Self-Formation of a Ru/ZnO Multifunctional Bilayer for the Next-Generation Interconnect Technology via Area-Selective Atomic Layer Deposition.

This study suggests a Ru/ZnO bilayer grown using area-selective atomic layer deposition (AS-ALD) as a multifunctional layer for advanced Cu metallization. As a diffusion barrier and glue layer, ZnO is selectively grown on SiO2 , excluding Cu, where Ru, as a liner and seed layer, is grown on both surfaces. Dodecanethiol (DDT) is used as an inhibitor for the AS-ALD of ZnO using diethylzinc and H2 O at 120 °C. H2 plasma treatment removes the DDT adsorbed on Cu, forming inhibitor-free surfaces. The ALD-Ru film is then successfully deposited at 220 °C using tricarbonyl(trimethylenemethane)ruthenium and O2 . The Cu/bilayer/Si structural and electrical properties are investigated to determine the diffusion barrier performance of the bilayer film. Copper silicide is not formed without the conductivity degradation of the Cu/bilayer/Si structure, even after annealing at 700 °C. The effect of ZnO on the Ru/SiO2 structure interfacial adhesion energy is investigated using a double-cantilever-beam test and is found to increase with ZnO between Ru and SiO2 . Consequently, the Ru/ZnO bilayer can be a multifunctional layer for advanced Cu interconnects. Additionally, the formation of a bottomless barrier by eliminating ZnO on the via bottom, or Cu, is expected to decrease the via resistance for the ever-shrinking Cu lines.

Gradient area-selective deposition for seamless gap-filling in 3D nanostructures through surface chemical reactivity control.

The integration of bottom-up fabrication techniques and top-down methods can overcome current limits in nanofabrication. For such integration, we propose a gradient area-selective deposition using atomic layer deposition to overcome the inherent limitation of 3D nanofabrication and demonstrate the applicability of the proposed method toward large-scale production of materials. Cp(CH3)5Ti(OMe)3 is used as a molecular surface inhibitor to prevent the growth of TiO2 film in the next atomic layer deposition process. Cp(CH3)5Ti(OMe)3 adsorption was controlled gradually in a 3D nanoscale hole to achieve gradient TiO2 growth. This resulted in the formation of perfectly seamless TiO2 films with a high-aspect-ratio hole structure. The experimental results were consistent with theoretical calculations based on density functional theory, Monte Carlo simulation, and the Johnson-Mehl-Avrami-Kolmogorov model. Since the gradient area-selective deposition TiO2 film formation is based on the fundamentals of molecular chemical and physical behaviours, this approach can be applied to other material systems in atomic layer deposition.

Elucidating the Reaction Mechanism of Atomic Layer Deposition of Al2O3 with a Series of Al(CH3)xCl3-x and Al(CyH2y+1)3 Precursors.

The adsorption of metalorganic and metal halide precursors on the SiO2 surface plays an essential role in thin-film deposition processes such as atomic layer deposition (ALD). In the case of aluminum oxide (Al2O3) films, the growth characteristics are influenced by the precursor structure, which controls both chemical reactivity and the geometrical constraints during deposition. In this work, a systematic study using a series of Al(CH3)xCl3-x (x = 0, 1, 2, and 3) and Al(CyH2y+1)3 (y = 1, 2, and 3) precursors is carried out using a combination of experimental spectroscopic techniques together with density functional theory calculations and Monte Carlo simulations to analyze differences across precursor molecules. Results show that reactivity and steric hindrance mutually influence the ALD surface reaction. The increase in the number of chlorine ligands in the precursor shifts the deposition temperature higher, an effect attributed to more favorable binding of the intermediate species due to higher Lewis acidity, while differences between precursors in film growth per cycle are shown to originate from variations in adsorption activation barriers and size-dependent saturation coverage. Comparison between the theoretical and experimental results indicates that the Al(CyH2y+1)3 precursors are favored to undergo two ligand exchange reactions upon adsorption at the surface, whereas only a single Cl-ligand exchange reaction is energetically favorable upon adsorption by the AlCl3 precursor. By pursuing the first-principles design of ALD precursors combined with experimental analysis of thin-film growth, this work enables a robust understanding of the effect of precursor chemistry on ALD processes.

Icephobic Coating through a Self-Formed Superhydrophobic Surface Using a Polymer and Microsized Particles.

