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Atomic layer deposition (ALD) is an efficient technique that allows atomic-level surface control of metal catalysts for the design and development of electrocatalytic materials. Herein, we report a strategy for efficient catalyst design using a particle ALD method to enhance the electrocatalytic glycerol-oxidation-reaction (GOR) performance. Atomically controlled thin SnO2 layers were deposited on a carbon-supported Pt nanoparticle (Pt/C) surface using the ALD technique. The resulting SnO2 overcoated Pt/C (ALD(SnO2)–Pt/C) was then heat-treated at 400 °C under a N2 atmosphere. The onset potential as a kinetic parameter decreased with ALD (SnO2) coatings. The turnover frequency (TOF) for the GOR showed similar values for the tested samples (TOF of Pt/C: 74.86 h−1 and TOF of ALD(SnO2)–Pt/C: 91.29 h−1). Interestingly, interactions between the ALD SnO2 overcoating and Pt nanoparticles improved the catalytic stability for the GOR, preventing sintering of Pt nanoparticle catalysts. This demonstrates that an ALD SnO2 coating on defect sites of Pt can diminish Pt sintering for the GOR. From the GOR in an electrochemical batch reactor, the ALD(SnO2)–Pt/C catalyst also generated more glyceraldehyde (GAD) product than uncoated Pt/C at a similar glycerol conversion level. The density functional theory (DFT) calculations suggest that the binding energies of glycerol and reaction intermediates change at the interface of the SnO2-coated Pt surface compared to those at the Pt surface only, thus affecting the reaction chemistry for the electrocatalytic GOR. This work highlights how we can control reaction performance measures such as catalytic stability and product selectivity by using the particle ALD technique for electrocatalytic reactions such as glycerol oxidation.

Gas sensors for Internet of Things applications should meet two requisites – low power consumption and easy mounting universally. To satisfy the conditions, gas sensors need to operate at lower temperature and be flexible. In this study, we demonstrate a flexible gas sensor operating at room temperature using vertically aligned two-dimensional SnS2 nanomaterials. The atomic layer deposition (ALD) technique allows direct growth of SnS2 on a plastic substrate. The morphological structure of SnS2 is engineered by effecting changes in the growth temperature and substrate surface, which leads to the excellent sensing performance with respect to NO2 gas along with superior gas selectivity. The gas response is as high as 309 at 1 ppm of NO2 at room temperature, and a reliably high response is also observed even below 500 ppb of NO2. The fabricated flexible gas sensor exhibits comparable sensing performance and stability upon bending. Furthermore, the ALD achieves excellent uniformity in both the structural and electrical properties of SnS2 over a 4 in. wafer, which is essential for mass production. Therefore, we believe that this work would contribute to realizing the practical application of highly sensitive flexible gas sensors.

Steel corrosion is a key engineering issue in the development of advanced nuclear reactors using liquid metals. The present study demonstrates that the steel corrosion behaviors can be systematically understood and classified based on the types of valence electrons of liquid metals, namely, s-electron liquid metals (s-LMs), such as liquid Na and Li, and p-electron liquid metals (p-LMs), such as liquid lead-bismuth eutectic (LBE) and Pb, where the conduction band is composed of s and p valence electrons, respectively. Through a comparative analysis of the physiochemical states of 3d transition metal atoms dissolved in liquid Na and liquid LBE by means of first-principles molecular dynamics (FPMD), it is shown that the 3d and 4s orbitals of the transition metals hardly interact with the s band of s-LMs, while they strongly interact with the p band of p-LMs in a covalent manner. This fact is consistently seen in the electronic states and the atomic configuration and can be successfully used to explain the differences in the steel corrosion behaviors observed between the liquid metals by experiments. The present findings provide fundamental insights into the corrosion chemistry of liquid metals.

