Atomic layer deposition for tuning the surface chemical composition of nickel iron phosphates for oxygen evolution reaction in alkaline electrolyzers.

Transition metal phosphates are promising catalysts for the oxygen evolution reaction (OER) in alkaline medium. Herein, Fe-doped Ni phosphates are deposited using plasma-enhanced atomic layer deposition (PE-ALD) at 300 °C. A sequence offFe phosphate PE-ALD cycles andnNi phosphate PE-ALD cycles is repeatedxtimes. The Fe to Ni ratio can be controlled by the cycle ratio (f/n), while the film thickness can be controlled by the number of cycles (xtimes (n+f)). 30 nm films with an Fe/Ni ratio of ∼10% and ∼37%, respectively, are evaluated in 1.0 M KOH solution. Remarkably, a significant difference in OER activity is found when the order of the Ni and Fe phosphate PE-ALD cycles in the deposition sequence is reversed. A 20%-45% larger current density is obtained for catalysts grown with an Fe phosphate PE-ALD cycle at the end compared to the Ni phosphate-terminated flavour. We attribute this to a higher concentration of Fe centers on the surface, as a consequence of the specific PE-ALD approach. Secondly, increasing the thickness of the catalyst films up to 160 nm results in an increase of the OER current density and active surface area, suggesting that the as-deposited smooth and continuous films are converted into electrolyte-permeable structures during catalyst activation and operation. This work demonstrates the ability of PE-ALD to control both the surface and bulk composition of thin film electrocatalysts, offering valuable opportunities to understand their impact on performance.

Metal Nanocatalyst Sintering Interrogated at Complementary Length Scales.

Metal nanoparticle (NP) sintering is a prime cause of catalyst degradation, limiting its economic lifetime and viability. To date, sintering phenomena are interrogated either at the bulk scale to probe averaged NP properties or at the level of individual NPs to visualize atomic motion. Yet, "mesoscale" strategies which bridge these worlds can chart NP populations at intermediate length scales but remain elusive due to characterization challenges. Here, a multi-pronged approach is developed to provide complementary information on Pt NP sintering covering multiple length scales. High-resolution scanning electron microscopy (HRSEM) and Monte Carlo simulation show that the size evolution of individual NPs depends on the number of coalescence events they undergo during their lifetime. In its turn, the probability of coalescence is strongly dependent on the NP's mesoscale environment, where local population heterogeneities generate NP-rich "hotspots" and NP-free zones during sintering. Surprisingly, advanced in situ synchrotron X-ray diffraction shows that not all NPs within the small NP sub-population are equally prone to sintering, depending on their crystallographic orientation on the support surface. The demonstrated approach shows that mesoscale heterogeneities in the NP population drive sintering and mitigation strategies demand their maximal elimination via advanced catalyst synthesis strategies.

Aligning time-resolved kinetics (TAP) and surface spectroscopy (AP-XPS) for a more comprehensive understanding of ALD-derived 2D and 3D model catalysts.

The spectro-kinetic characterization of complex catalytic materials, i.e. relating the observed reaction kinetics to spectroscopic descriptors of the catalyst state, presents a fundamental challenge with a potentially significant impact on various chemical technologies. We propose to reconcile the kinetic characteristics available from temporal analysis of products (TAP) pulse-response kinetic experiments with the spectroscopic data available from ambient pressure X-ray photoelectron spectroscopy (AP-XPS), using atomic layer deposition (ALD) to synthesize multicomponent model surfaces on 2D and 3D supports. The accumulated surface exposure to a key reactant (total number of collisions) is used as a common scale within which the results from the two techniques can be rigorously compared for microscopically-equivalent surfaces. This approach is illustrated by proof-of-principle TAP and AP-XPS experiments with PtIn/MgO/SiO2 catalysts for alkane dehydrogenation at 800 K. Similarly to industrially-relevant Pt-based bimetallic catalysts on high-surface area supports, the initial period of coke accumulation on the surface resulted in gradually decreased conversion and increased selectivity towards propylene. We were able to monitor the process of coke deposition with both AP-XPS and TAP. The evolution of the C 1s photoelectron spectra is aligned on the common exposure scale with the evolution of the coke amounts deposited per Pt site during a multi-pulse TAP experiment. Moreover, TAP provided quantitative kinetic descriptors of propane consumption and product mean residence time within this common exposure scale. The challenges and opportunities presented by this novel tandem methodology are discussed in the context of catalysis research.

