Cho, Kyeongjae
Permanent URI for this collectionhttps://hdl.handle.net/10735.1/3651
Kyeongjae Cho is a Professor of Materials Science. His research interests include:
- Computational modeling study of nanomaterials with applications to nanoelectronic devices
- Renewable energy technology
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Item A Fermi-Level-Pinning-Free 1D Electrical Contact at the Intrinsic 2D MoS₂–Metal Junction(Wiley-VCH Verlag, 2019-05-08) Yang, Z.; Kim, C.; Lee, K. Y.; Lee, M.; Appalakondaiah, S.; Ra, C. -H; Watanabe, K.; Taniguchi, T.; Cho, Kyeongiae; Hwang, E.; Hone, J.; Yoo, W. J.; 0000-0003-2698-7774 (Cho, K); Cho, KyeongiaeCurrently 2D crystals are being studied intensively for use in future nanoelectronics, as conventional semiconductor devices face challenges in high power consumption and short channel effects when scaled to the quantum limit. Toward this end, achieving barrier-free contact to 2D semiconductors has emerged as a major roadblock. In conventional contacts to bulk metals, the 2D semiconductor Fermi levels become pinned inside the bandgap, deviating from the ideal Schottky–Mott rule and resulting in significant suppression of carrier transport in the device. Here, MoS₂ polarity control is realized without extrinsic doping by employing a 1D elemental metal contact scheme. The use of high-work-function palladium (Pd) or gold (Au) enables a high-quality p-type dominant contact to intrinsic MoS₂, realizing Fermi level depinning. Field-effect transistors (FETs) with Pd edge contact and Au edge contact show high performance with the highest hole mobility reaching 330 and 432 cm² V⁻¹ s⁻¹ at 300 K, respectively. The ideal Fermi level alignment allows creation of p- and n-type FETs on the same intrinsic MoS₂ flake using Pd and low-work-function molybdenum (Mo) contacts, respectively. This device acts as an efficient inverter, a basic building block for semiconductor integrated circuits, with gain reaching 15 at V_{D} = 5 V. ©2019 WILEY-VCH Verlag GmbH & Co. KGaA, WeinheimItem Ab-Initio Design of Novel Cathode Material LiFeP₁₋ₓSiₓO₄ for Rechargeable Li-Ion Batteries(Elsevier Ltd, 2019-04-27) Yi, S.; Moon, J.; Cho, M.; Cho, Kyeongiae; 0000-0003-2698-7774 (Cho, K); Cho, KyeongiaeIn this study, newly designed cathode material LiFeP₁₋ₓSiₓO₄, with silicon mixed in LiFePO₄ is investigated using the density functional theory. Its most optimized structure is the olivine structure of the Pnma space group. Bonding length show the anti-site defect which hinders Li diffusivity is prevented in the LiFeP₁₋ₓSiₓO₄. Lithium migration energy barriers in the (010) path of LiFeP₁₋ₓSiₓO₄ (x = 0, 0.5, and 1) are calculated by using nudged elastic band calculations, and the average values are determined as 0.180, 0.245, and 0.280 eV for LiFePO₄, LiFeP₀․₅Si₀․₅O₄, and LiFeSiO₄, respectively. This signifies that the Li ionic diffusivity is degraded thermodynamically, which is contrary to that indicates by the calculated bonding length, however, the difference is negligibly small. Furthermore, the intercalation voltage increases up to 4.97 V, depending on the Si ratio to P, and is much higher than that of the pristine cathode materials LiFePO₄ (~3.47 V) enabling voltage optimization by Si substitution. The energy density is proportional to the intercalation voltage, hence the energy density is increased, respectively. Finally, the Total density of states show that the electronic conductivity of LiFeP₁₋ₓSiₓO₄ (x = 0–1) is better than that of LiFePO₄.Item Electrode-Electrolyte Interface for Solid State Li-Ion Batteries: Point Defects and Mechanical StrainSantosh, KC; Longo, Roberto C.; Xiong, Ka; Cho, Kyeongjae; 0000-0003-2698-7774 (Cho, K)In this work, we present an ab-initio investigation of point defects in solid electrolyte γ-Li₃PO₄ and in negative electrode-electrolyte interface (Li/γ-Li₃PO₄). Our results on Li defects on γ-Li₃PO₄ exhibit that Li interstitial defects dominate over vacancy defects, and that Li vacancy-interstitial pair defect formation energy in-the-interface is comparable to the sum of-Li vacancy defect in the