe for fault gases in oil-immersed transformers

Efficient detection and timely resolution of internal faults within synthetic ester oil transformers are imperative for ensuring the stability of power systems. This paper proposes the utilization of MoSTe monolayer modified with Cun and Pdn (n=1–3) clusters for detecting internal fault gases (C2H2, C2H4, and CH4) in transformers. The adsorption mechanism and electronic properties of target gases on the modified substrate surface are systematically studied through density functional theory analysis of adsorption energy, density of states, and deformation charge density. The results indicate that TMn clusters possess the capability to enhance the reactivity of the MoSTe surface, leading to varying degrees of improvement in conductivity and adsorption capacity. Different target gases exhibit distinct adsorption characteristics, with the modified monolayer showing strong adsorption capabilities for C2H2 and C2H4. The calculation of work function and recovery time further reveal the promising potential of Pdn-MoSTe monolayer as resistive gas sensing materials for detecting C2H2 and C2H4, while Cun-MoSTe monolayer are also identified as high-quality candidates for C2H4 sensing materials. This study is expected to facilitate the practical application of MoSTe monolayer in the field of transformer operational state monitoring, providing new insights for exploring novel gas sensing materials.

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.

First-principles study of CO2 hydrogenation to methanol on In-Ru alloys: Revealing the influence of surface In/Ru ratio on reaction mechanism and catalyst performance

Designing high-performance catalyst is vital in the field of CO2 methanolization. In this study, two In3Ru surfaces (In3Ru_i and In3Ru_r) were employed as computational models and the density functional theory was applied to study the influence of surface In/Ru ratio on their surface morphologies, reaction mechanisms and catalysis performance for methanol synthesis. Surface characterization reveals that In3Ru_i is higher in surface In/Ru ratio than In3Ru_r, and such difference facilitates CO2 adsorption on In3Ru_r. Being different in surface In/Ru ratio, two surfaces exhibit distinct variations in the reaction mechanism of methanol formation. For In3Ru_i, the “Formate” pathway dominates the first CO2 activation step which leads to methanol production. On the other hand, In3Ru_r prefers the “reverse water-gas shift” pathway (RWGS) in the initial step of CO2 activation, but this mechanism is unable to generate CH3OH due to the kinetic limitation of CO* hydrogenation. Based on the microkinetic modeling, In3Ru_i is superior in both CO2 production rate and CH3OH selectivity than the other one, suggesting higher surface In/Ru ratio benefits methanol formation, which complies well with the experiment. Overall, our study offers a new perspective with respect to how surface morphology of the bimetallic catalyst influences the reaction mechanisms of CO2 hydrogenation.

Analyzing the combustion characteristics of premixed methane-oxygen with different hydrogen addition ratios in a catalytic micro-combustor

Experimental and numerical study of premixed methane-oxygen combustion characteristics in a catalytic micro-combustor with different hydrogen addition ratios has been presented in this paper. The objective is to examine the effects of platinum catalysts and hydrogen additions on methane and oxygen combustion. The simulation of a three-dimensional micro rectangular model was carried out with a gas phase reaction mechanism combined with a surface reaction mechanism, and the model was validated with experimental results with a maximum deviation of just 1.56 percent. In the experimental phase, the effects of flammability limit, equivalence ratio, and inlet velocity were studied, while in the numerical phase, the effect of hydrogenation on combustion characteristics was investigated. Experimental results show that adding 10 % hydrogen to a premixed methane-oxygen mixture significantly increases its flammability limit. The maximum external wall temperature along the centerline was observed at an equivalent ratio of 1. Additionally, an increase in the inlet velocity leads to a corresponding increase in the external wall centerline temperature. Catalytic reaction wall temperatures show a gradual decline, with the highest temperatures located at the inlet. An observed trend revealed a decrease in the external wall centerline temperature as the hydrogen addition increased from 0 % to 40 % due to the reduced total heating value of the blended fuel. Due to its higher reactivity and ability to promote complete combustion, hydrogen also plays an important role in CH4 and O2 conversion. In addition, CO and CO2 emissions decreased with increased hydrogen percentage in fuel mixtures. Furthermore, hydrogen addition can reduce external wall heat losses as well. After adding 0–40 % hydrogen to a premixture of (CH4–O2) fuel, the total heat loss of the external wall was reduced from 19.48 W to 17.11 W.

