Number Of Atomic Layer Deposition Cycles Research Articles

Fine regulation of Cu-ZnO interfaces for enhanced CO2 hydrogenation to methanol by atomic layer depositing thin ZnO films on copper phyllosilicates

Regulation of abundant Cu-ZnO interfaces in Cu/ZnO catalysts is critical to the thermal hydrogenation of CO2 to methanol. Herein, Cu-ZnO interfaces were precisely regulated by depositing thin ZnO films on copper phyllosilicates (CuSiO3) through atomic layer deposition (ALD) to prepare Cu/ZnO/SiO2 composite catalysts (denoted as xZnO/CuSiO3, x is the number of ALD cycles) for CO2 hydrogenation to methanol. Interestingly, 5ZnO/CuSiO3 exhibited much higher methanol selectivity of 68.1 % and methanol space-time yield (STYMeOH) of 0.39 gMeOH h−1gcat−1 toward CO2 hydrogenation at 275 ℃ and 3 MPa, as compared to the pristine CuSiO3 (38.1 % and 0.24 gMeOH h−1gcat−1), suggesting the significant role of Cu-ZnO interfaces. Compared to ZnO/CuSiO3(IM) prepared by the conventional impregnation method, 5ZnO/CuSiO3 possessed much higher CO2 conversion (13.8 % vs. 10.1 %) and methanol selectivity (68.1 % vs. 56.2 %). Furthermore, the catalytic activities of the prepared Cu/ZnO catalysts can be effectively regulated by changing the thickness of ZnO-ALD films, in which 5ZnO/CuSiO3 showed the best catalytic activity. Various characterization methods were applied to demonstrate that ALD-ZnO was evenly laid flat on the surface of CuSiO3 to construct abundant Cu-ZnO interfaces during the H2 reduction treatment, which facilitated the dissociated activation of CO2 and formation of CH3O* reaction intermediate and simultaneously inhibited the generation of CO byproduct. In addition, the density functional theory (DFT) calculations revealed the stronger interaction between Cu and ZnO over 5ZnO/CuSiO3, which implied more Cu-ZnO interfaces were generated for methanol production. Accordingly, this study verifies the significance of Cu-ZnO interfaces for CO2 hydrogenation to methanol and provides a facile method to regulate Cu-ZnO interfaces by depositing ALD-ZnO films on the copper phyllosilicate precursor.

The Impact of ALD Precursor Choice on Nucleation and Growth of Dielectrics on 2D Materials

Recently, atomically thin two-dimensional (2D) transition metal dichalcogenides (TMDs) have received significant attention due to their unique optical and electrical properties, lending themselves to exciting applications such as microelectronics, sensing, catalysis, photonics, and more. The properties of TMDs can be acutely impacted by their environment due to their atomic thinness. For instance, in a TMD-based transistor with a high-k dielectric surrounding the TMD semiconductor, the dielectric could dope the channel via charge transfer; it can improve charge carrier mobility by screening the impact of charged impurities on scattering; or it can worsen charge carrier mobility by introducing defect states or interfacial roughness. As such, the quality and nature of the dielectric is critical, and ultimately those properties are determined by the means of dielectric deposition. Atomic layer deposition (ALD) is a common thin film deposition technique used for depositing high-k dielectrics for transistor devices. ALD relies on sequential self-limiting reactions between a precursor or co-reactant and a surface in order to deposit a material in a layer-by-layer manner with a high degree of control over thickness, composition, and uniformity. However, the ideal basal planes of 2D materials possess no dangling bonds or reactive functional groups, making their surfaces largely inert to ALD chemistry. Hence, when conventional ALD is performed on TMDs, nucleation and growth proceeds only at defect sites, grain boundaries, and the more reactive edge sites. This sparse nucleation leads to poor quality films of low density, high surface roughness, and pinholes.In this work, we employ physisorption-assisted ALD processes and study the nucleation and quality of the deposited dielectrics. We deposit AlOx on atomically thin monolayer MoS2 (itself on SiO2/Si) using a series of ALD precursors in order to investigate the impact of the ALD precursor on nucleation. Using scanning electron microscopy (SEM), we study film nucleation and continuity as a function of ALD precursor, cycle number, and temperature. After optimizing each process for each precursor in terms of temperature and purge time for maximized nucleation, we fabricate transistor devices in which the deposited AlOx serves as a seed layer for high-k HfO2 deposition to create the gate stack. Au contacts and a Pd top gate were used to complete the devices. Using x-ray photoelectron spectroscopy (XPS) and electrical testing, we investigate the character of the dielectric/MoS2 interface. We observe that the precursor used in the ALD process can lead to a wide range of coverages, with more conventional precursors resulting in sparse coverage, and novel precursors introduced in this study leading to nearly full coverage after just 3 nm of AlOx is deposited. We hypothesize that the improved coverage for the novel precursor is the result of enhanced interactions between the precursor and the 2D material due to its particular chemical structure. The reduced nucleation delay leads to a denser, smoother film with fewer defects at the 2D/3D material interface. The devices fabricated using the novel precursor and improved dielectric show excellent performance such as good on/off ratios (106), small device-to-device variation (ΔV T < 1 V), and low effective oxide thickness (~1 nm). This work provides useful insights into how ALD precursors could be designed to improve the quality of dielectrics on 2D materials, potentially improving the viability of 2D materials for wide ranging applications.

