Unraveling the Role of the Stoichiometry of Atomic Layer Deposited Nickel Cobalt Oxides on the Oxygen Evolution Reaction.

Nickel cobalt oxides (NCOs) are promising, non-precious oxygen evolution reaction (OER) electrocatalysts. However, the stoichiometry-dependent electrochemical behavior makes it crucial to understand the structure-OER relationship. In this work, NCO thin film model systems are prepared using atomic layer deposition. In-depth film characterization shows the phase transition from Ni-rich rock-salt films to Co-rich spinel films. Electrochemical analysis in 1 m KOH reveals a synergistic effect between Co and Ni with optimal performance for the 30 at.% Co film after 500 CV cycles. Electrochemical activation correlates with film composition, specifically increasing activation is observed for more Ni-rich films as its bulk transitions to the active (oxy)hydroxide phase. In parallel to this transition, the electrochemical surface area (ECSA) increases up to a factor 8. Using an original approach, the changes in ECSA are decoupled from intrinsic OER activity, leading to the conclusion that 70 at.% Co spinel phase NCO films are intrinsically the most active. The studies point to a chemical composition dependent OER mechanism: Co-rich spinel films show instantly high activities, while the more sustainable Ni-rich rock-salt films require extended activation to increase the ECSA and OER performance. The results highlight the added value of working with model systems to disclose structure-performance mechanisms.

Electrochemical Activation of Atomic-Layer-Deposited Nickel Oxide for Water Oxidation.

NiO-based electrocatalysts, known for their high activity, stability, and low cost in alkaline media, are recognized as promising candidates for the oxygen evolution reaction (OER). In parallel, atomic layer deposition (ALD) is actively researched for its ability to provide precise control over the synthesis of ultrathin electrocatalytic films, including film thickness, conformality, and chemical composition. This study examines how NiO bulk and surface properties affect the electrocatalytic performance for the OER while focusing on the prolonged electrochemical activation process. Two ALD methods, namely, plasma-assisted and thermal ALD, are employed as tools to deposit NiO films. Cyclic voltammetry analysis of ∼10 nm films in 1.0 M KOH solution reveals a multistep electrochemical activation process accompanied by phase transformation and delamination of activated nanostructures. The plasma-assisted ALD NiO film exhibits three times higher current density at 1.8 V vs RHE than its thermal ALD counterpart due to enhanced ß-NiOOH formation during activation, thereby improving the OER activity. Additionally, the rougher surface formed during activation enhanced the overall catalytic activity of the films. The goal is to unravel the relationship between material properties and the performance of the resulting OER, specifically focusing on how the design of the material by ALD can lead to the enhancement of its electrocatalytic performance.

Surface Modulation via Conjugated Bithiophene Ammonium Salt for Efficient Inverted Perovskite Solar Cells.

The metal halide perovskite absorbers are prone to surface defects, which severely limit the power conversion efficiencies (PCEs) and the operational stability of the perovskite solar cells (PSCs). Herein, trace amounts of bithiophene propylammonium iodide (bi-TPAI) are applied to modulate the surface properties of the gas-quenched perovskite. It is found that the bi-TPAI surface treatment has negligible impact on the perovskite morphology, but it can induce a defect passivation effect and facilitate the charge carrier extraction, contributing to the gain in the open-circuit voltage (Voc) and fill factor. As a result, the PCE of the gas-quenched sputtered NiOx-based inverted PSCs is enhanced from the initial 20.0% to 22.0%. Most importantly, the bi-TPAI treatment can largely alleviate or even eliminate the burn-in process during the maximum power point tracking measurement, improving the operational stability of the devices.

In Situ IR Spectroscopy Studies of Atomic Layer-Deposited SnO2 on Formamidinium-Based Lead Halide Perovskite.