Icephobic coatings have been extensively studied for decades to overcome the potential damage associated with ice formation in various devices that are operated under harsh weather conditions. Superhydrophobic surface coatings have been applied for icephobic coating applications owing to their low surface energy. In this study, an icephobic coating of a self-formed superhydrophobic surface using polydimethylsiloxane (PDMS) and SiO2 powder was investigated. The effect of superhydrophobicity on icephobicity was determined by varying the experimental parameters. Polyvinylidene fluoride (PVDF) was added to the PDMS solution to improve the mechanical properties of the icephobic layer. The PDMS-PVDF solution also showed a self-formation behavior into a superhydrophobic surface. In addition, the icephobicity and mechanical properties of the PDMS-PVDF mixture coating improved because of the multilevel nanostructure formed by physical and chemical interactions between the mixture and SiO2 powder. We believe that the proposed approach will be a suitable candidate for various practical applications of icephobicity and a model system to understand the correlation between superhydrophobicity and icephobicity.

Growth modulation of atomic layer deposition of HfO2 by combinations of H2O and O3 reactants.

Atomic layer deposition (ALD) is a thin film deposition technique based on self-saturated reactions between a precursor and reactant vacuum conditions. A typical ALD reaction consists of the first half-reaction of the precursor and the second half-reaction of the counter reactant, in which the terminal groups on the surface change after each half-reaction. In this study, the effects of counter reactants on the surface termination and growth characteristics of ALD HfO2 thin films formed on Si substrates using tetrakis(dimethylamino)-hafnium (TDMAH) as a precursor were investigated. Two counter reactants, H2O and O3, were individually employed, as well as in combination with consecutive exposure by H2O-O3 and O3-H2O. The film growth behaviors and properties differed when the sequence of exposure of the substrate to the reactants was varied. Based on X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) simulation, the changes are attributed to the effects of the surface terminations formed from different counter reactant combinations. The knowledge from this work could provide insight for precisely tuning the growth and properties of ALD films.

Toward Enhanced Humidity Stability of Triboelectric Mechanical Sensors via Atomic Layer Deposition.

Humid conditions can disrupt the triboelectric signal generation and reduce the accuracy of triboelectric mechanical sensors. This study demonstrates a novel design approach using atomic layer deposition (ALD) to enhance the humidity resistance of triboelectric mechanical sensors. Titanium oxide (TiOx) was deposited on polytetrafluoroethylene (PTFE) film as a moisture passivation layer. To determine the effective ALD process cycle, the TiOx layer was deposited with 100 to 2000 process cycles. The triboelectric behavior and surface chemical bonding states were analyzed before and after moisture exposure. The ALD-TiOx-deposited PTFE showed three times greater humidity stability than pristine PTFE film. Based on the characterization of TiOx on PTFE film, the passivation mechanism was proposed, and it was related to the role of the oxygen-deficient sites in the TiOx layer. This study could provide a novel way to design stable triboelectric mechanical sensors in highly humid environments.

Self-Formation of Superhydrophobic Surfaces through Interfacial Energy Engineering between Liquids and Particles.

The superhydrophobic surface has been used in ultradry surface applications, such as the maritime industry, windshields, non-sticky surfaces, anti-icing surfaces, self-cleaning surfaces, and so forth. However, one of the main hurdles for the production of superhydrophobic surfaces is high-cost fabrication methods. Here, we report a handy process of self-synthesis fabrication of superhydrophobic surfaces with daily supplies. Driven by the physics of biscuit dunking, we introduce a method to self-synthesize superhydrophobic surfaces from daily supplies by coating a substrate with a liquid (liquids of paraffin from candles or polydimethylsiloxane) and subsequently sprinkling powders (food-desiccant silica, alumina, sugar, salt, or flour). A mechanistic study revealed that the capillary force, governed by surface energy difference, liquid viscosity, and powder pore size, draws the liquid solution into the porous channels within the powders. The entire surface of powders, in turn, is covered with the low-surface-energy liquid to maintain the porosity, creating a 3D porous nanostructure, resulting in a water contact angle over 160°. This work provides a scientific understanding that technological developments are closely related to the science that can be seen in our daily lives. Also, we believe that further intensive studies extended from this work could enable to home-fabricate a superhydrophobic surface, such as a bathtub and sink in bathrooms and a cooking area and sink in kitchens.