electrode and Li ion interstitial defects in the electrolyte region. Our study reveals that the high Li ion defect formation energy is the determining factor for the low ionic conductivity across Li metal/electrolyte interface. Moreover, in a realistic interface, the mechanical strain at the interface increases with the concentration of the impurities produced as a result of the cycling of the battery or due to surface impurities, also affecting the electrostatic potential and charge distribution. Thus, the study of the Li metal/electrolyte interface provides information on the defect formation and mechanical stability and, hence, it helps to understand the realistic modeling of the interface-as a way to-improve the ionic conductivity and stability of future solid state Li-ion batteries.Item Enhanced P-Type Behavior in 2D WSe2 via Chemical Defect Engineering(Institute of Electrical and Electronics Engineers Inc.) Rai, A.; Park, J. H.; Zhang, Chenxi; Kwak, I.; Wolf, S.; Vishwanath, S.; Lin, X.; Furdyna, J.; Xing, H. G.; Cho, Kyeongjae; Kummel, A. C.; Banerjee, S. K.; 0000-0003-2698-7774 (Cho, K); 369148996084659752200 (Cho, K); Zhang, Chenxi; Cho, KyeongjaeDefect engineering of 2D semiconducting transition metal dichalcogenides (TMDCs) has been demonstrated to be a promising way to tune both their bandgaps and carrier concentrations. Moreover, controlled introduction of defects in the source/drain access regions of a TMDC FET can boost its performance by decreasing the contact resistance at the metallTMDC interface [1]. While chemical functionalization offers a facile route towards defect engineering in 2D TMDCs, several chemically-treated TMDCs have not been fully understood at the molecular level. In this study, chemical sulfur treatment (ST) utilizing ammonium sulfide [(NH4)2S] solution is shown to enhance the p-type behavior in 2D WSe2 via introduction of acceptor defect states near its valence band edge (VBE), with the results verified using detailed scanning tunneling microscopy (STM)/spectroscopy (STS) studies, field-effect transistor (FET) measurements and theoretical density-of-states (DOS) calculations.Item First-Principles Study of Metal-Graphene Edge Contact for Ballistic Josephson Junction(American Physical Society, 2019-06-05) Lee, Yeonghun; Hwang, Jeongwoon; Zhang, Fan; Cho, Kyeongjae; 0000-0003-4623-4200 (Zhang, F); 0000-0003-2698-7774 (Cho, K); 369148996084659752200 (Cho, K); Lee, Yeonghun; Hwang, Jeongwoon; Zhang, Fan; Cho, KyeongjaeEdge-contacted superconductor-graphene-superconductor Josephson junctions have been utilized to realize topological superconductivity, and have shown superconducting signatures in the quantum Hall regime. We perform first-principles calculations to interpret electronic couplings at the superconductor-graphene edge contacts by investigating various aspects in hybridization of molybdenum d orbitals and graphene π orbitals. We also reveal that interfacial oxygen defects play an important role in determining the doping type of graphene near the interface. © 2019 American Physical Society.Item In Situ Study of E-Beam Al And Hf Metal Deposition on Native Oxide InP (100)Dong, Hong; Santosh, KC; Azcatl, Angelica; Cabrera, Wilfredo; Qin, Xiaoye; Brennan, Barry; Zhernokletov, Dmitry; Cho, Kyeongjie; Wallace, Robert M.The interfacial chemistry of thin Al (∼3 nm) and Hf (∼2 nm) metal films deposited by electron beam (e-beam) evaporation on native oxide InP (100) samples at room temperature and after annealing has been studied by in situ angle resolved X-ray photoelectron spectroscopy and low energy ion scattering spectroscopy. The In-oxides are completely scavenged forming In-In/In-(Al/Hf) bonding after Al and Hf metal deposition. The P-oxide concentration is significantly decreased, and the P-oxide chemical states have been changed to more P-rich oxides upon metal deposition. Indium diffusion through these metals before and after annealing at 250 °C has also been characterized. First principles calculation shows that In has lower surface formation energy compared with Al and Hf metals, which is consistent