Perovskite photovoltaics has achieved conversion efficiencies of 26.0% by optimizing the optoelectronic properties of the absorber and its interfaces with charge transport layers (CTLs). However, commonly adopted organic CTLs can lead to parasitic absorption and device instability. Therefore, metal oxides like atomic layer-deposited (ALD) SnO2 in combination with fullerene-based electron transport layers have been introduced to enhance mechanical and thermal stability. Instead, when ALD SnO2 is directly processed on the absorber, i.e., without the fullerene layer, chemical modifications of the inorganic fraction of the perovskite occur, compromising the device performance. This study focuses on the organic fraction, particularly the formamidinium cation (FA+), in a CsFAPb(I,Br)3 perovskite. By employing in situ infrared spectroscopy, we investigate the impact of ALD processing on the perovskite, such as vacuum level, temperature, and exposure to half and full ALD cycles using tetrakis(dimethylamido)-Sn(IV) (TDMA-Sn) and H2O. We observe that exposing the absorber to vacuum conditions or water half-cycles has a negligible effect on the chemistry of the perovskite. However, prolonged exposure at 100 °C for 90 min results in a loss of 0.7% of the total formamidinium-related vibrational features compared to the pristine perovskite. Supported by density functional theory calculations, we speculate that FA+ deprotonates and that formamidine desorbs from the perovskite surface. Furthermore, the interaction between TDMA-Sn and FA+ induces more decomposition of the perovskite surface compared to vacuum, temperature, or H2O exposure. During the exposure to 10 ALD half-cycles of TDMA-Sn, 4% of the total FA+-related infrared features are lost compared to the pristine perovskite. Additionally, IR spectroscopy suggests the formation and trapping of sym-triazine, i.e., a decomposition product of FA+. These studies enable to decouple the effects occurring during direct ALD processing on the perovskite and highlight the crucial role of the Sn precursor in affecting the perovskite surface chemistry and compromising the device performance.

Optical Simulation-Aided Design and Engineering of Monolithic Perovskite/Silicon Tandem Solar Cells.

Monolithic perovskite/c-Si tandem solar cells have attracted enormous research attention and have achieved efficiencies above 30%. This work describes the development of monolithic tandem solar cells based on silicon heterojunction (SHJ) bottom- and perovskite top-cells and highlights light management techniques assisted by optical simulation. We first engineered (i)a-Si:H passivating layers for (100)-oriented flat c-Si surfaces and combined them with various (n)a-Si:H, (n)nc-Si:H, and (n)nc-SiOx:H interfacial layers for SHJ bottom-cells. In a symmetrical configuration, a long minority carrier lifetime of 16.9 ms was achieved when combining (i)a-Si:H bilayers with (n)nc-Si:H (extracted at the minority carrier density of 1015 cm-3). The perovskite sub-cell uses a photostable mixed-halide composition and surface passivation strategies to minimize energetic losses at charge-transport interfaces. This allows tandem efficiencies above 23% (a maximum of 24.6%) to be achieved using all three types of (n)-layers. Observations from experimentally prepared devices and optical simulations indicate that both (n)nc-SiOx:H and (n)nc-Si:H are promising for use in high-efficiency tandem solar cells. This is possible due to minimized reflection at the interfaces between the perovskite and SHJ sub-cells by optimized interference effects, demonstrating the applicability of such light management techniques to various tandem structures.

Spatial atmospheric pressure molecular layer deposition of alucone films using dimethylaluminum isopropoxide as the precursor.

Trimethylaluminum is the most used aluminum precursor in atomic and molecular layer deposition (ALD/MLD). It provides high growth-per-cycle (GPC), is highly reactive and is relatively low cost. However, in the deposition of hybrid alucone films, TMA tends to infiltrate into the films requiring very long purge steps and thereby limiting the deposition rate (nm s-1) of the process. From our previous studies, we know that dimethylaluminum isopropoxide (DMAI) could be a potential candidate to substitute TMA in alucone depositions as it does not seem to infiltrate into the films. In this study, we perform a more detailed investigation of MLD of alucone on an atmospheric pressure spatial MLD system using DMAI as the aluminum precursor. The effect of deposition temperature and reactant purge times on the overall GPC has been investigated and a decreasing GPC with increasing deposition temperature and increasing EG purge time has been observed. Furthermore, the DMAI alucone films have been compared for their chemical environment and degradation with the films prepared using TMA and EG, showing striking similarities between the two. The results demonstrate that DMAI can be used as an alternative precursor to TMA for MLD of alucone films and this work can be used as a guide for designing efficient MLD processes in the future.