Dataset for TiN Thin Films Prepared by Plasma-Enhanced Atomic Layer Deposition Using Tetrakis(dimethylamino)titanium (TDMAT) and Titanium Tetrachloride (TiCl4) Precursor.

A dataset in this report is regarding an article "Ultrathin Effective TiN Protective Films Prepared by Plasma-Enhanced Atomic Layer Deposition for High Performance Metallic Bipolar Plates of Polymer Electrolyte Membrane Fuel Cells" [1]. TiN (Titanium Nitride) thin films were deposited by Plasma-Enhanced Atomic Layer Deposition (PEALD) method using well known two types of precursor: using tetrakis(dimethylamino)titanium (TDMAT) and titanium tetrachloride (TiCl4), and plasma. Summarized reports, growth characteristics (growth rate as a function of each precursor pulse time, plasma power, precursor and plasma purge time, thickness depending on the number of PEALD cycles), each precursor structural information and the atomic force micrographs (AFM) data are herein demonstrated. For TDMAT-TiN, N2 plasma was used as a reactant whereas, H2+N2 plasma was used as TiCl4-TiN reactant. To apply the bipolar plate substrate, two types of TiN thin films were introduced into Stainless steel (SUS) 316L.

Tunable Color Coating of E-Textiles by Atomic Layer Deposition of Multilayer TiO2/Al2O3 Films.

We successfully fabricated a conductive E-textile and color-coated E-textile by depositing multilayer Al2O3/TiO2 on a conductive E-textile through atomic layer deposition (ALD). Pt was deposited on an E-textile as a conductive layer via low-temperature ALD. The color of the coated conductive E-textile could be tuned to violet, green, or pink by simply varying the thickness of the Al2O3 and TiO2 layers. Both experimental and simulation results revealed that seven different colors can be obtained with single-layer TiO2 and multilayer Al2O3/TiO2, depending on the film thickness and their refractive indices. This method is highly effective for enhancing the fastness of structural color on conductive E-textiles. Furthermore, the mechanical properties and chemical stability of the color-coated E-textiles were investigated. The color-coated E-textiles could withstand acidic and basic solutions, with almost negligible changes in their morphology; this in turn indicates their excellent chemical stability. These switchable stable color-based conductive E-textiles can be used as a platform to directly integrate future wearable electronics in textiles.

Surface Energy Change of Atomic-Scale Metal Oxide Thin Films by Phase Transformation.

Fine-tuning of the surface free energy (SFE) of a solid material facilitates its use in a wide range of applications requiring precise control of the ubiquitous presence of liquid on the surface. In this study, we found that the SFE of rare-earth oxide (REO) thin films deposited by atomic layer deposition (ALD) gradually decreased with increasing film thickness; however, these changes could not be understood by classical interaction models. Herein, the mechanism underlying the aforesaid decrease was systematically studied by measuring contact angles, surface potential, adhesion force, crystalline structures, chemical compositions, and morphologies of the REO films. A growth mode of the REO films was observed: layer-by-layer growth at the initial stage with an amorphous phase and subsequent crystalline island growth, accompanied by a change in the crystalline structure and orientation that affects the SFE. The portion of the surface crystalline facets terminated with (222) and (440) planes evolved with an increase in ALD cycles and film thickness, as an amorphous phase was transformed. Based on this information, we demonstrated an SFE-tuned liquid tweezer with selectivity to target liquid droplets. We believe that the results of this fundamental and practical study, with excellent selectivity to liquids, will have significant impacts on coating technology.

Analysis of Defect Recovery in Reduced Graphene Oxide and Its Application as a Heater for Self-Healing Polymers.

