Plasma-enhanced Atomic Layer Deposition Research Articles

Impact of bias stress and endurance switching on electrical characteristics of polycrystalline ZnO-TFTs with Al2O3 gate dielectric

Abstract This study experimentally investigates electrical characteristics and degradation phenomena in polycrystalline zinc oxide thin-film transistors (ZnO-TFTs). ZnO-TFTs with Al2O3 gate dielectric, Al-doped ZnO (AZO) source–drain contacts, and AZO gate electrode are fabricated using remote plasma-enhanced atomic layer deposition at a maximum process temperature of 190 °C. We employ positive bias stress (PBS), negative bias stress (NBS), and endurance cycling measurements to evaluate the ZnO-TFT performance and examine carrier dynamics at the channel-dielectric interface and at grain boundaries in the polycrystalline channel. DC transfer measurements yield a threshold voltage of −5.95 V, a field-effect mobility of 53.5 cm2/(V∙s), a subthreshold swing of 136 mV dec−1, and an on-/off-current ratio above 109. PBS and NBS measurements, analysed using stretched-exponential fitting, reveal the dynamics of carrier trapping and de-trapping between the channel layer and the gate insulator. Carrier de-trapping time is 88 s under NBS at −15 V, compared to 1856 s trapping time under PBS at +15 V. Endurance tests across 109 cycles assess switching characteristics and temporal changes in ZnO-TFTs, focusing on threshold voltage and field-effect mobility. The threshold voltage shift observed during endurance cycling is similar to that of NBS due to the contrast in carrier trapping/de-trapping time. A measured mobility hysteresis of 19% between the forward and reverse measurement directions suggests grain boundary effects mediated by the applied gate bias. These findings underscore the electrical resilience of polycrystalline ZnO-TFTs and the aptitude for 3D heterogeneous integration applications.

Active and stable plasma-enhanced ALD Pt@Ni-YSZ hydrogen electrode for steam reversible solid oxide cells

Designing and fabricating active and thermally stable bifunctional catalysts with minimal noble metal loadings are crucial for reversible solid oxide cells (rSOCs). This study employed Pt nanoparticles fabricated via plasma-enhanced atomic layer deposition (PEALD) to a nickel-yttria stabilized zirconia (Ni-YSZ) electrode to serve as effective catalysts in fuel cell and electrolysis modes. Despite the minimal Pt catalyst loading (<1 μg cm–2), the PEALD Pt@Ni-YSZ catalytic electrode exhibited superior electrochemical performance, (20 % higher than the bare cell), both in the fuel cell and electrolysis modes. Remarkably, this performance is sustained without any degradation over a 50 h duration at 700 °C. Dissimilar stabilization behaviors of the Pt catalysts occurred as distributed fine particles on Ni and anchored coarsened particles at the grain boundaries on YSZ surfaces. Furthermore, the mechanism of the enhanced hydrogen evolution/oxidation reactions with the PEALD Pt@Ni-YSZ electrode was verified using density functional theory simulations.

Fabrication and electrical properties of flexible polymer-based MIM capacitors of high-k nanolaminate dielectrics of HfO2–SnO2–TiO2 with ultrathin Al2O3 insertion layer by plasma-enhanced atomic layer deposition

Abstract Flexible metal–insulator–metal (MIM) capacitors of high-k nanolaminate HfO2–SnO2–TiO2 thin films were fabricated on several polymer substrates of polyethylene terephthalate, polyimide and epoxy resin at 80 °C by plasma-enhanced atomic layer deposition. The electrical properties were optimized by adjusting the sub-cycle ratio of Hf: Sn: Ti to 6: 5: 4. In order to reduce the leakage current density of flexible capacitors, the ultrathin Al2O3 layer varying from 0.5 to 1.5 nm was inserted to form Al2O3/HfO2–SnO2–TiO2/Al2O3 stacking capacitors. The effect of the Al2O3 insertion layer thickness and the super-cycle number of HfO2–SnO2–TiO2 on the capacitance density, leakage, and quadratic voltage linearity was investigated. Under optimal processing, flexible MIM capacitors could stand 40 000 bending cycles at curvature radius of 8.2 mm, indicative of better electrical stability. Moreover, compared with the polymer-based HfO2–SnO2–TiO2 capacitors, the introduction of 1 nm Al2O3 ultrathin layer greatly decreases the leakage current density by 4 orders of magnitude (10−8 A cm−2) with relative lower voltage linearity (350–540 ppm V−2), but the capacitance density also declines (∼3 fF μm−2) simultaneously. Despite this, the method of inserting Al2O3 ultra-thin layer is still an effective method to improve the electrical performances of polymer-based HfO2–SnO2–TiO2 nanolaminate capacitors for flexible electronics.