Enhanced Self-Assembled Monolayer Surface Coverage by ALD NiO in p-i-n Perovskite Solar Cells.

Metal halide perovskites have attracted tremendous attention due to their excellent electronic properties. Recent advancements in device performance and stability of perovskite solar cells (PSCs) have been achieved with the application of self-assembled monolayers (SAMs), serving as stand-alone hole transport layers in the p-i-n architecture. Specifically, phosphonic acid SAMs, directly functionalizing indium-tin oxide (ITO), are presently adopted for highly efficient devices. Despite their successes, so far, little is known about the surface coverage of SAMs on ITO used in PSCs application, which can affect the device performance, as non-covered areas can result in shunting or low open-circuit voltage. In this study, we investigate the surface coverage of SAMs on ITO and observe that the SAM of MeO-2PACz ([2-(3,6-dimethoxy-9H-carbazol-9-yl)ethyl]phosphonic acid) inhomogeneously covers the ITO substrate. Instead, when adopting an intermediate layer of NiO between ITO and the SAM, the homogeneity, and hence the surface coverage of the SAM, improve. In this work, NiO is processed by plasma-assisted atomic layer deposition (ALD) with Ni(MeCp)2 as the precursor and O2 plasma as the co-reactant. Specifically, the presence of ALD NiO leads to a homogeneous distribution of SAM molecules on the metal oxide area, accompanied by a high shunt resistance in the devices with respect to those with SAM directly processed on ITO. At the same time, the SAM is key to the improvement of the open-circuit voltage of NiO + MeO-2PACz devices compared to those with NiO alone. Thus, the combination of NiO and SAM results in a narrower distribution of device performance reaching a more than 20% efficient champion device. The enhancement of SAM coverage in the presence of NiO is corroborated by several characterization techniques including advanced imaging by transmission electron microscopy (TEM), elemental composition quantification by Rutherford backscattering spectrometry (RBS), and conductive atomic force microscopy (c-AFM) mapping. We believe this finding will further promote the usage of phosphonic acid based SAM molecules in perovskite PV.

Atomic insights into the oxygen incorporation in atomic layer deposited conductive nitrides and its mitigation by energetic ions.

Oxygen is often detected as impurity in metal and metal nitride films prepared by atomic layer deposition (ALD) and its presence has profound and adverse effects on the material properties. In this work, we present the case study of HfNx films prepared by plasma-assisted ALD by alternating exposures of CpHf(NMe2)3 and H2 plasma. First, we identify the primary source of O contamination in the film. Specifically, we find that the extent of O incorporation in HfNx films is determined by the flux of background H2O/O2 residual gases reaching the HfNx surface during the ALD process and leads to the formation of Hf-O bonds. Then, we report on the decrease in the concentration of Hf-O bonds in the film upon application of an external radiofrequency (rf) substrate bias during the H2 plasma step. The experimental work is accompanied by first principles calculations to gain insights into the O incorporation and its mitigation upon the impingement of energetic ions on the surface. Specifically, we find that the dissociative binding of H2O on a bare HfN surface is highly favored, resulting in surface Hf-OH groups and concomitant increase in the oxidation state of Hf. We also show that energetic cations (H+, H2+ and H3+) lead to the dissociation of surface Hf-OH bonds, H2O formation, and its subsequent desorption from the surface. The latter is followed by reduction of the Hf oxidation state, presumably by H˙ radicals. The atomic-level understanding obtained in this work on O incorporation and its abstraction are expected to be crucial to prevent O impurities in the HfNx films and contribute to the fabrication of other technologically relevant low resistivity ALD-grown transition metal nitride films.