with the observed indium diffusion behavior.Item In Situ Study of the Role of Substrate Temperature during Atomic Layer Deposition of HfO2 on InP(2013-10-16) Dong, Hong; Santosh, KC; Qin, Xiaoye; Brennan, Barry; McDonnell, Steven; Zhernokletov, Dmitry; Hinkle, Christopher L.; Kim, Jiyoung; Cho, Kyeongjie; Wallace, Robert M.; 70133685 (Kim, J)The dependence of the "self cleaning" effect of the substrate oxides on substrate temperature during atomic layer deposition (ALD) of HfO₂ on various chemically treated and native oxide InP (100) substrates is investigated using in situ X-ray photoelectron spectroscopy. The removal of In-oxide is found to be more efficient at higher ALD temperatures. The P oxidation states on native oxide and acid etched samples are seen to change, with the total P-oxide concentration remaining constant, after 10 cycles of ALD HfO₂ at different temperatures. An (NH₄)₂ S treatment is seen to effectively remove native oxides and passivate the InP surfaces independent of substrate temperature studied (200°C, 250°C and 300°C) before and after the ALD process. Density functional theory modeling provides insight into the mechanism of the changes in the P-oxide chemical states.Item Investigation of the Hydrothermal Aging of an Mn-Based Mullite SmMn₂O₅ Catalyst of NO Oxidation(Royal Society of Chemistry, 2017-10-20) Xue, L.; Xiong, K.; Chen, H.; Cho, Kyeongjae; Wang, Weichao; 0000-0003-2698-7774 (Cho, K); 0000-0001-5931-212X (Wang, W); 369148996084659752200 (Cho, K); Cho, Kyeongjae; Wang, WeichaoHydrothermal aging tests are important to carry out when evaluating the hydrothermal durability of heterogeneous catalysts in vehicle exhaust emission. Here, we explored the effect of aging on an efficient Mn-based mullite catalyst (SmMn₂O₅) of NO oxidation. The mullite catalyst was prepared via the hydrothermal method and was subsequently aged in air with a 10% H2O stream at 750 °C for 16 hours. The fresh and aged catalysts were structurally characterized using Powder X-ray diffraction(XRD), Raman, X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), high resolution-transmission electron microscope (HR-TEM), Brunauer-Emmett-Teller (BET) and temperature programmed desorption (TPD). For the performance evaluations, the samples were placed into a U-shape reactor furnace, and NO and NO2 concentrations were in situ recorded with an NOx analyzer. In contrast to fresh mullite, the aged sample showed a 25 °C higher light-off temperature and 11% conversion loss at its maximum conversion temperature of 300 °C. O2-TPD of the aged sample displayed a large decrease of the desorption area, consistent with an ∼3-fold loss of the BET specific surface area. Moreover, HRTEM, XPS and Raman spectroscopy results together indicated that a small portion of the mullite decomposed into perovskite SmMnO3 and Mn2O3, which further reduced the total quantity of Mn active sites. The reduction of the BET surface area and mullite decomposition together caused the decrease of the catalytic performance. We therefore expect maintaining the specific surface area to be important for preventing the loss of catalytic performance during the hydrothermal aging process. © 2017 The Royal Society of Chemistry.Item A Kinetic Monte Carlo Simulation Method of Van Der Waals Epitaxy for Atomistic Nucleation-Growth Processes of Transition Metal Dichalcogenides(Nature Publishing Group, 2018-08-31) Nie, Yifan; Liang, Chaoping; Cha, Pil-Ryung; Colombo, Luigi; Wallace, Robert M.; Cho, Kyeongjae; 0000-0003-4771-3633 (Nie, Y); Nie, Yifan; Liang, Chaoping; Cha, Pil-Ryung; Wallace, Robert M.; Cho, KyeongjaeControlled growth of crystalline solids is critical for device applications, and atomistic modeling methods have been developed for bulk crystalline solids. Kinetic Monte Carlo (KMC) simulation method provides detailed atomic scale processes during a solid growth over realistic time scales, but its application to the growth modeling of van der Waals (vdW) heterostructures has not yet been developed. Specifically, the growth of single-layered transition metal dichalcogenides (TMDs) is