Enhanced Oxidation Resistance and Interface Stability of Atomic-Layer-Deposited MoNx Electrodes via TiN Passivation for DRAM Cell Capacitor Applications.

The continuous miniaturization of dynamic random-access memory (DRAM) capacitors has amplified the demand for electrode materials featuring specific characteristics, such as low resistivity, high work function, chemical stability, excellent interface quality with high-k dielectrics, and superior mechanical properties. In this study, molybdenum nitride (MoNx) films were deposited using a plasma-enhanced atomic layer deposition (PEALD) employing bis(isopropylcyclopentadienyl)molybdenum(IV) dihydride and NH3 plasma for DRAM capacitor electrode applications. Depending on the deposition temperatures of the PEALD MoNx films ranging from 200 to 400 °C, the Mo/N ratio and crystal structure varied, transitioning from the cubic NaCl-B1-type MoN phase with Mo/N ratio of 1.4 to the cubic γ-Mo2N phase with Mo/N ratio of 1.9. Notably, MoNx films grown at 400 °C exhibited low resistivity (435 μΩ·cm), a high work function (5.28 eV), and superior mechanical hardness (11.3 GPa) compared to ALD TiN films. Despite these excellent properties, the PEALD MoNx electrode demonstrated insufficient chemical stability, particularly in terms of oxidation resistance and interface quality with ALD HfxZr1-xO2 (HZO) films. This resulted in poor morphology and the formation of significant oxygen-deficient HZO layers (such as HfO2-x), leading to considerable degradation in the electrical performance of metal-insulator-metal (MIM) capacitors. To mitigate this issue, a thin (2.5-14 nm) ALD TiN layer was introduced as a passivation layer between the MoNx bottom electrode and HZO dielectric. The TiN-passivated MoNx (TiN/MoNx) electrode showed substantially enhanced oxidation resistance and reduced interfacial reactions with the HZO dielectric. Consequently, MIM capacitors with TiN/MoNx bottom electrodes demonstrated outstanding electrical performance, including excellent dielectric properties, low leakage current density, and high mechanical strength. Hence, this study proposes a promising candidates for storage nodes in the next-generation DRAM capacitors.

Impact of plasma power on plasma enhanced atomic layer deposited TiO2 as a spacer

As the size of devices is scaled down, micro-patterning technology is increasing in importance. In micro-patterning, spacers require precise thickness and uniform deposition at low temperature. To meet these requirements, atomic layer deposition (ALD), which can be controlled to an accurate thickness, was introduced. Therefore, we investigated plasma-enhanced ALD using radicals for high reactivity. Optical emission spectroscopy and a Langmuir probe were used to evaluate plasma properties such as radical intensity and plasma density at different plasma powers. Regardless of plasma power, growth per cycle and compositions of Ti and O remained constant. X-ray photoelectron spectroscopy showed that application of 500 W decreased the area of Ti2O3 from 20.2 % to 4.5 % compared with 100 W due to the increased amount of oxygen radicals. X-ray reflectivity results showed a 4.09 g/cm3 density of TiO2 film at 100 W, which increased to 4.2 g/cm3 at 500 W, indicating a decrease of Ti2O3. Meanwhile, the wet etch rate of TiO2 film was 1.72 Å/min at 100 W and 0.8 Å/min at 500 W, and the denser film had superior etch resistance. Finally, transmission electron microscopy showed that step coverage of TiO2 films improved from 90.9 % to 99.9 % with increasing power. Thus, application of high power effectively improved the properties of TiO2 films.