Electrochemical Activation of Atomic Layer-Deposited Cobalt Phosphate Electrocatalysts for Water Oxidation.

The development of efficient and stable earth-abundant water oxidation catalysts is vital for economically feasible water-splitting systems. Cobalt phosphate (CoPi)-based catalysts belong to the relevant class of nonprecious electrocatalysts studied for the oxygen evolution reaction (OER). In this work, an in-depth investigation of the electrochemical activation of CoPi-based electrocatalysts by cyclic voltammetry (CV) is presented. Atomic layer deposition (ALD) is adopted because it enables the synthesis of CoPi films with cobalt-to-phosphorous ratios between 1.4 and 1.9. It is shown that the pristine chemical composition of the CoPi film strongly influences its OER activity in the early stages of the activation process as well as after prolonged exposure to the electrolyte. The best performing CoPi catalyst, displaying a current density of 3.9 mA cm-2 at 1.8 V versus reversible hydrogen electrode and a Tafel slope of 155 mV/dec at pH 8.0, is selected for an in-depth study of the evolution of its electrochemical properties, chemical composition, and electrochemical active surface area (ECSA) during the activation process. Upon the increase of the number of CV cycles, the OER performance increases, in parallel with the development of a noncatalytic wave in the CV scan, which points out to the reversible oxidation of Co2+ species to Co3+ species. X-ray photoelectron spectroscopy and Rutherford backscattering measurements indicate that phosphorous progressively leaches out the CoPi film bulk upon prolonged exposure to the electrolyte. In parallel, the ECSA of the films increases by up to a factor of 40, depending on the initial stoichiometry. The ECSA of the activated CoPi films shows a universal linear correlation with the OER activity for the whole range of CoPi chemical composition. It can be concluded that the adoption of ALD in CoPi-based electrocatalysis enables, next to the well-established control over film growth and properties, to disclose the mechanisms behind the CoPi electrocatalyst activation.

Proton Radiation Hardness of Perovskite Tandem Photovoltaics.

Monolithic [Cs0.05(MA0. 17FA0. 83)0.95]Pb(I0.83Br0.17)3/Cu(In,Ga)Se2 (perovskite/CIGS) tandem solar cells promise high performance and can be processed on flexible substrates, enabling cost-efficient and ultra-lightweight space photovoltaics with power-to-weight and power-to-cost ratios surpassing those of state-of-the-art III-V semiconductor-based multijunctions. However, to become a viable space technology, the full tandem stack must withstand the harsh radiation environments in space. Here, we design tailored operando and ex situ measurements to show that perovskite/CIGS cells retain over 85% of their initial efficiency even after 68 MeV proton irradiation at a dose of 2 × 1012 p+/cm2. We use photoluminescence microscopy to show that the local quasi-Fermi-level splitting of the perovskite top cell is unaffected. We identify that the efficiency losses arise primarily from increased recombination in the CIGS bottom cell and the nickel-oxide-based recombination contact. These results are corroborated by measurements of monolithic perovskite/silicon-heterojunction cells, which severely degrade to 1% of their initial efficiency due to radiation-induced recombination centers in silicon.

On the role of micro-porosity in affecting the environmental stability of atomic/molecular layer deposited (ZnO)a(Zn-O-C6H4-O)b films.

Atomic/molecular layer deposited (ALD/MLD) inorganic-organic thin films form a novel class of materials with tunable properties. In selected cases, hybrid materials are reported to show environmental instability, specifically towards moisture. In this article, we focus on zinc oxide/zincone multi-layers with the theoretical formula of (ZnO)a(Zn-O-C6H4-O)b. We show by means of ellipsometric porosimetry that micro-porosity in the range of 0.42 and 2 nm in the pristine zincone layer is responsible for its environmental degradation. During degradation, it is found that a relative micro-porosity content of 1.2 ± 0.1 vol% in the pristine zincone films evolves into micro-mesoporosity with a relative content of 39 ± 1 vol%. We also show that the micro-porosity in the zincone layer can be gradually suppressed when few cycles (a = 1-10) of ZnO are introduced. The resulting (ZnO)a(Zn-O-C6H4-O)b = 1 periodic multilayer is an environmentally stable film with a = 10. It is found that the suppressed micro-porosity is due to the development of continuous ZnO layers with a≥ 10.