The mechanism of water decomposition on surface of aluminum and gallium alloy during the hydrogen production process: A DFT study

The efficient hydrogen-production through the Aluminum-water reaction has become a prominent subject of interest. The impediment encountered in the reaction can be effectively alleviated by Aluminum-based alloy. In this study, density functional theory (DFT) was utilized to explore the mechanism of water decomposition stage on the surface of aluminum and gallium alloy (AGA). Through surface reaction calculations of 12 stable AGA configurations, it was gradually revealed that the optimal alloy ratio was gallium-to-aluminum at 3.5:1. Analysis of the density of states (DOS) indicated that the presence of gallium amplified the activity of surface aluminum. Moreover, frontier orbital theory and charge density maps confirmed that, due to the weak interaction between Ga and ions, the presence of H2 inhibited Ga passivation, thereby enhancing the reactivity of AGA. This paper provided valuable insights into the surface reaction mechanisms of AGA using DFT, offering theoretical support for hydrogen production processes.

Synthesis of Hydroxylamine via Ketone-Mediated Nitrate Electroreduction.

Hydroxylamine (HA, NH2OH) is a critical feedstock in the production of various chemicals and materials, and its efficient and sustainable synthesis is of great importance. Electroreduction of nitrate on Cu-based catalysts has emerged as a promising approach for green ammonia (NH3) production, but the electrosynthesis of HA remains challenging due to overreduction of HA to NH3. Herein, we report the first work on ketone-mediated HA synthesis using nitrate in water. A metal-organic-framework-derived Cu catalyst was developed to catalyze the reaction. Cyclopentanone (CP) was used to capture HA in situ to form CP oxime (CP-O) with C═N bonds, which is prone to hydrolysis. HA could be released easily after electrolysis, and CP was regenerated. It was demonstrated that CP-O could be formed with an excellent Faradaic efficiency of 47.8%, a corresponding formation rate of 34.9 mg h-1 cm-2, and a remarkable carbon selectivity of >99.9%. The hydrolysis of CP-O to release HA and CP regeneration was also optimized, resulting in 96.1 mmol L-1 of HA stabilized in the solution, which was significantly higher than direct nitrate reduction. Detailed in situ characterizations, control experiments, and theoretical calculations revealed the catalyst surface reconstruction and reaction mechanism, which showed that the coexistence of Cu0 and Cu+ facilitated the protonation and reduction of *NO2 and *NH2OH desorption, leading to the enhancement for HA production.

Reaction mechanisms of α,ω-bifunctional molecules toward atomic layer deposition versus molecular layer deposition

Atomic layer deposition (ALD) and molecular layer deposition (MLD) are key techniques used to fabricate high-quality thin films. Organic α,ω-bifunctional precursors often exhibit different growth behaviors depending on the functional groups as well as the chain length of the molecular backbone, so that some organic precursors produce thin films of organic-inorganic hybrid materials, while others may deposit purely inorganic thin films without incorporation of the hydrocarbon moiety. In this study, we investigated the surface reaction mechanisms of α,ω-bifunctional molecules (X(CH2)nX, n = 2, 3, 4, 5, 6, and X = OH, SH, NH2) with diethylzinc toward MLD and ALD using density functional theory (DFT) calculations. It was found that the length of the aliphatic alkyl chain and the terminal functional groups of bifunctional organic precursors significantly influences their reactivity, resulting in the possibility toward removal or incorporation of the organic moiety in the product. Bifunctional reactants with longer alkyl backbones (n > 4) showed higher reactivity for removal of the hydrocarbon chain, facilitated by a ω-2 hydrogen transfer reaction. Furthermore, a reactivity trend of SH > OH > NH2 for removal of the hydrocarbon chains was observed. Our study provides in-depth theoretical insights into the adsorption reaction mechanisms occurring when bifunctional molecules are employed as organic reactants in ALD and MLD processes.

Recent developments and challenges in resistance-based hydrogen gas sensors based on metal oxide semiconductors.

In recentyears, the energy crisis has made the world realize the importance and need for green energy. Hydrogen safety has always been a primary issue that needs to be addressed for the application and large-scale commercialization of hydrogen energy, and precise and rapid hydrogen gas sensing technology and equipment are important prerequisites for ensuring hydrogen safety. Based on metal oxide semiconductors (MOS), resistive hydrogen gas sensors (HGS) offer advantages, such as low cost, low power consumption, and high sensitivity. They are also easy to test, integrate, and suitable for detecting low concentrations of hydrogen gas in ambient air. Therefore, they are considered one of the most promising HGS. This article provides a comprehensive review of the surface reaction mechanisms and recent research progress in optimizing the gas sensing performance of MOS-based resistive hydrogen gas sensors (MOS-R-HGS). Particularly, the advancements in metal-assisted or doped MOS, mixed metal oxide (MO)-MOS composites, MOS-carbon composites, and metal-organic framework-derived (MOF)-MOS composites are extensively summarized. Finally, the future research directions and possibilities in this field are discussed.