Gold-induced photothermal background in on-chip surface enhanced stimulated Raman spectroscopy.

Surface enhanced Raman spectroscopy (SERS) and stimulated Raman spectroscopy (SRS) are well established techniques capable of boosting the strength of Raman scattering. The combination of both techniques (surface enhanced stimulated Raman spectroscopy, or SE-SRS) has been reported using plasmonic nanoparticles. In parallel, waveguide enhanced Raman spectroscopy has been developed using nanophotonic and nanoplasmonic waveguides. Here, we explore SE-SRS in nanoplasmonic waveguides. We demonstrate that a combined photothermal and thermo-optic effect in the gold material induces a strong background signal that limits the detection limit for the analyte. The experimental results are in line with theoretical estimates. We propose several methods to reduce or counteract this background.

An IR Spectroscopy Study of the Degradation of Surface Bound Azido-Groups in High Vacuum.

Controlled surface functionalization with azides to perform on surface "click chemistry" is desired for a large range of fields such as material engineering and biosensors. In this work, the stability of an azido-containing self-assembled monolayer in high vacuum is investigated using in situ Fourier transform infrared spectroscopy. The intensity of the antisymmetric azide stretching vibration is found to decrease over time, suggesting the degradation of the azido-group in high vacuum. The degradation is further investigated at three different temperatures and at seven different nitrogen pressures ranging from 1 × 10-6 mbar to 5 × 10-3 mbar. The degradation is found to increase at higher temperatures and at lower nitrogen pressures. The latter supporting the theory that the degradation reaction involves the decomposition into molecular nitrogen. For the condition with the highest degradation detected, only 63% of azides is found to remain at the surface after 8 h in vacuum. The findings show a significant loss in control of the surface functionalization. The instability of azides in high vacuum should therefore always be considered when depositing or postprocessing azido-containing layers.

Controlled synthesis of Fe-Pt nanoalloys using atomic layer deposition.

We report the phase and size-controlled synthesis of Fe-Pt nanoalloys, prepared via a two-step synthesis procedure. The first step is the deposition of bilayers consisting of iron oxide and Pt films of desired thicknesses using atomic layer deposition, followed by a temperature-programmed reduction treatment of the film under H2/N2 atmosphere. This method enables the phase pure synthesis of all three Fe-Pt alloy phases, namely Fe3Pt, FePt, and FePt3, as revealed by in situ x-ray diffraction and x-ray fluorescence measurements. It is also demonstrated that by changing the total thickness of the bilayers while keeping the Pt/(Pt + Fe) atomic ratio constant, the size of the resulting bimetallic nanoparticles can be tuned, as confirmed by scanning electron microscopic measurements.

Reaction mechanism of the Me3AuPMe3-H2 plasma-enhanced ALD process.

The reaction mechanism of the recently reported Me3AuPMe3-H2 plasma gold ALD process was investigated using in situ characterization techniques in a pump-type ALD system. In situ RAIRS and in vacuo XPS measurements confirm that the CH3 and PMe3 ligands remain on the gold surface after chemisorption of the precursor, causing self-limiting adsorption. Remaining surface groups are removed by the H2 plasma in the form of CH4 and likely as PHxMey groups, allowing chemisorption of new precursor molecules during the next exposure. The decomposition behaviour of the Me3AuPMe3 precursor on a Au surface is also presented and linked to the stability of the precursor ligands that govern the self-limiting growth during ALD. Desorption of the CH3 ligands occurs at all substrate temperatures during evacuation to high vacuum, occurring faster at higher temperatures. The PMe3 ligand is found to be less stable on a gold surface at higher substrate temperatures and is accompanied by an increase in precusor decomposition on a gold surface, indicating that the temperature dependent stability of the precursor ligands is an important factor to ensure self-limiting precursor adsorption during ALD. Remarkably, precursor decomposition does not occur on a SiO2 surface, in situ transmission absorption infrared experiments indicate that nucleation on a SiO2 surface occurs on Si-OH groups. Finally, we comment on the use of different co-reactants during PE-ALD of Au and we report on different PE-ALD growth with the reported O2 plasma and H2O process in pump-type versus flow-type ALD systems.

The co-reactant role during plasma enhanced atomic layer deposition of palladium.