Chemical Analysis of the Interface between Hybrid Organic-Inorganic Perovskite and Atomic Layer Deposited Al2O3.

Ultrathin metal oxides prepared by atomic layer deposition (ALD) have gained utmost attention as moisture and thermal stress barrier layers in perovskite solar cells (PSCs). We have recently shown that 10 cycles of ALD Al2O3 deposited directly on top of the CH3NH3PbI3- xCl x perovskite material, are effective in delivering a superior PSC performance with 18% efficiency (compared to 15% of the Al2O3-free cell) with a long-term humidity-stability of more than 60 days. Motivated by these results, the present contribution focuses on the chemical modification which the CH3NH3PbI3- xCl x perovskite undergoes upon growth of ALD Al2O3. Specifically, we combine in situ Infrared (IR) spectroscopy studies during film growth, together with X-ray photoelectron spectroscopy (XPS) analysis of the ALD Al2O3/perovskite interface. The IR-active signature of the NH3+ stretching mode of the perovskite undergoes minimal changes upon exposure to ALD cycles, suggesting no diffusion of ALD precursor and co-reactant (Al(CH3)3 and H2O) into the bulk of the perovskite. However, by analyzing the difference between the IR spectra associated with the Al2O3 coated perovskite and the pristine perovskite, respectively, changes occurring at the surface of perovskite are monitored. The abstraction of either NH3 or CH3NH2 from the perovskite surface is observed as deduced by the development of negative N-H bands associated with its stretching and bending modes. The IR investigations are corroborated by XPS study, confirming the abstraction of CH3NH2 from the perovskite surface, whereas no oxidation of its inorganic framework is observed within the ALD window process investigated in this work. In parallel, the growth of ALD Al2O3 on perovskite is witnessed by the appearance of characteristic IR-active Al-O-Al phonon and (OH)-Al═O stretching modes. Based on the IR and XPS investigations, a plausible growth mechanism of ALD Al2O3 on top of perovskite is presented.

Low-Temperature Plasma-Assisted Atomic-Layer-Deposited SnO2 as an Electron Transport Layer in Planar Perovskite Solar Cells.

In this work, we present an extensive characterization of plasma-assisted atomic-layer-deposited SnO2 layers, with the aim of identifying key material properties of SnO2 to serve as an efficient electron transport layer in perovskite solar cells (PSCs). Electrically resistive SnO2 films are fabricated at 50 °C, while a SnO2 film with a low electrical resistivity of 1.8 × 10-3 Ω cm, a carrier density of 9.6 × 1019 cm-3, and a high mobility of 36.0 cm2/V s is deposited at 200 °C. Ultraviolet photoelectron spectroscopy indicates a conduction band offset of ∼0.69 eV at the 50 °C SnO2/Cs0.05(MA0.17FA0.83)0.95Pb(I2.7Br0.3) interface. In contrast, a negligible conduction band offset is found between the 200 °C SnO2 and the perovskite. Surprisingly, comparable initial power conversion efficiencies (PCEs) of 17.5 and 17.8% are demonstrated for the champion cells using 15 nm thick SnO2 deposited at 50 and 200 °C, respectively. The latter gains in fill factor but loses in open-circuit voltage. Markedly, PSCs using the 200 °C compact SnO2 retain their initial performance at the maximum power point over 16 h under continuous one-sun illumination in inert atmosphere. Instead, the cell with the 50 °C SnO2 shows a decrease in PCE of approximately 50%.

Characterization of nano-porosity in molecular layer deposited films.