Research on two-dimensional (2D) metal dichalcogenides is rapidly expanding owing to their unique characteristics that do not exist in bulk materials. The industrially compatible development of these emerging materials is indispensable to facilitate the transition of 2D metal dichalcogenides from the research stage to the practical industrial application stage. However, an industrially relevant method, i.e., the low-temperature synthesis of wafer-scale, continuous, and orientation-controlled 2D metal dichalcogenides, still remains a significant challenge. Here, we report the low-temperature (≤350 °C) synthesis of uniform and continuous n-type SnS2 thin films via the combination of atomic layer deposition (ALD) of tin oxides and subsequent sulfurization. Well-crystallized and aligned SnS2 layers parallel to the substrate are demonstrated through the phase engineering of the ALD-grown tin oxide and the substrate surface. The additional H2S plasma treatment at 300 °C leads to the formation of stoichiometric SnS2. The formation of conformal SnS2 layers over a three-dimensional undulating hole structure is confirmed, which reveals the potential for applications beyond the planar structured architecture. The present results could be a step toward the realization of 2D metal dichalcogenides in industry.

Here, we demonstrate high-performance p-type thin film transistors (TFTs) with a SnO channel layer grown by atomic layer deposition (ALD). The performance of the SnO TFTs relies on hole carriers and defects in SnO and near the back-channel surface of SnO as well as the quality of the gate dielectric/SnO interface. The growth of SnO films at a high temperature of 210 °C effectively suppresses the hole carrier concentration, leading to a high on-current/off-current (Ion/Ioff) ratio. In addition, the SnO films grown at 210 °C achieve high field effect mobility (μFE) compared with the SnO films grown at lower temperatures because of their large grain size and lower impurity contents. However, the SnO films grown at 210 °C still contain defects and hole carriers, especially near the back-channel surface. The post-deposition process – back-channel surface passivation with ALD-grown Al2O3 followed by post-deposition annealing at 250 °C – considerably alleviates the defects and hole carriers, resulting in superior TFT performance (Ion/Ioff: 2 × 106, subthreshold swing: 1.8 V dec−1, μFE: ∼1 cm2 V−1 s−1). We expect that the SnO ALD and subsequent process will provide a new opportunity for producing high-performance p-type oxide TFTs.

Steels are easily corroded in a liquid lead-bismuth eutectic (LBE) because their components, such as Fe, Cr and Ni, exhibit a high solubility in the liquid LBE. To understand the reason for such a high solubility of these 3d transition metals, we have performed first-principles molecular dynamics calculations and analyzed the pair-correlation functions, electronic densities of states, and Bader charges and volumes of the 3d transition metals dissolved in the liquid LBE as impurities. The calculations show that the 4s and 3d orbitals of the 3d impurity atoms largely interact with the 6p band of the LBE, which generates bonding orbitals. We suggest that the high stability of 3d metals in the liquid LBE is caused by the interactions of the 4s and 3d orbitals with the 6p band. Spin polarization is induced by V, Cr, Mn, Fe and Co impurity atoms in a similar manner to the Slater-Pauling curve of solid transition metals, which exhibits a downward shift in the atomic number by approximately two. Based on the degree of spin polarization and the shifted trend of the Slater-Pauling curve, we suggest that Ni exhibits a higher solubility than Cr and Fe because of the differences in their interaction strengths between their 3d orbitals and the 6p band. In addition, the 4s and 3d orbitals of the 3d impurity atoms were found to interact more favorably with the Bi 6p band than the Pb 6p band, which is consistent with the fact that liquid Bi is more corrosive to steels than is liquid Pb.

Heteroleptic complexes of strontium (1–7) were prepared by employing β-diketonates and donor-functionalized alkoxides as coordinating ligands. The results illustrate the effect of alkoxide substituent groups on the overall structures of the complexes. The presence of a terminal methoxy group in the alkoxide ligands leads to the formation of trimeric complexes 1–4, whereas the substituents on the amine nitrogen prove to have less influence in determining the structure. The attempts to increase steric bulkiness of the aminoalkoxide ligands by introducing ethyl groups on the amine nitrogen and to the alkoxy carbon did not lead to a structural change from the dimeric form in 5–7 but resulted in structurally interesting strontium complexes. In trimeric complexes 2–4, the three strontium atoms were held together by two μ3-O bonds using alkoxide oxygen atoms and two μ2-O bonds using a combination of alkoxide and β-diketonate ligand oxygens. The strontium metal centers in these complexes exhibit seven-coordination states in 2 and 4, whereas 3 exhibits one six-coordinated and two seven-coordinated strontium metals in its structure. All of the complexes were characterized using FT-NMR, FT-IR, elemental analyses, and thermogravimetric (TG) analyses.