A mechanistic approach to determine the relationship between film structure, electronic properties, and photocatalytic activity of ALD ZnO thin films on glass gibers

Atomic layer deposition (ALD), a high-conformality thin-film deposition technique, offers the opportunity to immobilize photocatalytic materials on high surface area substrates. Textile substrates are inexpensive, easily accessible materials with a fibrous nature, making them high surface area scaffolds for photocatalytic applications. This study applied ZnO thin-film coatings to fabric structures with different numbers of ALD cycles. The effect of coating thickness on the surface and electronic properties of the films and their photocatalytic properties were investigated. SEM, XRD, PL, and UV–Vis were used to examine the surface morphology, crystal structure, defects, and optical properties of the ZnO thin films. As the film thickness increased, the crystal sizes and the number of defects in the structure increased. Contact angle and Hall Effect measurements revealed that these structural defects are present on the surface of the films. Optimum wettability, mobility, and photocatalytic efficiency values were observed in the 15-nm coated samples, resulting in the highest photocatalytic activity and a turning point.

Atomic layer deposited TiO2 nanofilm on titanium implant for reduced the release of particles.

Objective: Titanium implants are widely used in surgeries for their biocompatibility and mechanical properties. However, excessive titanium particle release can cause implant failure. This study explores Atomic Layer Deposition (ALD) to coat commercially pure titanium (Cp-Ti) with TiO2, aiming to improve its frictional and corrosion resistance while reducing particle release. By comparing TiO2 films with varying ALD cycle numbers, we assess surface properties, particle release, friction, and corrosion performance, providing insights into mitigating particle release from implants. Methods: Cp-Ti surfaces were prepared and coated with TiO2 films of 100, 300, and 500 ALD cycles. Surface characterization involved SEM, EDX, and XRD. Friction was tested using SEM, nanoindentation, and ICP-MS. Corrosion resistance was evaluated through immersion tests and electrochemical analysis. Cytotoxicity was assessed using BMSCs. Results: Surface characterization revealed smoother surfaces with increased ALD cycles, confirming successful TiO2 deposition. Friction testing showed reduced friction coefficients with higher ALD cycles, supported by nanoindentation results. Corrosion resistance improved with increasing ALD cycles, as evidenced by electrochemical tests and reduced titanium release. Cytotoxicity studies showed no significant cytotoxic effects. Conclusion: ALD-coated TiO2 films significantly enhance frictional and corrosion resistance of titanium implants while reducing particle release. The study underscores the importance of ALD cycle numbers in optimizing film performance, offering insights for designing implants with improved properties.

Microwave absorbing performance of reduced graphene oxide @ alumina fabricated by atomic layer deposition method

In this work, a series of alumina coating reduced graphene oxide (RGO@Al2O3) composites with core-shell structure was synthesized by the atomic layer deposition (ALD) method. The alumina (Al2O3) thickness of the RGO@Al2O3 could be controlled by changing the number of ALD cycles. The microstructure, high-temperature resistance, and microwave absorbing properties of the composites were investigated in detail. The composite could provide excellent high-temperature resistance and microwave absorbing properties. The composite started decomposition at 620 °C. The maximum reflection loss value of the composite obtained by applying 200 Al2O3 deposition cycles is −14.2 dB at 15.7 GHz, and its effective absorption bandwidth reaches 5.0 GHz (13.0–18.0 GHz). The results show that the RGO@Al2O3 composite has the potential application in high-temperature microwave absorbing fields, due to excellent high-temperature resistance, reflection loss, and effective absorption bandwidth.

Scalable Large-Area 2D-MoS2/Silicon-Nanowire Heterostructures for Enhancing Energy Storage Applications.

Two-dimensional (2D) transition-metal dichalcogenides have shown great potential for energy storage applications owing to their interlayer spacing, large surface area-to-volume ratio, superior electrical properties, and chemical compatibility. Further, increasing the surface area of such materials can lead to enhanced electrical, chemical, and optical response for energy storage and generation applications. Vertical silicon nanowires (SiNWs), also known as black-Si, are an ideal substrate for 2D material growth to produce high surface-area heterostructures, owing to their ultrahigh aspect ratio. Achieving this using an industrially scalable method paves the way for next-generation energy storage devices, enabling them to enter commercialization. This work demonstrates large surface area, commercially scalable, hybrid MoS2/SiNW heterostructures, as confirmed by Raman spectroscopy, with high tunability of the MoS2 layers down to the monolayer scale and conformal MoS2 growth, parallel to the silicon nanowires, as verified by transmission electron microscopy (TEM). This has been achieved using a two-step atomic layer deposition (ALD) process, allowing MoS2 to be grown directly onto the silicon nanowires without any damage to the substrate. The ALD cycle number accurately defines the layer number from monolayer to bulk. Introducing an ALD alumina (Al2O3) interface at the MoS2/SiNW boundary results in enhanced MoS2 quality and uniformity, demonstrated by an order of magnitude reduction in the B/A exciton photoluminescence (PL) intensity ratio to 0.3 and a reduction of the corresponding layer number. This high-quality layered growth on alumina can be utilized in applications such as for interfacial layers in high-capacity batteries or for photocathodes for water splitting. The alumina-free 100 ALD cycle heterostructures demonstrated no diminishing quality effects, lending themselves well to applications that require direct electrical contact with silicon and benefit from more layers, such as electrodes for high-capacity ion batteries.