Atomic layer deposition (ALD) of noble metals is an attractive technology potentially applied in nanoelectronics and catalysis. Unlike the combustion-like mechanism shown by other noble metal ALD processes, the main palladium (Pd) ALD process using palladium(ii)hexafluoroacetylacetonate [Pd(hfac)2] as precursor is based on true reducing surface chemistry. In this work, a thorough investigation of plasma-enhanced Pd ALD is carried out by employing this precursor with different plasmas (H2*, NH3*, O2*) and plasma sequences (H2* + O2*, O2* + H2*) as co-reactants at varying temperatures, providing insights in the co-reactant and temperature dependence of the Pd growth per cycle (GPC). At all temperatures, films grown with only reducing co-reactants contain a large amount of carbon, while an additional O2* in the co-reactant sequence helps to obtain Pd films with much lower impurity concentrations. Remarkably, in situ XRD and SEM show an abrupt release of the carbon impurities during annealing at moderate temperatures in different atmospheres. In vacuo XPS measurements reveal the remaining species on the as-deposited surface after every exposure. Links are established between the particular surface termination prior to the precursor pulse and the observed differences in GPC, highlighting hydrogen as the key growth facilitator and carbon and oxygen as growth inhibitors. The increase in GPC with temperature for ALD sequences with H2* or NH3* prior to the precursor pulse is explained by an increase in the amount of hydrogen species that reside on the Pd surface which are available for reaction with the Pd(hfac)2 precursor.

Study of the surface species during thermal and plasma-enhanced atomic layer deposition of titanium oxide films using in situ IR-spectroscopy and in vacuo X-ray photoelectron spectroscopy.

The thermal and plasma-enhanced atomic layer deposition (ALD) growth of titanium oxide using an alkylamine precursor - tetrakis(dimethylamino)titanium (TDMAT) - was investigated. The surface species present during both the precursor and co-reactant pulse were studied with in situ reflection mid-IR spectroscopy (FTIR) and in vacuo X-ray photoelectron spectroscopy (XPS). The thermal process using H2O vapor proceeds through a typical ligand exchange reaction mechanism. The plasma-enhanced ALD processes using H2O-plasma or O2-plasma exhibit an additional decomposition and combustion reaction mechanism. After the plasma exposure, imine (N[double bond, length as m-dash]C) and isocyanate (N[double bond, length as m-dash]C[double bond, length as m-dash]O) surface species were observed by in situ FTIR. In addition, nitrites (NOx) were detected using in vacuo XPS during the O2-plasma process. This study presents the importance of the use of in situ FTIR and in vacuo XPS as complementary techniques to learn more about the ALD reaction mechanism. While in situ FTIR is very sensitive to changes of chemical bonds at the surface, exact identification and quantification could only be done with the aid of in vacuo XPS.

Surface mobility and impact of precursor dosing during atomic layer deposition of platinum: in situ monitoring of nucleation and island growth.

The increasing interest in atomic layer deposition (ALD) of Pt for the controlled synthesis of supported nanoparticles for catalysis demands an in-depth understanding of the nucleation controlled growth behaviour. We present an in situ investigation of Pt ALD on planar Si substrates, with native SiO2, by means of X-ray fluorescence (XRF) and grazing incidence small-angle X-ray scattering (GISAXS), using a custom-built synchrotron-compatible high-vacuum ALD setup and focusing on the thermal Pt ALD process, comprising (methylcyclopentadienyl)trimethylplatinum (MeCpPtMe3) and O2 gas at 300 °C. The evolution in key scattering features provides insights into the growth kinetics of Pt deposits from small nuclei to isolated islands and coalesced worm-like structures. An analysis approach is introduced to extract dynamic information on the average real space parameters, such as Pt cluster shape, size, and spacing. The results indicate a nucleation stage, followed by a diffusion-mediated particle growth regime that is marked by a decrease in average areal density and the formation of laterally elongated Pt clusters. Growth of the Pt nanoparticles is thus not only governed by the adsorption of Pt precursor molecules from the gas-phase and subsequent combustion of the ligands, but is largely determined by adsorption of migrating Pt species on the surface and diffusion-driven particle coalescence. Moreover, the influence of the Pt precursor dose on the particle nucleation and growth is investigated. It is found that the precursor dose influences the deposition rate (number of Pt atoms per cycle), while the particle morphology for a specific Pt loading is independent of the precursor dose used in the ALD process. Our results prove that combining in situ GISAXS and XRF provides an excellent experimental strategy to obtain new fundamental insights about the role of deposition parameters on the morphology of Pt ALD depositions. This knowledge is vital to improve control over the Pt nucleation stage and enable efficient synthesis of supported nanocatalysts.