Plasma-enhanced atomic layer deposition of carbon films employing a cyclic process of N2/H2 plasma and α, α’-dichloro-p-xylene as a precursor

A novel concept and process were proposed for the plasma-enhanced atomic layer deposition (PE-ALD) of carbon films. α, α’-dichloro-p-xylene (DCX) was used to form the adsorption layer, which was modified using nitrogen/hydrogen (N2/H2) plasma. Through iterative molecular chemisorption and end-group substitution processes, the selective and precise control of carbon deposition by PE-ALD was achieved. The growth per cycle of this process was estimated to be 0.02–0.05 nm/cycle. To determine the chemical reactions that occurred during the PE-ALD process, the IR spectra observed using in-situ Fourier transform infrared spectroscopy were analyzed. The decrease in the Si-OH bond at 3740 cm−1 and the saturation of the increase in CH bending at 1250 cm−1 revealed that the deposition of a DCX monolayer via a dehydrochlorination reaction with isolated OH bonding on SiO2 has been successfully achieved. The change in N(−H)x stretching during the N2/H2 plasma treatment indicated the substitution of exposed C-Cl bonding with C-NH2 bonding on the chemisorbed DCX monolayer surface. Additionally, the composition of the carbon films after 200-cycle PE-ALD was analyzed. Finally, the realization of the concept for PE-ALD of carbon film was confirmed by surface analysis.

Mechanisms of electrical transition using a conformal MoOx cap on Mo-doped VO2 thermochromics

Mo-doped VO2 thin-films are deposited on the soda-lime glass by a reactive high-power impulse magnetron co-sputtering technique (R-HiPIMS). Rapid thermal annealing at 500 °C for 3 min is performed to achieve the fabrication under low thermal budget. To prevent VO2 from further oxidation, a conformal and semi-conducting MoOx film is applied as the capping layer by the plasma-enhanced atomic layer deposition (PE-ALD). After MoOx film is deposited, an electrical transition in the resistance ratio of 6–10 orders of magnitude has been found, especially for MoOx thicknesses less than 20 nm. A secondary phase of V2O3 plays an important role in abrupt change of current transportation. Also, the hysteresis of optical transition in transmittance at a wavelength of 2500 nm shows that both the width and transition temperature (TC) decrease with increasing the thickness of the MoOx cap. Moreover, the effect of localized surface plasmonic resonance (LSPR) due to the Karst-like structure has been detected by the absorption spectrum. The variations in LSPR peak, such as intensity, blue-shifting, and red-shifting, originated from either excess carrier or structure change are discussed. The high aspect ratio of surface morphology is further examined by atomic force microscopy. In addition, the coverage of MoOx on Mo-doped VO2 concerning the friction behavior is evaluated by lateral force microscopy (LFM), which is helpful in clarifying the responsible mechanisms during TC transition.

Silicon dioxide atomic layer deposition at low temperature for PDMS microlenses coating

The optical performance of a microlens is strongly affected by its surface roughness, which depends on its fabrication process. High-surface roughness leads to scattering issues, decreasing the optical efficiency of a microlens. In this work, a polydimethylsiloxane microlens was coated with a very thin-film of silicon dioxide (30 nm), deposited by plasma-enhanced atomic layer deposition at a low temperature (50 °C). The main goal was to passivate the polymeric microlens and reduce its surface roughness. Atomic force microscopy was performed before and after the silicon dioxide coating, confirming the surface roughness reduction by a factor of 3.2. The microlens was observed by scanning electron microscopy after silicon dioxide coating. Surface elemental composition analysis of the silicon dioxide thin-film was also performed through X-ray photoelectron spectroscopy, confirming the formation of silicon dioxide and a stoichiometric ratio of silicon to oxygen (Si:O) close to 27:58. The refractive index of the deposited film was measured by ellipsometry, obtaining a value of 1.4617 at 470 nm.

Plasma-enhanced atomic layer deposition of indium-free ZnSnOx thin films for thin-film transistors