currently facing tremendous challenges, and a detailed understanding based on KMC simulations would provide critical guidance to enable controlled growth of vdW heterostructures. In this work, a KMC simulation method is developed for the growth modeling on the vdW epitaxy of TMDs. The KMC method has introduced full material parameters for TMDs in bottom-up synthesis: metal and chalcogen adsorption/desorption/diffusion on substrate and grown TMD surface, TMD stacking sequence, chalcogen/metal ratio, flake edge diffusion and vacancy diffusion. The KMC processes result in multiple kinetic behaviors associated with various growth behaviors observed in experiments. Different phenomena observed during vdW epitaxy process are analysed in terms of complex competitions among multiple kinetic processes. The KMC method is used in the investigation and prediction of growth mechanisms, which provide qualitative suggestions to guide experimental study.Item Kinetic Stability of Bulk LiNiO₂ and Surface Degradation by Oxygen Evolution in LiNiO₂-Based Cathode Materials(Wiley-VCH Verlag Gmbh, 2018-11-02) Kong, Fantai; Liang, Chaoping; Wang, Luhua; Zheng, Yongping; Perananthan, Sahila; Longo, Roberto C.; Ferraris, John P.; Kim, Moon J.; Cho, Kyeongjae; Kong, Fantai; Liang, Chaoping; Wang, Luhua; Zheng, Yongping; Perananthan, Sahila; Longo, Roberto C.; Ferraris, John P.; Kim, Moon J.; Cho, KyeongjaeCapacity degradation by phase changes and oxygen evolution has been the largest obstacle for the ultimate commercialization of high-capacity LiNiO₂-based cathode materials. The ultimate thermodynamic and kinetic reasons of these limitations are not yet systematically studied, and the fundamental mechanisms are still poorly understood. In this work, both phenomena are studied by density functional theory simulations and validation experiments. It is found that during delithiation of LiNiO₂, decreased oxygen reduction induces a strong thermodynamic driving force for oxygen evolution in bulk. However, oxygen evolution is kinetically prohibited in the bulk phase due to a large oxygen migration kinetic barrier (2.4 eV). In contrast, surface regions provide a larger space for oxygen migration leading to facile oxygen evolution. These theoretical results are validated by experimental studies, and the kinetic stability of bulk LiNiO₂ is clearly confirmed. Based on these findings, a rational design strategy for protective surface coating is proposed.Item Modulation of Contact Resistance between Metal and Graphene by Controlling the Graphene Edge, Contact Area, and Point Defects: An Ab Initio Study(Amer Inst Physics) Ma, Bo; Gong, Cheng; Wen, Yanwei; Chen, Rong; Cho, Kyeongjae; Shan, BinA systematic first-principles non-equilibrium Green's function study is conducted on the contact resistance between a series of metals (Au, Ag, Pt, Cu, Ni, and Pd) and graphene in the side contact geometry. Different factors such as the termination of the graphene edge, contact area, and point defect in contacted graphene are investigated. Notable differences are observed in structural configurations and electronic transport characteristics of these metal-graphene contacts, depending on the metal species and aforementioned influencing factors. It is found that the enhanced chemical reactivity of the graphene due to dangling bonds from either the unsaturated graphene edge or point defects strengthens the metal-graphene bonding, leading to a considerable contact resistance reduction for weakly interacting metals Au and Ag. For stronger interacting metals Pt and Cu, a slightly reduced contact resistance is found due to such influencing factors. However, the wetting metals Ni and Pd most strongly hybridize with graphene, exhibiting negligible dependence on the above influencing factors. This study provides guidance for the optimization of metal-graphene contacts at an atomic scale.Item MoS₂ Functionalization for Ultra-Thin Atomic Layer Deposited DielectricsAzcatl, Angelica; McDonnell, Stephen; KC, Santosh; Peng, Xin; Dong, Hong; Qin, Xiaoye; Addou, Rafik; Mordi, Greg I.; Lu, Ning; Kim, Jiyoung; Kim, Moon