Rutile structured TiO2 films have received great attention as dielectric materials in capacitors of the next-generation dynamic random access memory (DRAM) due to their high dielectric constant (80–150). Ru or RuO2, which is one of the most promising electrode materials in DRAM capacitors, is indispensable to form the rutile structure. In this work, a series of the Ru-related layers with compositions ranging from Ru to RuO2via RuOx (x: ∼1.12) was used as a bottom electrode for the ALD growth of TiO2 films. It was found that the growth per cycle of TiO2 at the initial growth stage was drastically increased on RuOx (RuO2/Ru mixture) compared to Ru and RuO2. This is attributed to the drastic increase in the chemical activity of oxygen in the mixture film of RuO2/Ru. The catalytic decomposition of RuO2 with the help of Ru in the film played the crucial role for the increase in the active oxygen. Although RuO2 and Ru mostly retained their structures during the ALD of TiO2 or chemical etching using O3 gas, the RuOx film, which was composed of 56% RuO2 and 44% Ru, drastically changed its phase composition during the ALD of TiO2 at 250 °C and changed almost to Ru. Other chemical effects depending on the chemical composition and phase structure were also examined in detail.

Tantalum oxide (Ta2O5) and tantalum silicate (TaSiOx) films were grown by atomic layer deposition from TaCl5, SiCl4, and O3. Saturation of absorption was observed for TaCl5 at short TaCl5 pulses. However, long TaCl5 exposure resulted in a reduced growth per cycle of Ta2O5 and TaSiOx films due to concomitant etching. The saturated growth per cycle of Ta2O5 was ∼0.77 A per cycle at a deposition temperature of 300 °C and ∼1 A per cycle at 250 °C. Quadrupole mass spectrometry revealed that TaCl5 chemisorbed on the surface with negligible ligand removal. Subsequently, the reaction with O3 led to the formation of both chlorine oxides (ClxOy) and chlorine (Clx) as by-products. Si incorporation was found to be feasible using supercycles including SiCl4/O3 cycles although no SiO2 deposition was observed for SiCl4/O3 cycles only. At a deposition temperature of 300 °C, self-limiting growth was observed as a function of SiCl4 and O3 pulse time. This suggests that the adsorption of SiCl4 on Ta-terminated surfaces is more favorable than on Si-terminated ones, similar to the case of the equivalent H2O-based ALD process. The Cl impurity levels in Ta2O5 films from TaCl5 and O3 were found to be lower than those in films from TaCl5 and H2O. The Ta2O5 and TaSiOx films were amorphous as deposited. Ta2O5 crystallized into orthorhombic β-Ta2O5 at a temperature of 740 °C while TaSiOx showed no signs of crystallization up to 900 °C. Amorphous Ta2O5 and Ta0.6Si0.4Ox films showed dielectric constants of 31 and 24, respectively, and exhibited lower leakage current densities than those deposited from TaCl5, SiCl4, and H2O.

The effects of thin Al2O3 layers interposed between atomic layer deposited SrTiO3 (STO) films and Ru substrates on the growth and properties of STO films were examined. Although a 3–4 nm thick TiO2 barrier layer was necessary to completely suppress the oxygen diffusion from the underlying Ru(O) layer, which could result in uncontrolled excessive Sr incorporation into the film, a 2–3 nm thick Al2O3 barrier layer was sufficient to achieve the saturated oxygen blocking effect. Therefore, only a 0.4 nm thick Al2O3 layer could effectively suppress uncontrollable initial excessive incorporation of Sr, and a 1 nm thick Al2O3 layer had a blocking effect that was equivalent to that of a 3 nm thick TiO2 layer. STO films were crystallized in situ by the assistance of crystallized 2–3 nm thick STO seed layers that were pre-deposited and annealed. The bulk dielectric constant of STO calculated by the slope of equivalent oxide thickness vs. physical thickness was 173 on the 1 nm thick Al2O3/Ru substrate. However, further research is necessary to reduce the adverse contribution of the interfacial layers to achieve a scaling of the equivalent oxide thickness to ≪0.5 nm.