An appropriate synthesis technique for growing high-quality indium-free ZnSnOx (ZTO) films should be developed to achieve high-performance thin-film transistors (TFTs) utilizing ZTO films. This study investigated the growth characteristics and electrical properties of ZTO thin films grown via plasma-enhanced atomic layer deposition (PEALD) using bis(1-dimethylamino-2-methyl-2-propoxide)Sn, diethylzinc, and O2 plasma to optimize the composition and enhance the device performance. Deviations were observed in the growth per cycle when using PEALD for ZTO, compared with binary oxides. In the PEALD of the ZTO films, the introduction of the SnO2 sub-cycle enhanced the mass gain in the ZnO sub-cycle, whereas the mass gain in the SnO2 sub-cycle decreased with the addition of the ZnO sub-cycle. This was attributed to changes in the density of the functional groups on the reaction surface. Precise control over the composition was achieved, enabling the identification of the optimal Zn58Sn42Ox composition. Post-deposition annealing significantly improved the TFT performance, with devices showing enhanced mobility, positive shifts in the threshold voltage, and reduced subthreshold swing values. These improvements stemmed from reductions in oxygen vacancies and sub-gap defect states. These findings highlight the potential of PEALD-grown ZTO films for use in high-performance, cost-effective TFTs, facilitating their integration into modern semiconductor electronics.

Plasma-enhanced atomic layer deposition of silicon nitride thin films with different substrate biasing using Diiodosilane precursor

In this work, we report on Plasma-Enhanced Atomic Layer Deposition (PE-ALD) of SiNx films using Diiodosilane (DIS) precursor and N2-H2 plasma. Systematic studies as a function of DIS dosing time, plasma duration, plasma composition and deposition temperature are investigated. The material properties have been studied using X-ray photoelectron spectroscopy (XPS), X-Ray Reflectometry (XRR), Atomic Force Microscopy (AFM) and High-Resolution Transmission Electron Microscopy (HR-TEM). The optimal deposition parameters for achieving high-quality SiNx with a high growth per cycle (GPC) are first determined. We show that DIS offers a wide temperature window for SiNx deposition starting from 110 °C up to 300 °C, paving the way for a large choice of SiN-based applications. The impact of substrate biasing on SiNx film deposition and properties is also investigated. We show that high ion energies during the nitridation step can cause surface damage and void formation, thus affecting the SiNx quality. Overall, these results highlight the importance of this novel precursor for growing SiNx using PE-ALD and the possible swapping of the material properties by fine control of the substrate biasing, which can help to go far beyond the existing SiNx limitations.

Plasma-enhanced atomic layer deposition as a technique for controlling the composition and properties of indium-based transparent conductive oxides

Indium oxide and doped indium oxide films were successfully grown utilizing a plasma-enhanced atomic layer deposition supercycling process, which was found to be an effective means of controlling films’ composition and, hence, their properties. Using trimethylindium and oxygen plasma as an indium precursor and a co-reactant, respectively, a growth rate of approximately 1.26 Å per cycle was obtained based on thickness measurements by spectroscopic ellipsometry. Three distinct dopants, Sn, Ti, and Mo, have been incorporated into indium oxide. The effects of dopant type, cycle ratio of dopant to indium oxide, and thermal annealing on the structural, electrical, and optical properties were studied. The deposited films consisted of polycrystalline columnar grains perpendicular to the substrate with a cubic bixbyite structure and [111] as the favored growth direction. Thermal annealing had a significant effect on the film characteristics, resulting in an order of magnitude reduction in resistivity, as well as changes in transmittance in the near-infrared (NIR) and ultraviolet (UV) regions. The lowest resistivities achieved for Sn-doped, Ti-doped, and Mo-doped were 2.8 × 10−4, 4.2 × 10−4, and 6.1 × 10−4 Ω cm, respectively. The changes are attributed to dopant activation, as the UV shift between the differently doped samples may be linked to the Moss–Burstein effect and the NIR behavior can be explained by an increase in charge carrier density, as predicted by the Drude model. The three dopants primarily provide a trade-off between electrical resistance and NIR transparency. Mo-doped films exhibited the highest near-infrared transparency, while Sn-doped films offered the lowest sheet resistance.