J.; Cho, Kyeongjae; Wallace, Robert M.; 70133685 (Kim, J)The effect of room temperature ultraviolet-ozone (UV-O₃) exposure of MoS₂ on the uniformity of subsequent atomic layer deposition of Al₂O₃ is investigated. It is found that a UV-O₃ pre-treatment removes adsorbed carbon contamination from the MoS₂ surface and also functionalizes the MoS₂ surface through the formation of a weak sulfur-oxygen bond without any evidence of molybdenum-sulfur bond disruption. This is supported by first principles density functional theory calculations which show that oxygen bonded to a surface sulfur atom while the sulfur is simultaneously back-bonded to three molybdenum atoms is a thermodynamically favorable configuration. The adsorbed oxygen increases the reactivity of MoS₂ surface and provides nucleation sites for atomic layer deposition of Al₂O₃. The enhanced nucleation is found to be dependent on the thin film deposition temperature.Item Multicomponent Silicate Cathode Materials for Rechargeable Li-ion Batteries: An Ab Initio StudyLongo, Roberto C.; Xiong, Ka; Cho, KyeongjaeA first principles investigation is performed to study the structural and electrochemical properties of new multicomponent silicate materials that can be suitable for the cathode of rechargeable Li-ion batteries. The distribution of different transition metals in the silicate structure alters the structural and electronic properties of the crystal, affecting its kinetics, redox potentials and both ionic and electronic conductivities. We also explain the effect of the multiple interactions between Li ions and the transition metals. These multicomponent structures represent a very powerful strategy to control the electrochemical performance of the silicates. In this work, we finally address the implications of such strategy on the design of Li-ion batteries.Item Nucleation and Growth of WSe₂: Enabling Large Grain Transition Metal Dichalcogenides(IOP Publishing Ltd, 2017-09-22) Yue, Ruoyu; Nie, Yifan; Walsh, Lee A.; Addou, Rafik; Liang, Chaoping; Lu, Ning; Barton, Adam T.; Zhu, Hui; Che, Zifan; Barrera, Diego; Cheng, Lanxia; Cha, Pil-Ryung; Chabal, Yves J.; Hsu, Julia W. P.; Kim, Jiyoung; Kim, Moon J.; Colombo, Luigi; Wallace, Robert M.; Cho, Kyeongjae; Hinkle, Christopher L.; 0000-0002-2910-2938 (Liang, C); Yue, Ruoyu; Nie, Yifan; Walsh, Lee A.; Addou, Rafik; Liang, Chaoping; Lu, Ning; Barton, Adam T.; Zhu, Hui; Che, Zifan; Barrera, Diego; Cheng, Lanxia; Chabal, Yves J.; Hsu, Julia W. P.; Kim, Jiyoung; Kim, Moon J.; Wallace, Robert M.; Cho, Kyeongjae; Hinkle, Christopher L.The limited grain size (< 200 nm) for transition metal dichalcogenides (TMDs) grown by molecular beam epitaxy (MBE) reported in the literature thus far is unsuitable for high-performance device applications. In this work, the fundamental nucleation and growth behavior of WSe₂ is investigated through a detailed experimental design combined with on-lattice, diffusion-based first principles kinetic modeling to enable large area TMD growth. A three-stage adsorption-diffusion-attachment mechanism is identified and the adatom stage is revealed to play a significant role in the nucleation behavior. To limit the nucleation density and promote 2D layered growth, it is necessary to have a low metal flux in conjunction with an elevated substrate temperature. At the same time, providing a Se-rich environment further limits the formation of W-rich nuclei which suppresses vertical growth and promotes 2D growth. The fundamental understanding gained through this investigation has enabled an increase of over one order of magnitude in grain size for WSe₂ thus far, and provides valuable insight into improving the growth of other TMD compounds by MBE and other growth techniques such as chemical vapor deposition (CVD).Item Organic-Inorganic Hybrid Semiconductor Thin Films Deposited Using Molecular-Atomic Layer Deposition (MALD)(Royal Society of Chemistry) Huang, Jie; Zhang, Hengji; Lucero, Antonio; Cheng, Lanxia; KC, Santosh; Wang, Jian; Hsu, Julia W. P.; Cho, Kyeongjae; Kim, Jiyoung; 0000 0003 8600 0978 (Hsu, JWP); 