Low‐Temperature Atomic Layer Deposition Synthesis of Vanadium Sulfide (Ultra)Thin Films for Nanotubular Supercapacitors

Herein, the synthesis of vanadium sulfide (VxSy) by atomic layer deposition (ALD) based on the use of tetrakis(dimethylamino) vanadium (IV) and hydrogen sulfide is presented for the first time. The (ultra)thin films VxSy are synthesized in a wide range of temperatures (100–225 °C) and extensively characterized by different methods. The chemical composition of the VxSy (ultra)thin films reveals different vanadium oxidation states and sulfur‐based species. Extensive X‐ray photoelectron spectroscopy analysis studies the effect of different ALD parameters on the VxSy chemical composition. Encouraged by the rich chemistry properties of vanadium‐based compounds and based on the variable valences of vanadium, the electrochemical properties of ALD VxSy (ultra)thin films as electrode material for supercapacitors are further explored. Thereby, nanotubular composites are fabricated by coating TiO2 nanotube layers (TNTs) with different numbers of VxSy ALD cycles at low temperature (100 °C). Long‐term cycling tests reveal a gradual decline of electrochemical performance due to the progressive VxSy thin films dissolution under the experimental conditions. Nevertheless, VxSy‐coated TNTs exhibit significantly superior capacitance properties as compared to the blank counterparts. The enhanced capacitance properties exhibited are derived from the presence of chemically stable and electrochemically active S‐based species on the TNTs surface.

Toward an Insulator-to-Metal Transition (IMT) in VOx Deposited by ALD: Huge Effect on Large IR Transmission Range

Vanadium dioxide (VO2) exhibits an insulating-to-metallic transition (IMT) from an insulating monoclinic to a metallic rutile phase at a IMT temperature (TIMT) of about 68 °C. This transition is accompanied by a decrease in electrical resistivity of 5 orders of magnitude and a drastic change in optical properties. Until recently, several works described the fundamental nature of the phase transition in a contradictory way, attributing it either to a structure-induced electron-phonon interaction: the Peierls transition [1], or to a strong electron-electron correlation: the Mott transition [2]. Nowadays, theoretical and experimental results [3-6] tend to show that the phase transition is affected by the crystal and electronic structures according to a mechanism combining the two opposed mechanisms and thus called collaborative Mott-Peierls transition.In order to achieve the growth of high-quality and conformal VO2 thin films and with a low thermal budget, Atomic Layer Deposition (ALD) is one of the most suitable ones, among physical and chemical vapor deposition techniques [7]. In this aim, vanadium oxide (VOx) films were deposited on both silicon (100) and glass substrates (figure with and without VOx) at 240°C using vanadium tri-isopropoxide (VTIP) asV-precursor and water as oxydant reagent. Deposited films, with thicknesses ranging from 30 nm to 120 nm depending on the number of ALD cycles, were annealed during one hour under a reducing atmosphere (forming gas) at four temperatures ranging from 400°C to 550°C with 50°C steps. Thanks to X-ray diffraction (XRD), and transmission electron microscopy (TEM), unannealed films were found amorphous independently of the substrate. Annealed films were found polycrystalline with a mixture of both VO2 and V2O5 (or V6O13) phases with crystallite lateral size up to 300 nm. RBS analysis showed how the chemical stoichiometry evolves with annealing temperature. The V content remains constant with annealing temperature while the O content and the film density were both decreasing under reducing conditions. By means of XPS measurements, at a temperature below TIMT, different valence states of V element were identified with a majority of V4+ ions and a minority of V3+ and V5+ ions. At a temperature above TIMT, a valence state modification occurs with a reduction of the V4+ ion concentration in favor of the V3+ and V5+ones. Cooling back under TIMT led almost to the same valence states initial reorganization with a majority of V4+.The variation of electrical and optical properties of VOx films occurring during IMT was also investigated. It was found that the resistivity r decreased down to 10-1 Ω.cm with a rising temperature above TIMT, and the r rose again with decreasing temperature with a hysteresis by contrast to the first drop. Dramatically, the optical transmittances of VOx films on Si wafer, measured with FTIR, displayed an important reduction during IMT of almost 70% in a broad spectral range from 2 to 20 µm wavelength. The optical properties of VOx on a glass substrate in UV-visible spectral range at IMT evidenced a modification of dielectric constant at IMT. Raman spectroscopy of VOx films around IMT showed the disappearance of low-temperature VO2 peaks, characteristic for this transition.In conclusion, crystalline VOx films were successfully produced by an ALD process and subsequent annealing at 500°C leading to films with reversible and reproducible IMT occurring at ~70°C. The important variation of some electrical or optical properties in infrared range paves the way for the light and heat monitoring in many applications including thermal stealth, heat management, tunable thermochromic or electrochromic windows.[1] Goodenough, J. B. The two components of the crystallographic transition in VO2.[2] Zylbersztejn, A. & Mott, N. F. Metal–insulator transition in vanadium dioxide. Phys. Rev. B 11, 4383–4395 (1975).[3] Cocker, T. L.; Titova, L. V.; Fourmaux, S.; Holloway, G.; Bandulet, H.-C.; Brassard, D.; Kieffer, J.-C.; El Khakani, M. A.; Hegmann, F. A. Phase Diagram of the Ultrafast Photoinduced, Insulator-Metal Transition in Vanadium Dioxide. Phys. Rev. B 2012,85, No. 155120.[4] Yao, T. et al. Understanding the Nature of the Kinetic Process in a VO2 Metal-Insulator Transition. Phys. Rev. Lett. 2010, 105, No. 226405.[5] Weber, C. et al. Vanadium dioxide: A Peierls–Mott insulator stable against disorder. Phys. Rev. Lett. 108, 256402 (2012).[6] Koethe, T. et al. Transfer of spectral weight and symmetry across the metal–insulator transition in VO2. Phys. Rev. Lett. 97, 116402(2006).[7] Prasadam, V. P. et al. Atomic layer deposition of vanadium oxides: process and application review. Mater. Today Chem. 12, 396–423 (2019). Figure 1