Molecular layer deposition (MLD) delivers (ultra-) thin organic and hybrid materials, with atomic-level thickness control. However, such layers are often reported to be unstable under ambient conditions, due to the interaction of water and oxygen with the hybrid structure, consequently limiting their applications. In this contribution, we investigate the impact of porosity in MLD layers on their degradation. Alucone layers were deposited by means of trimethylaluminium and ethylene glycol, adopting both temporal and spatial MLD and characterized by means of FT-IR spectroscopy, spectroscopic ellipsometry, and ellipsometric porosimetry. The highest growth per cycle (GPC) achieved by spatial MLD resulted in alucone layers with very low stability in ambient air, leading to their conversion to AlOx. Alucones deposited by means of temporal MLD, instead, showed a lower GPC and a higher ambient stability. Ellipsometric porosimetry showed the presence of open nano-porosity in pristine alucone layers. Pores with a diameter in the range of 0.42-2 nm were probed, with a relative content between 1.5% and 5%, respectively, which are attributed to the temporal and spatial MLD layers. We concluded that a correlation exists between the process GPC, the open-porosity relative content, and the degradation of alucone layers.

Tuning Material Properties of Oxides and Nitrides by Substrate Biasing during Plasma-Enhanced Atomic Layer Deposition on Planar and 3D Substrate Topographies.

Oxide and nitride thin-films of Ti, Hf, and Si serve numerous applications owing to the diverse range of their material properties. It is therefore imperative to have proper control over these properties during materials processing. Ion-surface interactions during plasma processing techniques can influence the properties of a growing film. In this work, we investigated the effects of controlling ion characteristics (energy, dose) on the properties of the aforementioned materials during plasma-enhanced atomic layer deposition (PEALD) on planar and 3D substrate topographies. We used a 200 mm remote PEALD system equipped with substrate biasing to control the energy and dose of ions by varying the magnitude and duration of the applied bias, respectively, during plasma exposure. Implementing substrate biasing in these forms enhanced PEALD process capability by providing two additional parameters for tuning a wide range of material properties. Below the regimes of ion-induced degradation, enhancing ion energies with substrate biasing during PEALD increased the refractive index and mass density of TiO x and HfO x and enabled control over their crystalline properties. PEALD of these oxides with substrate biasing at 150 °C led to the formation of crystalline material at the low temperature, which would otherwise yield amorphous films for deposition without biasing. Enhanced ion energies drastically reduced the resistivity of conductive TiN x and HfN x films. Furthermore, biasing during PEALD enabled the residual stress of these materials to be altered from tensile to compressive. The properties of SiO x were slightly improved whereas those of SiN x were degraded as a function of substrate biasing. PEALD on 3D trench nanostructures with biasing induced differing film properties at different regions of the 3D substrate. On the basis of the results presented herein, prospects afforded by the implementation of this technique during PEALD, such as enabling new routes for topographically selective deposition on 3D substrates, are discussed.

Low temperature growth of gallium oxide thin films via plasma enhanced atomic layer deposition.

Herein we describe an efficient low temperature (60-160 °C) plasma enhanced atomic layer deposition (PEALD) process for gallium oxide (Ga2O3) thin films using hexakis(dimethylamido)digallium [Ga(NMe2)3]2 with oxygen (O2) plasma on Si(100). The use of O2 plasma was found to have a significant improvement on the growth rate and deposition temperature when compared to former Ga2O3 processes. The process yielded the second highest growth rates (1.5 Å per cycle) in terms of Ga2O3 ALD and the lowest temperature to date for the ALD growth of Ga2O3 and typical ALD characteristics were determined. From in situ quartz crystal microbalance (QCM) studies and ex situ ellipsometry measurements, it was deduced that the process is initially substrate-inhibited. Complementary analytical techniques were employed to investigate the crystallinity (grazing-incidence X-ray diffraction), composition (Rutherford backscattering analysis/nuclear reaction analysis/X-ray photoelectron spectroscopy), morphology (X-ray reflectivity/atomic force microscopy) which revealed the formation of amorphous, homogeneous and nearly stoichiometric Ga2O3 thin films of high purity (carbon and nitrogen <2 at.%) under optimised process conditions. Tauc plots obtained via UV-Vis spectroscopy yielded a band gap of 4.9 eV and the transmittance values were more than 80%. Upon annealing at 1000 °C, the transformation to oxygen rich polycrystalline ß-gallium oxide took place, which also resulted in the densification and roughening of the layer, accompanied by a slight reduction in the band gap. This work outlines a fast and efficient method for the low temperature ALD growth of Ga2O3 thin films and provides the means to deposit Ga2O3 upon thermally sensitive polymers like polyethylene terephthalate.