Reduced graphene oxide (RGO) obtained from graphene oxide has received much attention because of its simple and cost-effective manufacturing process. Previous studies have demonstrated the scalable production of RGO with relatively high quality; however, irreducible defects on RGO deteriorate the unique intrinsic physical properties of graphene, such as high-mobility electrical charge transport, limiting its potential applicability. Using the enhanced chemical reactivity of such defects, atomic layer deposition (ALD) can be a useful method to selectively passivate the defect sites. Herein, we analyzed the selective formation of Pt by ALD on the defect sites of RGO and investigated the effect of Pt formation on the electrical properties of RGO by using ultrafast terahertz (THz) laser spectroscopy. Time-resolved THz measurements directly corroborated that the degree of the defect-recovering property of ALD Pt-treated RGO appearing as Auger-type sub-picosecond relaxation, which is otherwise absent in pristine RGO. In addition, the conductivity improvement of Pt-recovered RGO was theoretically explained by density functional theory calculations. The ALD Pt-passivated RGO yielded a superior platform for the fabrication of a highly conductive and transparent graphene heater. By using the ALD Pt/RGO heater embedded underneath scratched self-healing polymer materials, we also demonstrated the effective recovery property of self-healing polymers with high-performance heating capability. Our work is expected to result in significant advances toward practical applications for RGO-based flexible and transparent electronics.

Reaction Mechanism of Area-Selective Atomic Layer Deposition for Al2O3 Nanopatterns.

The reaction mechanism of area-selective atomic layer deposition (AS-ALD) of Al2O3 thin films using self-assembled monolayers (SAMs) was systematically investigated by theoretical and experimental studies. Trimethylaluminum (TMA) and H2O were used as the precursor and oxidant, respectively, with octadecylphosphonic acid (ODPA) as an SAM to block Al2O3 film formation. However, Al2O3 layers began to form on the ODPA SAMs after several cycles, despite reports that CH3-terminated SAMs cannot react with TMA. We showed that TMA does not react chemically with the SAM but is physically adsorbed, acting as a nucleation site for Al2O3 film growth. Moreover, the amount of physisorbed TMA was affected by the partial pressure. By controlling it, we developed a new AS-ALD Al2O3 process with high selectivity, which produces films of ∼60 nm thickness over 370 cycles. The successful deposition of Al2O3 thin film patterns using this process is a breakthrough technique in the field of nanotechnology.

Atomic layer deposition of 1D and 2D nickel nanostructures on graphite.

One-dimensional (1D) nanowires (NWs) and two-dimensional (2D) thin films of Ni were deposited on highly ordered pyrolytic graphite (HOPG) by atomic layer deposition (ALD), using NH3 as a counter reactant. Thermal ALD using NH3 gas forms 1D NWs along step edges, while NH3 plasma enables the deposition of a continuous 2D film over the whole surface. The lateral and vertical growth rates of the Ni NWs are numerically modeled as a function of the number of ALD cycles. Pretreatment with NH3 gas promotes selectivity in deposition by the reduction of oxygenated functionalities on the HOPG surface. On the other hand, NH3 plasma pretreatment generates surface nitrogen species, and results in a morphological change in the basal plane of graphite, leading to active nucleation across the surface during ALD. The effects of surface nitrogen species on the nucleation of ALD Ni were theoretically studied by density functional theory calculations. Our results suggest that the properties of Ni NWs, such as their density and width, and the formation of Ni thin films on carbon surfaces can be controlled by appropriate use of NH3.

Self-Limiting Layer Synthesis of Transition Metal Dichalcogenides.

This work reports the self-limiting synthesis of an atomically thin, two dimensional transition metal dichalcogenides (2D TMDCs) in the form of MoS2. The layer controllability and large area uniformity essential for electronic and optical device applications is achieved through atomic layer deposition in what is named self-limiting layer synthesis (SLS); a process in which the number of layers is determined by temperature rather than process cycles due to the chemically inactive nature of 2D MoS2. Through spectroscopic and microscopic investigation it is demonstrated that SLS is capable of producing MoS2 with a wafer-scale (~10 cm) layer-number uniformity of more than 90%, which when used as the active layer in a top-gated field-effect transistor, produces an on/off ratio as high as 10(8). This process is also shown to be applicable to WSe2, with a PN diode fabricated from a MoS2/WSe2 heterostructure exhibiting gate-tunable rectifying characteristics.

Improved Corrosion Resistance and Mechanical Properties of CrN Hard Coatings with an Atomic Layer Deposited Al2O3 Interlayer.