Chemical Reactivity and Alteration of Pyrite Mineral in the Kubi Gold Concession in Ghana

Pyrite is the most common among the group of sulfide minerals in the Earth and abundant in most geological settings. This gangue mineral in association with garnet, hematite, magnetite, and other sulfide minerals acts as an indicator mineral in the Kubi concession of the Asante Gold corporation in Ghana. X-ray diffraction (XRD), air annealing in a furnace, energy-dispersive x-ray spectroscopy (EDX), and X-ray photoelectron spectroscopy (XPS) were applied to investigate the crystal structure, identify individual elements, permanence, transformation, and chemical/electronic properties of such pyrite. The study aims to identify individual elements and to gain an understanding of the surface reaction mechanisms, as well as the properties of precipitated pyrite particles observed during the hydrothermal formation of the ore deposit. XRD shows that pristine and annealed samples contain some hematite and quartz besides pyrite. Results from air annealing indicate that the relationship between pyrite and hematite-magnetite is controlled by temperature. EDX reveals that the sample has O and C as contaminants, while XPS in addition reveals Ba, Au, P, Al, and N. These elements are attributed to pyrite that bonds metallically or covalently to neighboring ligands/impurity minerals such as oxides, chalcogenide sulfides, as well as the gangue alteration minerals of magnetite and hematite in the pyrite sample.These findings suggest that during the hydrothermal flow regime, pyrite, pathfinder elements, and impurity minerals/metals were in contact with quartz minerals before undergoing hematite transformation, which thus becomes an indicator mineral in the Kubi gold concession.

Influence of Organic Coating Thickness on Electrochemical Impedance Spectroscopy Response

Electrochemical Impedance Spectroscopy (EIS) is a non-destructive and powerful technique for characterizing corrosion systems, allowing for the evaluation of surface reaction mechanisms, mass transport, kinetic evolution, and corrosion levels of materials. This study aims to analyze the progression of corrosion using EIS, with a focus on the influence of organic coating thickness. For this purpose, layers of high-purity epoxy paint were applied to carbon steel plates with thicknesses of 50 µm, 80 µm, and 100 µm. During the research, a direct correlation was observed between coating thickness and corrosion resistance, emphasizing the importance of identifying the optimal thickness for each type of coating. Additionally, it was found that thicker coatings may experience electrode penetration due to the tensions generated during deposition, resulting in cracks between the layers, while thinner coatings allow electrolyte penetration as they do not provide adequate protection to the base steel. Therefore, the 80 µm thickness demonstrated greater resistance to corrosion compared to the other tested thicknesses.

Detailed kinetic modeling of catalytic oxidative coupling of methane

The oxidative coupling of methane (OCM) at high temperature over monolithic Pt-based catalysts operated at short contact times is investigated as an attractive method for methane upgrading to higher value products like ethylene and acetylene. An experimental measurement campaign aiming at elucidating the effect of operation parameters on the catalyst performance revealed that lower N2 dilution, lower CH4/O2 ratio, and higher space velocities promote high C2 yields. A maximum C2 yield of 10 % with 94 % CH4 conversion was obtained at a CH4/O2 ratio of 1.1, 50 % N2 dilution, and a space velocity of 4.5 × 105 h−1. Since both heterogenous and homogenous gas-phase chemistry together are required for determining C2 formation pathways, a detailed OCM surface reaction mechanism over Pt is presented consisting of 26 species and 86 reactions that are consistent from the view of thermodynamics and micro-kinetic reversibility. The combination of this OCM surface mechanism with a detailed gas-phase mechanism allows a numerical micro-kinetic description of the experimental measurements. The simulations presented in this study suggest that C2 formation takes place in the gas-phase at temperature above 1200 K with both oxidative and pyrolytic pathways for methane dehydrogenation to form CH3 radicals, whose coupling results in C2H6, C2H4 and C2H2 formation. Furthermore, the simultaneous presence of sufficient oxygen content and heat are vital for high C2 species yields.

Effect of Donor Nb(V) Doping on the Surface Reactivity, Electrical, Optical and Photocatalytic Properties of Nanocrystalline TiO2.

In this work, we primarily aimed to study the Nb(V) doping effect on the surface activity and optical and electrical properties of nanocrystalline TiO2 obtained through flame-spray pyrolysis. Materials were characterized using X-ray diffraction, Raman spectroscopy and IR, UV and visible spectroscopy. The mechanism of surface reaction with acetone was studied using in situ DRIFTs. It was found that the TiO2-Nb-4 material demonstrated a higher conversion of acetone at a temperature of 300 °C than pure TiO2, which was due to the presence of more active forms of chemisorbed oxygen, as well as higher Lewis acidity of the surface. Conduction activation energies (Eact) were calculated for thin films based on TiO2-Nb materials. The results of the MB photobleaching experiment showed a non-monotonic change in the photocatalytic properties of materials with an increase in Nb(V) content, which was caused by a combination of factors, such as specific surface area, phase composition, concentration of charge carriers as well as their recombination due to lattice point defects.

