Cation Interdiffusion Research Articles

Investigation of sub-nm binary oxidic surface modifications on mixed ionic electronic conductors with ToF-SIMS: Oxidic overlayer stability and ionic interdiffusion behavior

Modifications of mixed ionic electronic conductor (MIEC) surfaces are a promising approach to improve oxygen exchange reaction (OER) kinetics and can have a tremendous impact on surface charges and secondary ion yields. Utilizing time-of-flight secondary ion mass spectrometry (ToF-SIMS), we examined degradation, segregation, and cation interdiffusion behaviors on La0.6Sr0.4CoO3-δ (LSC) and Pr0.2Ce0.8O2-δ (PCO) thin films modified with ∼0.5 nm CaO, TiO2, and SnO2 overlayers after annealing at 700 °C and 800 °C, respectively. Surface profiles (AFM; ToF-SIMS) and depth profiles (ToF-SIMS) revealed structural and chemical transformations, including particle formation and surface roughening. The overlayer stability varied significantly for different overlayers on the same material and for the same overlayer on LSC and PCO. All oxidic overlayers were more stable on PCO than LSC. Depth profiling indicated that 40Ca+ ions penetrated the entire LSC and PCO layers (30 nm). 48Ti+ aligns more accurately with a typical analytical solution to Fick’s diffusion equation for finite systems, showing higher diffusion coefficients in LSC than PCO. 120Sn+ exhibited minimal penetration, indicating high stability on the surface and less intermixing with either MIEC. These results hint at the need to differentiate between the stability of the binary oxides on the surface and the bulk diffusivity.

Role of Ag Addition on the Microscopic Material Properties of (Ag,Cu)(In,Ga)Se2 Absorbers and Their Effects on Losses in the Open‐Circuit Voltage of Corresponding Devices

ABSTRACTAg alloying of Cu(In,Ga)Se2 (CIGSe) absorbers in thin‐film solar cells leads to improved crystallization of these absorber layers at lower substrate temperatures than for Ag‐free CIGSe thin films as well as to enhanced cation interdiffusion, resulting in reduced Ga/In gradients. However, the role of Ag in the microscopic structure–property relationships in the (Ag,Cu)(In,Ga)Se2 thin‐film solar cells as well as a correlation between the various microscopic properties of the polycrystalline ACIGSe absorber and open‐circuit voltage of the corresponding solar cell device has not been reported earlier. In the present work, we study the effect of Ag addition by analyzing the differences in the various bulk, grain‐boundary, optoelectronic, emission, and absorption‐edge properties of ACIGSe absorbers with that of a reference CIGSe absorber. By comparing thin‐film solar cells with similar band‐gap energies ranging from about 1.1 to about 1.2 eV, we were able to correlate the differences in their absorber material properties with the differences in the device performance of the corresponding solar cells. Various microscopic origins of open‐circuit voltage losses were identified, such as strong Ga/In gradients and local compositional variations within individual grains of ACIGSe layers, which are linked to absorption‐edge broadening, lateral fluctuations in luminescence‐energy distribution, and band tailing, thus contributing to radiative VOC losses. A correlation established between the effective electron lifetime, average grain size, and lifetime at the grain boundaries indicates that enhanced nonradiative recombination at grain boundaries is a major contributor to the overall VOC deficit in ACIGSe solar cells. Although the alloying with Ag has been effective in increasing the grain size and the effective electron lifetime, still, the Ga/In gradients and the grain‐boundary recombination in the ACIGSe absorbers must be reduced further to improve the solar‐cell performance.

Self-assembled Sm0.5Sr0.5CoO3-δ-Ce0.8Sm0.2O2-δ composite for solid oxide electrolysis cells

The anode is the key material that constrains the performance of solid oxide electrolysis cells (SOECs). Here, we have developed self-assembled Sm0.5Sr0.5CoO3-δ-Ce0.8Sm0.2O2-δ (SSC-SDC) composite by the co-synthesis strategy and studied its electrochemical performance as the anode for SOECs. The surface and interface properties of the self-assembled SSC-SDC composite were systematically studied. The SDC lattice expansion and the SSC lattice contraction of the SSC-SDC composite have been shown by XRD analysis, ascribed to the strong cation interdiffusion during the self-assembly process. The self-assembled SSC-SDC also exhibits superior oxygen evolution activity and displays a larger oxygen desorption peak than the physically mixed SSC&SDC. A higher proportion of adsorbed oxygen species on the surface of the self-assembled SSC-SDC than the physically mixed SSC&SDC also have been shown by XPS results. The cell with the self-assembled SSC-SDC as anode exhibits ca. 2.1 times higher current density than the physically mixed SSC&SDC as anode. Meanwhile, the polarization resistance of the cell with self-assembled SSC-SDC as the anode is 0.0957 Ω cm2, which is only 40 % of that observed in the cell where SSC and SDC are physically mixed as the anode. This novel self-assembly strategy shows great potential for preparing high-performance oxygen electrodes.