Activity and Durability of ALD-ZrO2 Coated IrO2 Film in Sulfuric Acid

The technology of power-to-gas (P2G) is drawing attention in and outside Japan for its ability to store renewable energy as hydrogen [1]. For the aspect of P2G, the water electrolyzer plays important role to produce “Green Hydrogen” [2]. On Sep. 26, 2022, Hydrogen energy ministerial meeting was held as online special event. In the open session, the water electrolysis is one of the main topics of the session, and due to the demand for “Green Hydrogen”, installed capacity of water electrolyzer has been required for the huge size of its module [3].In Japan, proton exchange membrane water electrolysis (PEMWE) with small size produced by Kobelco Eco-Solutions Corp have released already installed over 200 units for 25 years. Recently, the PEMWE with MW-class as installed in Yamanashi Hydrogen Company has also applied for the demonstration project [3]. However, the conventional electrocatalysts for PEMWE uses precious metal materials, and especially, the iridium oxide (IrO2) is used as an anode. As the iridium is by-product of platinum, its resources is very poor. Moreover, it is reported that the low loading of IrO₂ easily causes the degradation under dynamic operation condition simulated variable renewable energies (VRE) [4]. From this point of view, the durability of anode against VRE should be required for “Green Hydrogen” production. We focused on ZrO2 which has high stability in acidic solution [5]. Moreover, we found that an oxide-based film which is formed by Atomic Layer Deposition (ALD) showed bi-functional effects on the electrocatalyst for the oxygen reduction reaction; it can reflect the electrochemical properties of the substrate and it can also protect the consumption of the substrate by potential scan. In order to apply for PEMWE, we have investigated the catalytic activity of IrO2 electrodes deposited with ZrO2 using ALD for the oxygen evolution reaction (OER).IrO2 film on Ti rod as substrate was fabricated by thermal decomposition under air atmosphere at 400°C for 10 min. The loading amount of IrO2 was 2.35 mg cm-2 at constant. ZrO2 was deposited on IrO2 film by using ALD at 225°C, the film thickness of ZrO2 was varied in the range of 2 to 10 nm that calculated from the number of ALD cycles. After coating, the heat treatment was performed under air atmosphere at 400oC for 10 min. We used conventional three electrode cell with each sample as working electrode while the reversible hydrogen electrode (RHE) and carbon plate were used as reference and counter electrode to demonstrate the electrochemical measurement in 1 M H2SO4 at 303 K. After the pretreatment, the cyclic voltammetry was demonstrated in the range of 0.05 to 1.2 V. In order to evaluate the OER activity of samples, the slow scan voltammetry (SSV) was performed from 1.2 to 2.0 V vs. RHE.Figure 1 shows the polarization curves of OER on the ALD-ZrO2 of 5 nm coated on IrO2 with and without heat treatment (5nm, 5nm(HT)). The result of IrO2 with and without heat treatment (0nm, 0nm(HT)) are also shown in the Fig. 1. These results are IR-free data. The vertical axis is based on geometric current density (i geo). In the case of IrO2, the i geo of 0nm was larger than 0nm(HT). On the other hand, the i geo of 5nm(HT) was obviously larger than that 5nm in the case of ALD-ZrO2 of 5 nm coated on IrO2, and the i geo of 5nm(HT) at 1.55 V was almost same as that of 0nm(HT). The redox peak of Ir(IV)/Ir(V) or Ir(IV)/Ir(VI) was observed in the cyclic voltammogram (CV) of 5nm(HT) around 1.2 V. This peak also obtained in the CVs of both 0nm and 0nm(HT). However, it is not clearly shown in the CV of 5nm. From the results of SEM-EDX, the coating of ZrO2 of 5nm(HT) was remained after electrochemical measurement while the that of ZrO2 of 5nm was removed after electrochemical measurement. Therefore, the heat treatment after ALD coating was effective for enhancing OER activity.Acknowledgement: This work is partially supported by the Suzuki Foundation and JFE 21st Century Foundation.Reference Fuel Cell RD & D in Japan 2022, Fuel Cell Development Information Center (FCDIC), pp.8. Fuel Cell Development Information Center (FCDIC), Tolyo (2023).K. Ota, A. Ishihara, K. Matsuzawa, and S. Mitsushima, Electrochemistry, 78, 970 (2010).https://www.meti.go.jp/english/press/2020/1015_001.html M. Alia, and G. C. Anderson, J. Electrochem. Soc., 166, F282 (2019).A. Ishihara, Y. Ohgi, K. Matsuzawa, S. Mitsushima, and K. Ota, Electrochim. Acta, 55, 8005 (2010). Figure 1