Designing Nanoparticles and Nanoalloys for Gas-Phase Catalysis with Controlled Surface Reactivity Using Colloidal Synthesis and Atomic Layer Deposition.

Supported nanoparticles are commonly applied in heterogeneous catalysis. The catalytic performance of these solid catalysts is, for a given support, dependent on the nanoparticle size, shape, and composition, thus necessitating synthesis techniques that allow for preparing these materials with fine control over those properties. Such control can be exploited to deconvolute their effects on the catalyst's performance, which is the basis for knowledge-driven catalyst design. In this regard, bottom-up synthesis procedures based on colloidal chemistry or atomic layer deposition (ALD) have proven successful in achieving the desired level of control for a variety of fundamental studies. This review aims to give an account of recent progress made in the two aforementioned synthesis techniques for the application of controlled catalytic materials in gas-phase catalysis. For each technique, the focus goes to mono- and bimetallic materials, as well as to recent efforts in enhancing their performance by embedding colloidal templates in porous oxide phases or by the deposition of oxide overlayers via ALD. As a recent extension to the latter, the concept of area-selective ALD for advanced atomic-scale catalyst design is discussed.

Integrated silicon nitride electro-optic modulators with atomic layer deposited overlays.

Silicon nitride (SiN) is currently the most prominent CMOS-compatible platform for photonics at wavelengths <1 µm. However, realizing fast electro-optic (EO) modulators, the key components of any integrated optics platform, remains challenging in SiN. Modulators based on the plasma dispersion effect, as in silicon, are not available. Despite the fact that significant second-harmonic generation has been reported for silicon-rich SiN, no efficient Pockels effect-based modulators have been demonstrated. Here we report the back-end CMOS-compatible atomic layer deposition (ALD) of conventional second-order nonlinear crystals, zinc oxide, and zinc sulfide, on existing SiN waveguide circuits. Using these ALD overlays, we demonstrate EO modulation in ring resonators.

Formation and Functioning of Bimetallic Nanocatalysts: The Power of X-ray Probes.

Bimetallic nanocatalysts are key enablers of current chemical technologies, including car exhaust converters and fuel cells, and play a crucial role in industry to promote a wide range of chemical reactions. However, owing to significant characterization challenges, insights in the dynamic phenomena that shape and change the working state of the catalyst await further refinement. Herein, we discuss the atomic-scale processes leading to mono- and bimetallic nanoparticle formation and highlight the dynamics and kinetics of lifetime changes in bimetallic catalysts with showcase examples for Pt-based systems. We discuss how in situ and operando X-ray spectroscopy, scattering, and diffraction can be used as a complementary toolbox to interrogate the working principles of today's and tomorrow's bimetallic nanocatalysts.

Surface species during ALD of platinum observed with in situ reflection IR spectroscopy.

Thermal atomic layer deposition (ALD) and plasma-enhanced ALD (PE-ALD) of Pt, using MeCpPtMe3 as the precursor and O2 gas or O2 plasma as the reactant, are studied with in situ reflection Fourier transform infrared spectroscopy (FTIR) at different substrate temperatures. This is done to identify the functional groups present during Pt ALD and investigate the origin of the temperature dependent growth rate of the thermal process. Evidence is given that CH and C[double bond, length as m-dash]C containing species are present on the surface after precursor exposure at low substrate temperatures (<150 °C), poisoning the surface during thermal ALD. Both species are removed by O2 plasma enabling PE-ALD below 150 °C through combustion reactions. Above 150 °C, no CH stretching modes were detected and the C[double bond, length as m-dash]C vibration diminished, indicating dehydrogenation reactions and ligand restructuring. In addition, the PE-ALD FTIR spectra revealed the presence of combustion reaction products on the surface after precursor exposure. These were removed during the reactant exposure and during this exposure the formation of surface OH groups was found for both high and low substrate temperatures. We conclude that the decrease in the growth rate for the thermal process is caused by the inability of the surface to properly dehydrogenate and restructure the poisoning precursor ligands.