Dynamic Ellipsometric Porosimetry Investigation of Permeation Pathways in Moisture Barrier Layers on Polymers.

The quality assessment of moisture permeation barrier layers needs to include both water permeation pathways, namely through bulk nanoporosity and local macroscale defects. Ellipsometric porosimetry (EP) has been already demonstrated a valuable tool for the identification of nanoporosity in inorganic thin film barriers, but the intrinsic lack of sensitivity toward the detection of macroscale defects prevents the overall barrier characterization. In this contribution, dynamic EP measurements are reported and shown to be sensitive to the detection of macroscale defects in SiO2 layers on polyethylene naphthalate substrate. In detail, the infiltration of probe molecules, leading to changes in optical properties of the polymeric substrate, is followed in time and related to permeation through macroscale defects.

Metal-Organic Covalent Network Chemical Vapor Deposition for Gas Separation.

The chemical vapor deposition (CVD) polymerization of metalloporphyrin building units is demonstrated to provide an easily up-scalable one-step method toward the deposition of a new class of dense and defect-free metal-organic covalent network (MOCN) layers. The resulting hyper-thin and flexible MOCN layers exhibit outstanding gas-separation performances for multiple gas pairs.

Low-Temperature Plasma-Assisted Atomic Layer Deposition of Silicon Nitride Moisture Permeation Barrier Layers.

Encapsulation of organic (opto-)electronic devices, such as organic light-emitting diodes (OLEDs), photovoltaic cells, and field-effect transistors, is required to minimize device degradation induced by moisture and oxygen ingress. SiNx moisture permeation barriers have been fabricated using a very recently developed low-temperature plasma-assisted atomic layer deposition (ALD) approach, consisting of half-reactions of the substrate with the precursor SiH2(NH(t)Bu)2 and with N2-fed plasma. The deposited films have been characterized in terms of their refractive index and chemical composition by spectroscopic ellipsometry (SE), X-ray photoelectron spectroscopy (XPS), and Fourier-transform infrared spectroscopy (FTIR). The SiNx thin-film refractive index ranges from 1.80 to 1.90 for films deposited at 80 °C up to 200 °C, respectively, and the C, O, and H impurity levels decrease when the deposition temperature increases. The relative open porosity content of the layers has been studied by means of multisolvent ellipsometric porosimetry (EP), adopting three solvents with different kinetic diameters: water (∼0.3 nm), ethanol (∼0.4 nm), and toluene (∼0.6 nm). Irrespective of the deposition temperature, and hence the impurity content in the SiNx films, no uptake of any adsorptive has been observed, pointing to the absence of open pores larger than 0.3 nm in diameter. Instead, multilayer development has been observed, leading to type II isotherms that, according to the IUPAC classification, are characteristic of nonporous layers. The calcium test has been performed in a climate chamber at 20 °C and 50% relative humidity to determine the intrinsic water vapor transmission rate (WVTR) of SiNx barriers deposited at 120 °C. Intrinsic WVTR values in the range of 10(-6) g/m2/day indicate excellent barrier properties for ALD SiNx layers as thin as 10 nm, competing with that of state-of-the-art plasma-enhanced chemical vapor-deposited SiNx layers of a few hundred nanometers in thickness.