Stepwise Growth of Crystalline MoS2 in Atomic Layer Deposition

Transition metal dichalcogenides (TMDCs) are layered materials in which each layer is weakly bound by van der Waals forces. TMDCs have interesting intrinsic properties, including high mobility and excellent electrostatic controllability, even at monolayer thickness. Hence, they have emerged as promising materials for widespread applications in nanoelectronics, optoelectronics, gas sensors, etc. The aforementioned properties of TMDCs are significantly affected by the structuralquality and crystallinity. Accordingly, scalable techniques have been sought for synthesizing well-crystallized TMDCs.Atomic layer deposition (ALD) is considered a promising growth technique for transition metal dichalcogenides (TMDCs) because it ensures uniformity and homogeneity of the TMDC grains. However, the poor crystallinity of ALD-grown TMDCs remains a critical challenge. Although crystallinity depends on the growth mechanism, the growth behavior of crystalline TMDCs in ALD is unclear. We investigated the growth behavior of highly crystallized molybdenum disulfide (MoS2) by ALD at 650 oC with an extra pulse of remote H2 plasma. Growth at high temperatures using the activated species aided surface diffusion of the adsorbates. The ALD process facilitates repeated growth and saturation of MoS2, unlike the normal ALD of 3D bulk materials, where the film thickness monotonically increases with the number of ALD cycles. This unique behavior resulted from the evolution of the basal plane without dangling bonds. On the basal plane, MoS2 lateral growth dominates vertical growth, and prolonged incubation is required for nucleation on the basal plane. The grain size is small (up to two monolayers) because of the limited mobility on SiO2, and the grains of the third layer grow to a few hundred nanometers. These findings provide insights into the development of ALD technology for application to high-quality TMDCs.

Atomic Layer Deposition of HfAlOx for High-k Gate Dielectrics

Nowadays, the downscaling of CMOS devices requires continued effort to propose high performance components with extremely compact size. Surely, this trend is not achievable without extremely enhanced High-k gate stack materials, inter alia. For years, HfO2-based dielectrics deposited using ALD (Atomic Layer Deposition) technique are perfect dielectrics of choice for various devices and applications (Memristor, resistive random access memory, ferroelectric random access memory, antiferrolectric capacitances, ferroelectric FET...).As such, HfAlOx films present a good compromise between HfO2 and Al2O3 in term of coupling properties and insulating capabilities in comparison with both single HfO2 and Al2O3 films. The purpose of this work is to evaluate binary high-k HfAlOx dielectrics deposited by ALD technique. ALD is well suited for deposition of ultrathin films with exceptional capabilities enabling precise thickness, stoichiometry control and conformal growth at atomic scale. In this work, we focused on Al2O3/HfO2 films fabricated using two approaches: (i) repeatedly alternating the deposition of two different and separate extremely thin oxides (Al2O3 and HfO2; particular focus on HfO2/Al2O3/HfO2/Al2O3/HfO2 multilayer stack with equivalent Al fraction around 30%); (ii) combination of ALD super cycles allowing the formation HfAlOx layers. We analyze the general performance and the behavior of the binary high-k HfAlOx dielectrics (10 nm thin layers deposited at 300°C using TiCl4-TMA-H2O precursors) using physico-chemical (X-ray photoelectron spectroscopy XPS, X-ray reflectometry XRR, wavelength dispersive X-ray fluorescence WDXRF) and electrical measurements (Hg probe measurements, MIM capacitance).The incorporation of Al2O3 in the composition of the HfO2 gate dielectrics allows a perfect monitoring of physico-chemical properties varying from HfO2 layers to Al2O3 layers by controlling the number of Al2O3 and HfO2 ALD cycles. In this respect, we were able to monitor the Al fraction in the range of 5% to ~86% in the mixed binary dielectrics (Figure 1: XRR density of mixed binary layers vs Al/[Al+Hf] ratio, Figure 2: Al and Hf fractions in the mixed layer determined by WDXRF and XPS analysis).The electrical characteristics of the HfAlOx dielectrics confirm the influence of the Al fraction in the HfO2 layer. The leakage currents of the mixed layers decreases with increasing the Al fraction (Figure 3: J/E characteristics of mixed and stacked HfAlOx layers). The breakdown voltages for all mixed HfAlOx layers are greater than that of reference HfO2 layer. On the other hand, the shown multilayer presents an intermediate leakage currents profiles between the two mixed HfAlOx (25%Al and 40%Al). Thus, the incorporation of Al in the construction of HfAlOx system is likely to decrease the number of defects. Furthermore, the fully integrated MIM structures exhibit areal capacitance in the range 10-15 nF/mm2 of ALD-based high-k HfAlOx (10 to 12 nm) depending on the Al fraction. Thus, ALD-HfAlOx with various composition highlight the potential tremendous for high-κ capacitances stack for CMOS semiconductor devices. Figure 1