Plasma-enhanced atomic layer deposition of Sn-doped indium oxide semiconductor nano-films for thin-film transistors

Sn-doped indium oxide (ITO) semiconductor nano-films are fabricated by plasma-enhanced atomic layer deposition using trimethylindium (TMIn), tetrakis(dimethylamino)tin (TDMASn), and O2plasma as the sources of In, Sn and O, respectively. A shared temperature window of 150 °C- 200 °C is observed for the deposition of ITO nano-films. The introduction of Sn into indium oxide is found to increase the concentration of oxygen into the ITO films and inhibit crystallization. Furthermore, two oxidation states are observed for In and Sn, respectively. With the increment of interfaces of In-O/Sn-O in the ITO films, the relative percentage of In3+ions increases and that of Sn4+decreases, which is generated by interfacial competing reactions. By optimizing the channel component, the In0.77Sn0.23O1.11thin-film transistors (TFTs) demonstrate high performance, includingμFEof 52.7 cm2V-1s-1, and a highION/IOFFof ∼5 × 109. Moreover, the devices show excellent positive bias temperature stress stability at 3 MV cm-1and 85 °C, i.e. a minimalVthshift of 0.017 V after 4 ks stress. This work highlights the successful application of ITO semiconductor nano-films by ALD for TFTs.

Plasma-Enhanced Atomic Layer Deposition of Hematite for Photoelectrochemical Water Splitting Applications

Plasma-Enhanced Atomic Layer Deposition of Hematite for Photoelectrochemical Water Splitting Applications

Influence of High-κ Dielectrics Integration on ALD-Based MoS2 Field-Effect Transistor Performance.

The integration of high-κ dielectrics on MoS2 field-effect transistors (FETs) is essential for the realization of MoS2 in ultrascaled nanoelectronic devices and circuits. Most studies covering this topic are based on exfoliated MoS2 flakes or chemical vapor deposition (CVD) grown MoS2 films, whereas other techniques, such as atomic layer deposition (ALD), are also gaining attention for the growth of MoS2 in recent years. In this work, we grow large-area MoS2 by means of plasma-enhanced (PE-)ALD and evaluate the influence of high-κ dielectrics on the properties of ALD-based MoS2 FETs through electrical characterization combined with surface-chemical and high-resolution scanning transmission electron microscopy (HR-STEM) analyses. We grow HfO x , AlO x , or both by means of PE-ALD or thermal ALD on our fabricated devices and show that, in addition to the dielectric constant, three other major parameters related to the processing of the dielectrics can simultaneously affect the MoS2 FET electrical characteristics and govern its doping. These parameters are the stoichiometry of the dielectric, its carbon impurity content, and the degree to which the MoS2 surface oxidizes upon the dielectric growth. When grown at 100 °C, our HfO x films are oxygen-vacant whereas our AlO x films are oxygen-rich. In addition, carbon impurities are incorporated into the dielectrics at low deposition temperatures, being one of the likely causes of the MoS2 FET overall n-type performance in all of the studied cases. Our investigations also reveal that PE-ALD of HfO x or AlO x oxidizes the MoS2 surface, whereas thermal ALD AlO x leaves MoS2 almost intact. In this respect, if thermal ALD AlO x of proper thickness is grown between MoS2 and HfO x , it can reduce the degree to which the MoS2 surface oxidizes by HfO x and meanwhile improve the total dielectric constant, altogether leading to the most optimal electrical performance in ALD-based MoS2 FETs.

Atomic Layer Deposition of Cu Catalysts on Gas Diffusion Electrodes for Electrochemical CO2 Reduction

Electrochemical CO2 conversion is gaining attention as an important process for carbon fixation through the use of renewable electricity to address the climate change crisis. Copper is a unique single-element catalyst that can induce C-C coupling reactions to generate high-value-added compounds. The triple phase boundary has been successfully controlled at the catalyst interface using gas diffusion electrodes (GDEs) over the past few years, resulting in high C-C coupling performance. Therefore, methods to engineer the catalyst interface on the 3D structure of GDE are of significant importance. Generally, the catalyst on the GDE is introduced through physical vaper deposition (PVD) using sputtering or E-beam evaporation, or through solution methods such as spray coating and drop-casting of nano-particles. However, the porous and tortuous 3D structure of the GDE often result in limited conformality and difficulty in obtaining a uniform and controlled infiltration of the catalyst into the support structure.In this study, we synthesized Cu catalysts directly onto GDE surfaces using plasma-enhanced atomic layer deposition (PE-ALD), which allowed for precise tuning of the catalyst size and loading at the nanoscale [1]. The synthesized catalysts were confirmed to be polycrystalline Cu nanoparticles using grazing incidence X-ray diffraction. To demonstrate the advantages of the conformal and tunable control of PE-ALD deposition, we deposited the same areal mass loading of Cu catalyst onto the GDE substrates using PVD, and compared the CO2 reduction activity in an H-cell environment. The PE-ALD Cu catalyst showed more than 3 times higher current density than the PVD catalyst at the same electrode potential, a low (~10%) Faradaic efficiency (FE) for the hydrogen evolution reaction (HER), and greater than 75% FE for C-C coupling to form C2+ products including ethylene and ethanol, which is comparable to the highest performances reported to date for metallic Cu catalysts in a H-cell environment. Furthermore, stable operation was observed for a duration of 15 hours, with minimal changes in activity and selectivity. In conclusion, the introduction of catalysts using PE-ALD on GDE electrodes represents a powerful new synthesis method that can increase both C-C coupling performance and selectivity compared to PVD deposition, due to its adjustable Cu nanoparticle size and high conformality. Reference 1) J. D. Lenef, S.Y. Lee, K. M. Fuelling, K. E. Rivera Cruz, A. Prajapati, D. O. D. Cornejo, T. H. Cho, K. Sun, E. Alvarado, T. S. Arthur, C. A. Roberts, C. Hahn, C. C. L. McCrory, N. P. Dasgupta, Nano Lett. 23, 10779-10787 (2023)