Kinetics of Lifetime Changes in Bimetallic Nanocatalysts Revealed by Quick X-ray Absorption Spectroscopy.

Alloyed metal nanocatalysts are of environmental and economic importance in a plethora of chemical technologies. During the catalyst lifetime, supported alloy nanoparticles undergo dynamic changes which are well-recognized but still poorly understood. High-temperature O2 -H2 redox cycling was applied to mimic the lifetime changes in model Pt13 In9 nanocatalysts, while monitoring the induced changes by in situ quick X-ray absorption spectroscopy with one-second resolution. The different reaction steps involved in repeated Pt13 In9 segregation-alloying are identified and kinetically characterized at the single-cycle level. Over longer time scales, sintering phenomena are substantiated and the intraparticle structure is revealed throughout the catalyst lifetime. The in situ time-resolved observation of the dynamic habits of alloyed nanoparticles and their kinetic description can impact catalysis and other fields involving (bi)metallic nanoalloys.

Atomic layer deposited second-order nonlinear optical metamaterial for back-end integration with CMOS-compatible nanophotonic circuitry.

We report the fabrication of artificial unidimensional crystals exhibiting an effective bulk second-order nonlinearity. The crystals are created by cycling atomic layer deposition of three dielectric materials such that the resulting metamaterial is noncentrosymmetric in the direction of the deposition. Characterization of the structures by second-harmonic generation Maker-fringe measurements shows that the main component of their nonlinear susceptibility tensor is about 5 pm/V, which is comparable to well-established materials and more than an order of magnitude greater than reported for a similar crystal [Appl. Phys. Lett.107, 121903 (2015)APPLAB0003-695110.1063/1.4931492]. Our demonstration opens new possibilities for second-order nonlinear effects on CMOS-compatible nanophotonic platforms.

Controlling Pt nanoparticle sintering by sub-monolayer MgO ALD thin films.

Metal nanoparticle (NP) sintering is a major cause of catalyst deactivation, as NP growth reduces the surface area available for reaction. A promising route to halt sintering is to deposit a protective overcoat on the catalyst surface, followed by annealing to generate overlayer porosity for gas transport to the NPs. Yet, such a combined deposition-annealing approach lacks structural control over the cracked protection layer and the number of NP surface atoms available for reaction. Herein, we exploit the tailoring capabilities of atomic layer deposition (ALD) to deposit MgO overcoats on archetypal Pt NP catalysts with thicknesses ranging from sub-monolayers to nm-range thin films. Two different ALD processes are studied for the growth of MgO overcoats on Pt NPs anchored on a SiO2 support, using Mg(EtCp)2 and H2O, and Mg(TMHD)2 and O3, respectively. Spectroscopic ellipsometry and X-ray photoelectron spectroscopy measurements reveal significant growth on both SiO2 and Pt for the former process, while the latter exhibits a drastically lower growth per cycle with an initial chemical selectivity towards Pt. These differences in MgO growth characteristics have implications for the availability of uncoated Pt surface atoms at different stages of the ALD process, as probed by low energy ion scattering, and for the sintering behavior during O2 annealing, as monitored in situ with grazing incidence small angle X-ray scattering (in situ GISAXS). The Mg(TMHD)2-O3 ALD process enables exquisite coverage control allowing a balance between physically blocking the Pt surface to prevent sintering and keeping Pt surface atoms free for reaction. This approach avoids the need for post-annealing, hence also safeguarding the structural integrity of the as-deposited overcoat.

Atomic layer deposition of TiO2 on surface modified nanoporous low-k films.

This paper explores the effects of different plasma treatments on low dielectric constant (low-k) materials and the consequences for the growth behavior of atomic layer deposition (ALD) on these modified substrates. An O2 and a He/H2 plasma treatment were performed on SiCOH low-k films to modify their chemical surface groups. Transmission FTIR and water contact angle (WCA) analysis showed that the O2 plasma changed the hydrophobic surface completely into a hydrophilic surface, while the He/H2 plasma changed it only partially. In a next step, in situ X-ray fluorescence (XRF), ellipsometric porosimetry (EP), and Rutherford backscattering spectroscopy (RBS) were used to characterize ALD growth of TiO2 on these substrates. The initial growth of TiO2 was found to be inhibited in the original low-k film containing only Si-CH3 surface groups, while immediate growth was observed in the hydrophilic O2 plasma treated film. The latter film was uniformly filled with TiO2 after 8 ALD cycles, while pore filling was delayed to 17 ALD cycles in the hydrophobic film. For the He/H2 plasma treated film, containing both Si-OH and Si-CH3 groups, the in situ XRF data showed that TiO2 could no longer be deposited in the He/H2 plasma treated film after 8 ALD cycles, while EP measurements revealed a remaining porosity. This can be explained by the faster deposition of TiO2 in the hydrophilic top part of the film than in the hydrophobic bulk which leaves the bulk porous, as confirmed by RBS depth profiling. The outcome of this research is not only of interest for the development of advanced interconnects in ULSI technology, but also demonstrates that ALD combined with RBS analysis is a handy approach to analyze the modifications induced by a plasma treatment on a nanoporous thin film.