ALD-Based IrOx/Ir Supported Electrocatalysts for Water Electrolysis Technology

Hydrogen (H2) is an alternative energy vector to replace fossil fuels, with potential applications like hydrogen fuel cell-powered vehicles and in the chemical industry. H2 production through polymer electrolyte membrane (PEM) water electrolysis (WE) appears to be a highly promising technology. While iridium oxide is the most commonly used anode oxygen evolution reaction (OER) catalyst for PEMWE, its scarcity makes it an extremely critical raw material. In order to obtain active and stable anodes with an ultra-low iridium loading, we are developing a strategy based on doped metal oxides as conductive supports, on which iridium-based thin films and/or nanostructures are deposited using atomic layer deposition (ALD). ALD can indeed allow the control of the amount of deposited species at sub-nanometric scale by changing the number of ALD cycles, thus ensuring a minimal iridium loading for efficient OER catalysis. In this study, the influence of the temperature of deposition was investigated to obtain either IrOx ultrathin films or Ir nanoparticles. The morphology and composition of these deposits were characterized by scanning and transmission electron microscopy, X-ray photoelectron spectroscopy and X-ray diffraction. The nature and crystallinity of these electrocatalysts will indeed have a huge impact on their catalytic activity and the subsequent electrode’s efficiency as well as in their long-term durability. In brief, we will present the production of nano-structured OER electrocatalysts, in which the bulk consists of a sufficiently conductive metal oxide support with the surface uniformly coated with an ultra-low loading of iridium deposited via conformal ALD.

Scaling a Gas Phase Residual Lithium Conversion Process on Ni-Rich NMC Cathode Materials in Commercial Fluidized Bed Reactors

‘Residual lithium’, the LiOH and Li2CO3 surface contamination that is ubiquitous to Ni-rich NMC manufacturing, is a significant obstacle in the large-scale production and handling of high-nickel layered oxides. These hydroxide and carbonate surface phases influence reproducibility and shelf stability of the NMC powder and cause gelation and particle aggregation during electrode casting. There is ample evidence in the literature that atomic layer deposition (ALD) possesses a two-fold solution to this problem.1-3 First, reactive organometallic species such as trimethylaluminum (TMA) can convert insulating residual lithium to a Li-rich LixAlyO conducting layer. Customizable ALD layers can then be added to inhibit the re-formation of the carbonate layer and to deter negative side reactions of the CAM surface with the liquid electrolyte. While highly impactful, these studies have mostly been relegated to small, lab-scale demonstrations of <50 g. As such, there remains a need to enable this ALD-assisted-technology for high-throughput commercial applications.In this talk, we will explore the progression of a residual lithium conversion process from lab (10 – 1000 mL) to industrial-scale (10 L – 100 L) fluidized bed equipment and how scale and material-dependent parameters can impact performance. Using a commercial NMC 811 cathode as a case study, we first applied aluminum phosphate ALD coatings on a lab-scale fluidized bed reactor to examine the interfacial and electrochemical changes of the CAM material under various process conditions. ICP-OES measurements confirmed linear and reproducible deposition versus ALD cycle number between 200- 300°C. XPS analysis showed the ALD coated NMC 811 powder had an 80% reduction in Li2CO3 versus the pristine material and that a reduction persisted even after 10 days of storage in atmospheric conditions. At standard (0.5C/1C) cycling to 4.4V, AlPO4 coatings increased cycle life by 44% versus the uncoated powder. Under optimized conditions, the process was scaled first to 1 kg and finally to 10 kg in a pilot-scale reactor. In-situ mass spectrometry indicated that residual lithium conversion byproducts such as CO2 could be used to monitor reaction progress and optimize chemical usage efficiency. Fluidization aids including vibration and mechanical stirring were used to inhibit and break up powder agglomerates. ICP-OES and electrochemical cycling data confirmed reproducible deposition and cycle life benefits versus the small scale runs and pristine materials, demonstrating a pathway for these ALD-enhanced materials to transition from lab-scale demonstration to viable product. We will discuss strategies for continuing the scaling process to 100 kg batches for commercial applications.[1] M. Young et al., The Journal of Physical Chemistry C 2019 123 (39), 23783-23790[2] P. Darapaneni et al., ACS Applied Energy Materials 2022, 5, 8, 9870–9876[3] J. Li et al., Coatings 2022, 12(1), 84