Ru Decoration By PEALD for Bifunctional Oxygen Electrocatalysis in Solid Oxide Cells

Solid oxide cells (SOCs) are electrochemical devices that have garnered significant attention due to their high efficiency, fuel flexibility, and reversibility for operation in both fuel cell and the electrolysis modes. However, the relatively high operating temperature (typically > 800 °C) required presents various challenges such as fast degradation, high operating costs, and slow start-up. To overcome these issues, significant efforts have been made to decrease the operating temperature, but this causes a dramatic decrease in performance due to the low catalytic activity of typical electrode materials. One strategy to increase the catalytic activity is to introduce highly active nanoparticles onto a conventional electrode backbone, but while noble metals such as Ru and Ir have been utilized as oxygen evolution reaction (OER) catalysts, their widespread application in SOECs is hindered by their high cost and limited availability.In this presentation, we demonstrate a highly effective approach to enhance air electrode performance through the deposition of an ultrathin layer of metallic Ru, as thin as ∼7.5 Å, onto (La0.6Sr0.4)0.95Co0.2Fe0.8O3-δ (LSCF) using plasma-enhanced atomic layer deposition (PEALD). The Ru-decorated cell exhibited a current density of 656 mA cm–2 at 1.3 V, significantly outperforming a bare cell (440 mA cm–2 at 1.3 V). The decorated cell also showed a largely enhanced cell durability, which is ascribed to the beneficial role of SrRuO3 that emerges from the reaction between PEALD-based Ru and surface-segregated Sr species, in suppressing Sr segregation and maintaining favorable oxygen desorption kinetics. Further, the PEALD Ru coating on LSCF also reduces the resistance to the oxygen reduction reaction (ORR), highlighting the bifunctional electrocatalytic activities for reversible fuel cells. When the LSCF electrode of a test cell is decorated with ∼7.5 Å of the Ru overcoat and tested in fuel cell mode at 700 °C, this results in a current density of 656 mA cm-2 at 1.3 V in electrolysis mode and a peak power density of 803 mW cm-2, corresponding to an enhancement of 49.1% and 31.9%, respectively, compared to the pristine cell.

Deposition Kinetics and Characteristics of Peald Igzo Films Using Tetrahydrofuran-Adducted in & Ga Precursors

As the down-scaling of semiconductor materials, silicon compatible emerging materials have extensively researched for next generation display and 3D structured devices. In particular, oxide semiconductors are considered a promising candidate for backplane applications in display. Among them, indium-gallium-zinc oxide (IGZO) using plasma enhanced atomic layer deposition (PEALD) has excellent properties, like high mobility, low leakage current, high transparecy and low temperature processablility. However, conventional precursors for IGZO still have some prolems to solve such as low deposition rate, low thermal stability and high price. In this study, we developed indium precursor (Trimethylindium Tetrahydrofuran, DIP-4) and gallium precursor (Trimethylgallium Tetrahydrofuran, DGP-2) to overcome the shortcomings of the conventional In & Ga precursors. ALD characteristics of the films deposited using the newly developed the precursors were confirmed through the source feeding time saturation and linearity. Furthermore, the incubation time of In, Ga and Zn oxide films according to the different bottom layer was respectively verified and calculated using the developed DIP-4, DGP-2 and commercially used DEZn. In order form a multilayer IGZO thin film, application of the incubation factors at IGZO process were experimentally demonstrated. Thickness of the IGZO films can be easily controlled through modulation of the incubation factors. The physical and chemical properties of the films were analyzed by X-ray diffraction, X-ray reflectrometer, X-ray photoelectron spectroscopy, transmission electron microscope. Figure 1