0000-0003-2698-7774 (Cho, K); 0000-0003-2781-5149 (Kim, J); Huang, Jie; Zhang, Hengji; Lucero, Antonio; Cheng, Lanxia; KC, Santosh; Wang, Jian; Hsu, Julia W. P.; Cho, Kyeongjae; Kim, JiyoungMolecular-atomic layer deposition (MALD) is employed to fabricate hydroquinone (HQ)/diethyl zinc (DEZ) organic-inorganic hybrid semiconductor thin films with accurate thickness control, sharp interfaces, and low deposition temperature. Self-limiting growth is observed for both HQ and DEZ precursors. The growth rate remains constant at approximately 2.8 Å per cycle at 150°C. The hybrid materials exhibit n-type semiconducting behavior with a field effect mobility of approximately 5.7 cm² V⁻¹ s⁻¹ and an on/off ratio of over 103 following post annealing at 200°C in nitrogen. The resulting films are characterized using ellipsometry, Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), UV-Vis spectroscopy, transistor behavior, and Hall-effect measurements. Density functional theory (DFT) and many-body perturbation theory within the GW approximation are also performed to assist the explanation and understanding of the experimental results. This research offers n-channel materials as valuable candidates for efficient organic CMOS devices. © 2016.Item Phase Stability of Li-Mn-O Oxides as Cathode Materials for Li-ion Batteries: Insights from ab initio Calculations(Royal Society of Chemistry) Longo, R. C.; Kong, F. T.; KC, Santosh; Park, M. S.; Yoon, J.; Yeon, D-H; Park, J-H; Doo, S-G; Cho, KyeongjaeIn this work, we present a density-functional theory (DFT) investigation of the phase stability, electrochemical stability and phase transformation mechanisms of the layered and over-lithiated Mn oxides. This study includes the thermodynamic stability of Li and oxygen vacancies, to examine the electrochemical activation mechanisms of these cathode materials. The DFT calculations provide phase diagrams of the Li-Mn-O system in both physical and chemical potential spaces, including the crystals containing vacancies as independent phases. The results show the ranges of electrochemical activity for both layered LiMnO₂ and over-lithiated Li₂MnO₃. By using a thermodynamic model analysis, we found that the required temperature for oxygen evolution and Li vacancy formation is too high to be compatible with any practical synthesis temperature. Using solid-state transition calculations, we have identified the key steps in the phase transition mechanism of the layered LiMnO₂ into the spinel phase. The calculated effects of pH on the Li-Mn-O phase stability elucidated the mechanism of Mn² formation from the spinel phase under acidic conditions.;Item Quantum Transport and Band Structure Evolution under High Magnetic Field in Few-Layer Tellurene(American Chemical Society) Qiu, G.; Wang, Y.; Nie, Yifan; Zheng, Yongping; Cho, Kyeongjae; Wu, W.; Ye, P. D.; 0000-0003-4771-3633 (Nie, Y); 0000-0003-2698-7774 (Cho, K); 369148996084659752200 (Cho, K); Nie, Yifan; Zheng, Yongping; Cho, KyeongjaeQuantum Hall effect (QHE) is a macroscopic manifestation of quantized states that only occurs in confined two-dimensional electron gas (2DEG) systems. Experimentally, QHE is hosted in high-mobility 2DEG with large external magnetic field at low temperature. Two-dimensional van der Waals materials, such as graphene and black phosphorus, are considered interesting material systems to study quantum transport because they could unveil unique host material properties due to the easy accessibility of monolayer or few-layer thin films at the 2D quantum limit. For the first time, we report direct observation of QHE in a novel low-dimensional material system, tellurene. High-quality 2D tellurene thin films were acquired from recently reported hydrothermal method with high hole mobility of nearly 3000 cm2/(V s) at low temperatures, which allows the observation of well-developed Shubnikov-de Haas (SdH) oscillations and QHE. A four-fold degeneracy of Landau levels in SdH oscillations and QHE was revealed. Quantum oscillations were investigated under different gate biases, tilted magnetic fields, and various