Determination of film thicknesses of metal oxides prepared by atomic layer deposition on SBA-15

ZrO2 and CeO2 films were grown in SBA-15 by Atomic Layer Deposition (ALD) to loadings of 0.92 g oxide/g SBA-15. Scanning Transmission Electron Microscopy (STEM) with Energy Dispersive Spectra (EDS) showed that the oxides grew uniformly inside the mesopores. Film thicknesses were then analyzed as a function of the number of ALD cycles using three methods: 1) mass changes assuming bulk densities for the films; 2) changes in pore size from Barret-Joyner-Halenda (BJH) analysis with N2 adsorption isotherms; and 3) small-angle X-ray scattering (SAXS). Film thicknesses assuming bulk densities were between 6 and 8 times smaller than those obtained from BJH analysis. SAXS analysis gave film thicknesses that were approximately twice that obtained from bulk densities. Possible explanations of the discrepancies between these methods are discussed.

Multicolored microwave absorbers with dynamic frequency modulation

Microwave-absorbing materials are extensively used in intelligent electronic devices and stealth technologies where the ability to dynamically adjust microwave-absorbing capacity in response to specific requirements is vitally important. Herein, we report a new approach for constructing dynamically tunable microwave absorbers with ultrawide tunable frequency ranges that are simultaneously endowed with vibrant structural colors. The methodology produces structural colors and adjusts absorption properties by constructing ZnO coatings with precisely adjustable thicknesses on a polypyrrole/melamine foam (PPy/MF) surface by atomic layer deposition (ALD) in conjunction with a pressure-driven strategy that regulates the compression ratio. The electrical conductivity, electromagnetic parameters, thickness, and pore size of the ZnO-coated PPy/MF (ZnO/PPy/MF) are effectively adjusted, and simply applying external pressure widens the tunable frequency range and the effective absorption bandwidth. As a result, the effective absorption frequency of ZnO/PPy/MF is dynamically adjustable from the S band to the Ku band, thereby covering 94.3% of the entire microwave spectrum. Moreover, the brilliant and uniform structural colors of ZnO/PPy/MF, which span various color categories, are precisely regulated by tuning the thickness of the ZnO coating by adjusting the number of ALD cycles. ZnO/PPy/MF is strongly hydrophobic, which endows it with remarkable self-cleaning properties. Therefore, ZnO/PPy/MF provides a conceptually novel platform for the development of next-generation smart microwave-absorbing materials due to its integrated dynamic frequency-regulating ability, brilliant structural coloration, and self-cleaning features.

Atomic layer deposition of calcium fluoride for barrier coating applications

We report on the development of an atomic layer deposition (ALD) process for calcium fluoride thin films using bis(N,N-di-i-propylformamidinato)calcium(II) and anhydrous HF as reactants. Deposition rates were observed to be linear versus the number of ALD cycles performed, varying between 0.4 and 0.3 Å/cycle at substrate temperatures ranging from 175 to 250 °C, respectively. The optical properties of the resulting nanocrystalline CaF2 films were characterized by spectroscopic ellipsometry and show good transparency down to a UV wavelength of 193 nm, and good agreement with reference refractive index parameters. One motivation for the development of this ALD process is for chemical barrier applications in fluorine-containing chemistries. The robustness of the coating was tested by reactive ion etching of CaF2 films deposited on silicon in an SF6 plasma, yielding an Si:CaF2 etch ratio of greater than 2000:1 at a plasma power of 300 W.

Direct atomic layer deposition of ultra-thin Al2O3 and HfO2 films on gold-supported monolayer MoS2