Ag/CNT Catalyst Synthesized by Plasma-Enhanced Atomic Layer Deposition for Anion Exchange Membrane Fuel Cells

Anion exchange membrane fuel cells (AEMFCs) have recently gained attention as a viable alternative to proton exchange membrane fuel cells (PEMFC), offering the potential for high output without relying on expensive platinum (Pt) catalysts. PEMFCs operate in an acidic environment characterized by a high concentration of H+, necessitating the use of platinum-based catalysts to ensure both performance and stability in such conditions. In contrast, AEMFCs operate in an alkaline environment (OH-), affording the use of high-performance catalysts like silver (Ag), which is sensitive to acidity. Moreover, the cost of Ag is approximately 1/50 of Pt, offering significant cost advantages for fuel cell commercialization. Atomic layer deposition (ALD) has garnered substantial attention as a valuable technique for crafting high-performance nano-catalysts. ALD's self-limiting nature, based on the sequential exposure of vaporized precursors and reactants, enables precise control over catalyst size and composition. In this study, we employed plasma-enhanced ALD (PEALD) to fabricate cutting-edge AEMFC cathodes comprised of carbon nanotubes (CNTs) adorned with Ag. This approach yielded impressive results, achieving an AEMFC output exceeding 300 mW cm-2 or more than 2 W mgAg -1 at 65 °C with a CNT cathode featuring an exceedingly low Ag loading of less than 0.15 mg cm-2. Notably, this represents the world's highest reported Ag-AEMFC performance to date. The Ag-decorated cathode created through ALD played a pivotal role in significantly reducing resistance in the polarization region, a major contributor to overall energy losses in AEMFCs. Additionally, when evaluating the durability of the Ag-decorated CNT anode in an alkaline environment, we observed excellent long-term stability. In this presentation, we will discuss a more detailed exploration of the relationship between AEMFC performance, featuring ALD-fabricated Ag-CNT catalysts, and the intricate catalyst structure.

(Invited) Role of Oxidant Gas for Atomic Layer Deposition of HfxZr1−XO2 Thin Films on Ferroelectricity of Metal-Ferroelectric-Metal Capacitors