A new approach was adopted to improve the corrosion resistance of CrN hard coatings by inserting a Al2O3 layer through atomic layer deposition. The influence of the addition of a Al2O3 interlayer, its thickness, and the position of its insertion on the microstructure, surface roughness, corrosion behavior, and mechanical properties of the coatings was investigated. The results indicated that addition of a dense atomic layer deposited Al2O3 interlayer led to a significant decrease in the average grain size and surface roughness and to greatly improved corrosion resistance and corrosion durability of CrN coatings while maintaining their mechanical properties. Increasing the thickness of the Al2O3 interlayer and altering its insertion position so that it was near the surface of the coating also resulted in superior performance of the coating. The mechanism of this effect can be explained by the dense Al2O3 interlayer acting as a good sealing layer that inhibits charge transfer, diffusion of corrosive substances, and dislocation motion.

Real-time detection of chlorine gas using Ni/Si shell/core nanowires.

We demonstrate the selective adsorption of Ni/Si shell/core nanowires (Ni-Si NWs) with a Ni outer shell and a Si inner core on molecularly patterned substrates and their application to sensors for the detection of chlorine gas, a toxic halogen gas. The molecularly patterned substrates consisted of polar SiO2 regions and nonpolar regions of self-assembled monolayers of octadecyltrichlorosilane (OTS). The NWs showed selective adsorption on the polar SiO2 regions, avoiding assembly on the nonpolar OTS regions. Utilizing these assembled Ni-Si NWs, we demonstrate a sensor for the detection of chlorine gas. The utilization of Ni-Si NWs resulted in a much larger sensor response of approximately 23% to 5 ppm of chlorine gas compared to bare Ni NWs, due to the increased surface-to-volume ratio of the Ni-Si shell/core structure. We expect that our sensor will be utilized in the future for the real-time detection of halogen gases including chlorine with high sensitivity and fast response.

Internal and external atomic steps in graphite exhibit dramatically different physical and chemical properties.

We report on the physical and chemical properties of atomic steps on the surface of highly oriented pyrolytic graphite (HOPG) investigated using atomic force microscopy. Two types of step edges are identified: internal (formed during crystal growth) and external (formed by mechanical cleavage of bulk HOPG). The external steps exhibit higher friction than the internal steps due to the broken bonds of the exposed edge C atoms, while carbon atoms in the internal steps are not exposed. The reactivity of the atomic steps is manifested in a variety of ways, including the preferential attachment of Pt nanoparticles deposited on HOPG when using atomic layer deposition and KOH clusters formed during drop casting from aqueous solutions. These phenomena imply that only external atomic steps can be used for selective electrodeposition for nanoscale electronic devices.

One-step hydrothermal synthesis of graphene decorated V2O5 nanobelts for enhanced electrochemical energy storage.

Graphene-decorated V2O5 nanobelts (GVNBs) were synthesized via a low-temperature hydrothermal method in a single step. V2O5 nanobelts (VNBs) were formed in the presence of graphene oxide, a mild oxidant, which also enhanced the conductivity of GVNBs. From the electron energy loss spectroscopy analysis, the reduced graphene oxide (rGO) are inserted into the layered crystal structure of V2O5 nanobelts, which further confirmed the enhanced conductivity of the nanobelts. The electrochemical energy-storage capacity of GVNBs was investigated for supercapacitor applications. The specific capacitance of GVNBs was evaluated using cyclic voltammetry (CV) and charge/discharge (CD) studies. The GVNBs having V2O5-rich composite, namely, V3G1 (VO/GO = 3:1), showed superior specific capacitance in comparison to the other composites (V1G1 and V1G3) and the pure materials. Moreover, the V3G1 composite showed excellent cyclic stability and the capacitance retention of about 82% was observed even after 5000 cycles.

Selective metal deposition at graphene line defects by atomic layer deposition.

One-dimensional defects in graphene have a strong influence on its physical properties, such as electrical charge transport and mechanical strength. With enhanced chemical reactivity, such defects may also allow us to selectively functionalize the material and systematically tune the properties of graphene. Here we demonstrate the selective deposition of metal at chemical vapour deposited graphene's line defects, notably grain boundaries, by atomic layer deposition. Atomic layer deposition allows us to deposit Pt predominantly on graphene's grain boundaries, folds and cracks due to the enhanced chemical reactivity of these line defects, which is directly confirmed by transmission electron microscopy imaging. The selective functionalization of graphene defect sites, together with the nanowire morphology of deposited Pt, yields a superior platform for sensing applications. Using Pt-graphene hybrid structures, we demonstrate high-performance hydrogen gas sensors at room temperature and show its advantages over other evaporative Pt deposition methods, in which Pt decorates the graphene surface non-selectively.