Atomic layer deposition of yttrium oxide as a protective coating for lithium metal anodes.

Metallic lithium (Li) is considered as one of the highly interesting anode materials for advanced batteries due to its large theoretical capacity, small material density and the high cell voltages that can be obtained in batteries using Li anodes. However, Li dendrite growth and unstable solid electrolyte interphase (SEI) formation emerged during the plating-stripping process, leading to low coulombic efficiency, rapid battery degradation and serious safety issues. These disadvantages form the major challenges towards commercialization. In this work, an ultra-thin and uniform Y2O3 layer is coated on Li metal anodes by atomic layer deposition (ALD) for improving the stability of Li metal batteries. Elucidation by in vacuo X-ray photoelectron spectroscopy (XPS) revealed different growth of a Y2O3 layer on metallic Li compared to that on a silicon wafer, which is traditionally used for ALD processes. The Y-precursor, i.e., Y(EtCp)2(iPr-amd), firstly reacts with metallic Li and forms a "decomposition" layer, leading to nonlinear growth at the preliminary stage (up to around 20 ALD cycles). Only after the bare Li surface has been fully covered does standard ALD growth start. The ALD Y2O3 layer on metallic Li is able to effectively prevent the growth of Li dendrites, giving rise to an even plating-stripping process in symmetric Li metal cells with more stable performance and prolonged lifespan. Improved electrochemical performance through the Y2O3 protective layer has also been investigated in Y2O3-coated Li||LiMn2O4 asymmetrical full cells. This work indicates that ALD Y2O3 coating is an attractive method to stabilize Li metal anodes for battery devices.

Depositing ALD-oxides on MLD-metalcones: enhancing initial growth through O2 plasma densification.

Flexible devices are experiencing a steady increase in popularity, which brings the need of suitable protective/functional coatings for these applications. On the one hand, Atomic Layer Deposition (ALD) produces thin films with great purity, few pinholes and good conformality, but flexibility is rather limited. On the other hand, Molecular Layer Deposition (MLD) can produce partially/fully organic coatings with good flexibility, but stability concerns limit their applications. Therefore, combining ALD and MLD to obtain materials with good flexibility and improved characteristics holds great potential. In this article, we utilised O2 plasma treatments on various metalcone films to improve the compatibility of sequential ALD/MLD depositions. During plasma modification, in situ spectroscopic ellipsometry measurements (in situ SE) suggested that mainly the near-surface region of the metalcone layer was affected by the plasma treatment, locally converting the metalcone into a metal-oxide structure. This structure shielded the underlying metalcone layer from the plasma, thus resulting in a saturative-type behaviour even during extended plasma exposures. X-Ray reflectivity measurements (XRR) could only be fitted with bilayer models, while Fourier-Transform InfraRed spectroscopy (FTIR) showed an absorption decrease in the C-O band and an increase in the CO region. Additionally, film air stability seemed improved by this treatment. ALD-oxides were grown on these plasma-treated metalcones (PT-metalcones), and results were compared to pristine ones. While ALD growth on pristine metalcones always suffered from a delay, after which linear growth was achieved, oxides on PT-metalcones exhibited linear growth immediately, from cycle one. We therefore conclude that, upon O2 plasma exposure, metalcones are densified into a metalcone/oxide bilayer, where the oxide shields the underlying film from further oxidation. And, if an ALD oxide coating is to be deposited on top of these structures, this plasma treatment will make the structure more suitable for post-processing. In applications that require the combination of ALD/MLD multistacks, the use of an intermittent plasma treatment can prove useful.