Modeling the Atomic Layer Deposition of Metal Thin Films: Studying the Surface Reaction Mechanism By Density Functional Theory Simulations

Atomic layer deposition (ALD) is widely used in microelectronics and semiconductor industry to deposit thin films as part of device fabrication in nano- or subnano-dimensions. The key advantages of ALD are the conformality and precise thickness control at the atomic scale, which are difficult for physical or traditional chemical vapor deposition methods. The atomic scale understanding of ALD is vital and essential to design and optimize the deposition process, where density functional theory (DFT) calculations play an important role in providing detailed reaction mechanism, theoretical screening of suitable precursors and estimated growth-per-cycle (GPC).In this study, we show our recent works on DFT calculations of the growth mechanism study of Cobalt (Co) thin film by plasma-enhanced ALD1,2. We first addressed the surface reaction mechanism at the metal precursor pulse and plasma half-cycle on NHx-terminated Co surfaces, which corresponds to the steady growth for the PE-ALD. The adsorption and reactions of metal precursors (CoCp2) on NHx terminated metal surfaces were investigated with the inclusion of van der Waals corrections. The plausible reaction pathways include: precursor adsorption, hydrogen transfer, CpH formation and CpH desorption. The direct Cp dissociation mechanism is not considered on these NHx-terminated metal surfaces due to experimentally observed minimal C impurities at the deposited metal thin films, which indicates that most of the Cp ligand is removed completely. The barrier for proton transfer was calculated using climbing image nudged elastic band (CI-NEB) method.The reactions at the initial stages on typical H:Si(100) surface are investigated to gain atomic insight on the effect of different substrates on the elimination of Cp ligands. Our work is important to reveal the mechanism and feasibility of atomic layer deposition of metals using N-plasma.In addition, we present our recent works3, 4 on the thermal ALD of Co using reducing agent Zn(DMP)2 and thermal ALD of Fe4Zn9 thin film with diethyl zinc (DEZ). Our DFT results show that by selecting suitable reducing agent, we can control the deposited thin films to be Zn-free high quality Co thin film or desired intermetallic thin film with high Zn content.These DFT results are important to understand the reaction mechanism for ALD and provides new knowledge in depositing the thin films by adjusting the reducing agents.

Enhancement of Conformality of Silicon Nitride Thin Films by ABC‐Type Atomic Layer Deposition

AbstractAtomic layer deposition (ALD) is utilized for the fabrication of miniaturized electronic devices with nanometer‐scale features. However, the conventional ALD process on high‐aspect‐ratio (HAR) substrates often results in the deposition of thin films with suboptimal conformality over the depth of the trench structures. This study introduces an ABC‐type ALD of silicon nitride (SiNx) employing vapor‐deliverable tert‐butyl chloride (TBC) as a surface inhibitor. Herein, density functional theory (DFT) calculations elucidate the surface reaction mechanisms, confirming the inhibition of the Si precursor by the t‐butyl moiety. Notably, the ABC‐type ALD exhibits reduced growth per cycle relative to the conventional process while avoiding detectable carbon contamination in the SiNx thin films. Applying this process to substrates with trench structures revealed a substantial improvement in conformality following the introduction of TBC. Furthermore, the step coverage of the deposited SiNx can be modulated by adjusting TBC exposure, enabling greater film thickness at the bottom than that at the top of the trench. The proposed method of modulating ALD processes holds potential for the high‐volume manufacturing of semiconductor devices with HAR structures.

Chemisorption and Surface Reaction of Hafnium Precursors on the Hydroxylated Si(100) Surface

Hafnium oxide (HfO2) is widely recognized as one of the most promising high-k dielectric materials due to its remarkable properties such as high permittivity, wide band gap, and excellent thermal and chemical stability. The atomic layer deposition (ALD) of HfO2 has attracted significant attention in recent decades since it enables uniform and conformal deposition of HfO2 thin films on various substrates. In this study, we examined the initial surface reactions of a series of homoleptic hafnium precursors on hydroxylated Si(100) surfaces using density functional theory calculations. Our theoretical findings align with previous experimental studies, indicating that hafnium amides exhibit higher reactivity compared to other precursors such as hafnium alkoxides and hafnium halides in surface reactions. Interestingly, we found that the chemisorption and reactivity of hafnium precursors are considerably affected by their thermal stability and size. For alkoxide precursors, which have similar thermal stabilities, the size of alkoxide ligands is an important factor in determining their reactivity. Conversely, the reactivity of hafnium halides, which have ligands of similar sizes, is primarily governed by their thermal stability. These insights are valuable for understanding the surface reaction mechanisms of precursors on hydroxylated Si(100) surfaces and for designing new materials, particularly heteroleptic precursors, in future research.