Since the first report of ferroelectricity in HfxZr1−xO2 (HZO) in 2011 [1], a lot of attention has been devoted for future non-volatile memory device applications due to its scalability (< 10 nm), low thermal budget (< 400°C) and matured atomic layer deposition (ALD) technique [2]. The thermal ALD process using H2O or O3 is generally employed for the fabrication of ferroelectric HZO thin films. On the other hand, the effect of the plasma-enhanced ALD process using O2 plasma gas on the crystallinity and ferroelectricity has not been systematically clarified. In this paper, we report the importance of ALD oxidant gases for HZO films using H2O or O2 plasma on the ferroelectricity of metal–ferroelectric–metal (MFM) capacitors.MFM capacitors with the H2O- and O2 plasma-based HZO films were fabricated as follows. A 10-nm-thick HZO films were deposited on a TiN bottom-electrode (BE-TiN) by ALD at 300°C using H2O or O2 plasma as oxidant gases and (Hf/Zr)[N(C2H5)CH3]4 (Hf:Zr = 1:1) cocktail precursor. The Hf/Zr ratios in both types of HZO films were estimated to be 0.4/0.6 using X-ray photoelectron spectroscopy (XPS). Next, a post-deposition annealing (PDA) process was carried out at 400 °C for 1 min under a N2 atmosphere. Finally, a TiN top-electrode was deposited by DC sputtering.First, the crystallinity and remanent polarization (2P r = P r + − P r −) of the H2O- and O2 plasma-based HZO films were investigated. Nanocrystals with ferroelectric orthorhombic (O), tetragonal (T), cubic (C) phases partially existed in the O2 plasma-based film after the ALD process, while an amorphous structure dominantly existed in the H2O-based film, analyzed by the grazing-incidence X-ray diffraction analysis and cross-sectional transmission electron microscopy images [3]. This could be because of a strong oxidation power and high energy ion/electron bombardment of O2 plasma. After the PDA process, the O phase was formed more in the O2 plasma-based HZO film than the H2O-based film. Therefore, the nanocrystal grains in the as-grown O2 plasma-based HZO film could play an important role as nuclei for the crystallization and formation of O phase [3,4]. From the polarization–electric field hysteresis curves, the PDA-treated O2 plasma-based capacitor exhibited 2P r of 20 µC/cm2, which was 1.5 times higher than that (13 µC/cm2) of the H2O-based capacitor. Thus, these results indicate that the crystallization and O phase formation of HZO films were promoted by using O2 plasma gas as an ALD oxidant, resulted in a higher 2P r.Next, endurance properties of these MFM capacitors were evaluated. In the wake-up state, both capacitors showed almost the same increase rate (~8%) of switching polarization (P sw). In the fatigued state, on the other hand, the O2 plasma-based capacitor exhibited less P sw degradation (~33%) after 106 cycles, whereas the P sw of H2O-based capacitor decreased by ~47%. To clarify these different fatigue properties, the TiOxNy interface reaction layer (IRL) formation at the HZO/BE-TiN interface was analyzed using synchrotron hard X-ray photoelectron spectroscopy (HAXPES). For the HAXPES Ti 2p spectra, the Ti-O peak intensity for the O2 plasma-based capacitor was larger than that of the H2O-based capacitor [5]. Therefore, an oxygen-rich TiON-IRL could be formed at the HZO/BE-TiN interface during ALD process due to the stronger oxidizing power of O2 plasma. Additional oxygen vacancies (VO) were reported to formed in HfO2-based films during field cycling due to the interface reaction between the HfO2-based film and TiN electrode. Moreover, one of the origins of the P sw degradation was thought to be domain pinning caused by VO [6]. Therefore, an oxygen-rich TiON-IRL for the MFM capacitor with the O2 plasma-based HZO film could prevent the interface reaction and formation of additional VO in HZO films, led to superior fatigue properties.In summary, the MFM capacitor with the O2 plasma-based HZO film showed superior 2Pr and fatigue resistance compared to those of the H2O-based one. Based on these experimental results, it is important to consider the selection of an ALD oxidant for fabrication of HZO-based MFM capacitors.This work was partly supported by JSPS KAKENHI (Nos. JP21J01667, JP20H02189, and JP18J22998) and MEXT Leading Initiative for Excellent Young Researchers (No. JPMXS0320220213). The HAXPES measurements were performed under approval of the NIMS Synchrotron X-ray Station (2020A4602 and 2020A4651).[1] J. Müller et al., Appl. Phys. Lett. 99, 112901 (2011).[2] J.-H. Kim et al., ACS Appl. Electron. Mater. 5, 4726 (2023).[3] T. Onaya et al., APL Mater. 10, 051110 (2022).[4] T. Onaya et al., Microelectron. Eng. 215, 111013 (2019).[5] T. Onaya et al., Solid State Electron. 210, 108801 (2023).[6] M. Pešić et al., Adv. Funct. Mater. 26, 4601 (2016).

Plasma-enhanced atomic layer deposition of titanium nitride for superconducting devices

This study examines the superconducting properties of titanium nitride (TiN) deposited via plasma-enhanced atomic layer deposition on both planar and three-dimensional (3D) structures. Our deposition method achieves consistent uniformity, maintaining sheet resistance (R□) &amp;gt; 95% across a 6-in. wafer, crucial for large-scale superconducting device fabrication and yield optimization. The planar films, akin to reactive-sputtered TiN, reached a critical temperature (Tc) of 4.35 K at a thickness of ≈40 nm. For aspect ratios (ARs) between 2 and 40, we observed a single transition of ≈2 K at ARs between 2 and 10.5, and multiple transitions at ARs &amp;gt; 10.5. We discuss mechanisms influencing superconducting properties in the 3D structures, aligning with current and future superconducting technologies.