In this paper, the atomic layer deposition (ALD) of ultra-thin films (<4 nm) of Al2O3 and HfO2 on gold-supported monolayer (1L) MoS2 is investigated, providing an insight on the mechanisms ruling the nucleation in the early stages of the ALD process. A preliminary multiscale characterization of large area 1L-MoS2 exfoliated on sputter-grown Au/Ni films demonstrated: (i) a tensile strain (from 0.1 to 0.3%) and p-type doping (from 1 × 1012 to 4 × 1012 cm−2) distribution at micro-scale; (ii) an almost conformal MoS2 membrane to the Au grains topography, with some locally detached regions, indicating the occurrence of strain variations at the nanoscale; (iii) atomic scale variability (from ∼ 4.0 to ∼ 4.5 Å) in the Mo-Au atomic distances was detected, depending on the local configuration of Au nanograins. Ab initio DFT calculations of a free-standing MoS2 layer and a simplified MoS2/Au(111) interface model showed a significant influence of the Au substrate on the MoS2 energy band structure, whereas small differences were accounted for the adsorption of H2O, TMA (co-reactant, and Al-precursor, respectively) molecules, and a slight improved adsorption was predicted for TDMAHf (Hf-precursor). This suggests a crucial role of nanoscale morphological effects, such as the experimentally observed local curvature and strain of the MoS2 membrane, in the enhanced physisorption of the precursors. Afterwards the nucleation and growth of Al2O3 an HfO2 films onto 1L-MoS2/Au was investigated in detail, by monitoring the surface coverage as a function of the number (N) of ALD cycles, with N from 10 to 120. At low N values, a slower growth rate of the initially formed nuclei was observed for HfO2, probably due to the bulky nature of the TDMAHf precursor as compared to TMA. On the other hand, the formation of continuous films was obtained in both cases for N > 80 ALD cycles, corresponding to ∼ 3.6 nm Al2O3 and ∼ 3.1 nm HfO2. Current mapping on these ultra-thin films by conductive-AFM showed, for the same applied bias, a uniform insulating behavior of Al2O3 and the occurrence of few localized breakdown spots in the case of HfO2, associated to a less compact films regions. Finally, an increase of the 1L-MoS2 tensile strain was observed by Raman mapping after encapsulation with both high-κ films, accompanied by a reduction in the PL intensity, explained by the effects of strain and the higher effective dielectric constant of the surrounding environment.

Enhanced Energy Transfer between Nitrogen‐Vacancy Centers and 2D MoS2 Films Accurately Fabricated by Atomic Layer Deposition

AbstractEnergy transfer between 2D MoS2 films and fluorescent emitters is widely used in biological detection and imaging. In this paper, by regulating the thickness of the MoS2 film on the diamond surface through the number of atomic layer deposition (ALD) cycles, the energy transfer efficiency between the nitrogen vacancy (NV) center and the MoS2 film is improved and precisely controlled. When the number of ALD cycles is 8, the energy transfer efficiency between the 2D MoS2 film and the NV center is 86.35%. Furthermore, when the number of ALD cycles is more significant than 140, compared with 2D and 3D graphene structures, the energy transfer efficiency of the NV center is increased by 126.55% and 24.60%, respectively. Meantime, the fluorescence lifetime of the NV center is reduced in the presence of the MoS2 film, indicating that the MoS2 film provides a new, additional fluorescence decay channel for the NV center in the MoS2 film and the NV center system. Moreover, ALD can also effectively improve the tightness of the contact interface between the MoS2 film and the diamond. This paper provides a new method and experimental basis for regulating the photon emission behavior of emitters.

Enhanced CO Functionality on Carbon Papers Ensures Lowering Nucleation Delay of ALD for Ru towards Unprecedented Alkaline HER Activity.

The success in lowering the nucleation delay for Atomic Layer Deposition (ALD) of Ru on carbon surfaces is mitigated by constructive pretreatments resulting enhancement of CO functionality. Treatment of the carbon papers (CP) allowed Ru species deposition for minimum number of ALD cycles (25 cycles) with good conformality. The development of electrocatalysts from single atoms to nanoparticles (NPs) on conductive supports with low metal loadings, thus improving performance, is essential in electrocatalysis. For alkaline hydrogen evolution reaction, ALD decorated CPs with Ru exhibit low onset potentials of ≈4.7mV versus reversable hydrogen electrode (RHE) (at 10mAcm-2 ) and a high turnover frequency of 1.92 H2 s-1 at 30mV versus RHE. The Ru decorated CPs show comparable to higher catalytic activity than of Platinum (Pt) decorated CP also developed by ALD. The current representation of unfamiliar catalytic activities of Ru active centers developed by ALD, pave a bright and sustainable path for energy conversion reactions.

In situ analysis of nucleation reactions during TiCl4/H2O atomic layer deposition on SiO2 and H-terminated Si surfaces treated with a silane small molecule inhibitor

Small-molecule inhibitors have recently been introduced for passivation during area-selective deposition (ASD). Small silanes like (N,N-dimethylamino)trimethylsilane (DMATMS) selectively react with −OH sites on SiO2 to form a less reactive –OSi(CH3)3 terminated surface. The –OSi(CH3)3 surface termination can inhibit many atomic layer deposition (ALD) processes, including TiCl4/H2O ALD. However, the mechanisms by which ALD is inhibited and by which selectivity is eventually lost are not well understood. This study uses in situ Fourier-transform infrared spectroscopy to probe the adsorption of DMATMS on SiO2 and the subsequent reactions when the passivated surface is exposed to TiCl4/H2O ALD. The chemisorption of DMATMS on isolated –OH groups on SiO2 is shown to inhibit the reaction with TiCl4. Further, we find that starting with an inherently inhibiting H-terminated Si surface, DMATMS can also react with residual –OH groups and reduce the extent of nucleation. Finally, using Rutherford backscattering spectrometry, the effectiveness of DMATMS passivation on SiO2 and H-terminated Si is quantified during extended ALD cycle numbers. The insight into the mechanisms of passivation by DMATMS and passivation loss can enable the rational design of highly selective ASD processes by carefully matching compatible surfaces, passivating agents, and ALD precursors.