temperatures, and the results manifest the inherent information on the electronic structure of Te. Anomalies in both temperature-dependent oscillation amplitudes and transport characteristics were observed that are ascribed to the interplay between the Zeeman effect and spin-orbit coupling, as depicted by the density functional theory calculations. ©2018 American Chemical Society.Item Selectivity of Metal Oxide Atomic Layer Deposition on Hydrogen Terminated and Oxidized Si(001)-(2x1) Surface(A V S Amer Inst Physics, 2014-02-10) Longo, Roberto C.; McDonnell, Stephen; Dick, D.; Wallace, Robert M.; Chabal, Yves J.; Owen, James H. G.; Ballard, Josh B.; Randall, John N.; Cho, Kyeongjae; 0000 0000 4239 3958 (Chabal, YJ); 89624105 (Chabal, YJ)In this work, the authors used density-functional theory methods and x-ray photoelectron spectroscopy to study the chemical composition and growth rate of HfO₂, Al₂O₃, and TiO₂ thin films grown by in-situ atomic layer deposition on both oxidized and hydrogen-terminated Si(001) surfaces. The growth rate of all films is found to be lower on hydrogen-terminated Si with respect to the oxidized Si surface. However, the degree of selectivity is found to be dependent of the deposition material. TiO₂ is found to be highly selective with depositions on the hydrogen terminated silicon having growth rates up to 180 times lower than those on oxidized Si, while similar depositions of HfO₂ and Al₂O₃ resulted in growth rates more than half that on oxidized silicon. By means of density-functional theory methods, the authors elucidate the origin of the different growth rates obtained for the three different precursors, from both energetic and kinetic points of view.Item Spurious Dangling Bond Formation During Atomically Precise Hydrogen Depassivation Lithography on Si(100): The Role of Liberated Hydrogen(A V S Amer Inst Physics) Ballard, Joshua B.; Owen, James H. G.; Alexander, Justin D.; Owen, William R.; Fuchs, Ehud; Randall, John N.; Longo, Roberto C.; Cho, KyeongjaeThe production of spurious dangling bonds during the hydrogen depassivation lithography process on Si(100)-H is studied. It is shown that the number of spurious dangling bonds produced depends on the size of the primary pattern on the surface, not on the electron dose, indicating that the spurious dangling bonds are formed via an interaction of the liberated hydrogen with the surface. It is also shown that repassivation may occur if hydrogen depassivation lithography is performed near an already patterned area. Finally, it is argued that the product of the interaction is a single dangling bond next to a monohydride silicon on a silicon dimer, with a reaction probability much in excess of that previously observed.Item Superior Low-Temperature NO Catalytic Performance of PrMn₂O₅ over SmMn₂O₅ Mullite-Type Catalysts(Royal Society of Chemistry, 2019) Thampy, Sampreetha; Ashburn, Nickolas; Liu, C.; Xiong, K.; Dillon, Sean; Zheng, Yongping; Chabal, Yves J.; Cho, Kyeongjae; Hsu, Julia W. P.; 0000-0002-7821-3001 (Hsu, JWP); 0000-0002-6435-0347 (Chabal, YJ); 0000-0003-2698-7774 (Cho, K); 369148996084659752200 (Cho, K); Thampy, Sampreetha; Ashburn, Nickolas; Dillon, Sean; Zheng, Yongping; Chabal, Yves J.; Cho, Kyeongjae; Hsu, Julia W. P.By studying their surface chemistry, metal-oxygen bond strength, and critical energy barrier heights, we elucidate the differences in the NO oxidation catalytic performance of PrMn₂O₅ and SmMn₂O₅ mullite-type oxides. The 50% conversion temperature is lower (230 °C vs. 275 °C) and the maximum conversion efficiency is higher (81% at 282 °C vs. 68% at 314 °C) for PrMn₂O₅ compared to SmMn₂O₅, despite having a ∼15% lower specific surface area. Furthermore, PrMn₂O₅ exhibits higher maximum efficiency compared to Pt/Al₂O₃. Combined experimental and theoretical findings indicate that the superior catalytic performance of PrMn₂O₅ at low temperatures arises from the presence of more labile and reactive surface lattice oxygen due to weaker Mn-O bond strength and lower thermal stability of surface NOₓ ad-species. ©2019 The Royal Society of Chemistry.