Holistic view on cation interdiffusion during processing and operation of garnet all-solid-state batteries

All-solid-state batteries based on the active cathode material LiCoO2 (LCO), a garnet-type Li7La3Zr2O12 (LLZO) electrolyte and a Li-metal anode are attracting a lot of attention as a robust and safe alternative to conventional lithium-ion batteries. The challenges in the practical realization of such cells are related to high-temperature sintering, which compacts the ceramic powder but also leads to undesirable material interactions such as cation interdiffusion and secondary phase formation. Even if high initial capacities can be achieved, the all-inorganic cells suffer from a strong capacity drop due to various degradation phenomena during processing and operation, which are not yet fully understood. In this study, the thermodynamic and kinetic aspects of co-sintering as well as the structural evolution of materials and interfaces during processing and operation of co-sintered LCO-LLZO cathodes are investigated in detail. A thermodynamic model for the interdiffusion of cations is derived and the effects of the diffusion of Al- and Co-ions, which occurs during the processing and cycling of the cells, are investigated. In LLZO, the diffusion of 0.13 Co per formula unit (pfu) has a negligible effect on ionic and electronic conductivity and electrochemical stability. In contrast, the substitution of 0.01 pfu Al and the induced disorder in the layer structure of LCO increases the polarization during cycling. All-inorganic cells fabricated with optimized sintering parameters to minimize interdiffusion between LCO and LLZO show good initial performance but similar degradation during cycling, as the used processing parameters result in a more porous microstructure leading to the development of cracks along the LLZO/LCO interface. The results obtained highlight the inherent instabilities of all-ceramic cathodes with unprotected LCO/LLZO interfaces, which require precise tuning of materials and processing parameters to achieve both high mechanical stability and low interdiffusion.

Synthesis and characteristics of densified GDC-LSO composite as a new apatite-based electrolyte for intermediate-temperature solid oxide fuel cells (IT-SOFC)

Developing solid-state ionic conductors with desirable charge-transport efficiency and reasonable durability is a fundamental and long-lasting challenge for solid-oxide fuel cells (SOFCs). Ceria-based electrolytes, as one of the most common types of electrolytes for intermediate-temperature solid-oxide fuel cells (IT-SOFCs), offer a high surface-exchange coefficient and faster kinetics in the triple phase boundaries (TPBs); however, they suffer to some extent of electronic conductivity in the reducing atmosphere and gradual phase transitions. Here in this work, we have reported a novel co-doped IT-SOFC electrolyte composite combining the apatite structure of Lanthanum Silicate (LSO) with the fluorite structure of Gadolinium-doped Ceria (GDC), which showed a high ionic conductivity and a minimal electronic leak. The resulting GDC-LSO composite electrolyte also achieved an OCV (open-circuit voltage) of 1 V at 800 °C, implying a significant improvement in the OCV values reported for the typical ceria-based electrolytes (∼0.75 V). The sample was prepared using 40 wt% GDC and 60 wt% LSO (40GDC-60LSO) showed a maximum electrical conductivity of 25 mS cm−1 at 800 °C with good densification properties (>95 % relative density). The cell electrochemical performance measurement was conducted using a 3.0 vol% humified H2 stream at the anode side while the cathode side was exposed to the air at 800 °C. The interdiffusion of cations between La3+ in the LSO phase and Ce4+ and Gd3+ in the GDC phase was detected by XRD and EDX results after sintering samples at 1500 °C for 4 h using 0.5 wt% PVA or 0.5 wt% Ethyl cellulose (EC) as the binder. The proposed GDC-LSO composite could help better understand the influence of compositional constituents and processing variables on the densification and electrical properties of the electrolyte materials for the IT-SOFCs.

Unraveling the pivotal role of heterointerfaces on oxide ion transport in solid oxide fuel cells

Overcoming fundamental key issues affecting performance and stability has been recognized as the most important challenge for the commercialization of solid oxide fuel cells (SOFCs). Here, we employed a multipronged approach based on advanced nanoscale analyses coupled with electrochemical evaluation to elucidate the interrelation among ohmic resistance, oxide ion transport, and cation interdiffusion mainly occurring at the interlayer-electrolyte heterointerfaces. The presence of an interdiffusion layer (IDL), formed from the interdiffusion of Ce, Gd, and Zr during high-temperature sintering of conventional screen-printed gadolinia-doped ceria (GDC) interlayer on yttria-stabilized zirconia (YSZ) electrolyte, inadvertently acts as a major barrier to oxide ion transport and results in a significant increase of the ohmic resistance. An effective way to suppress the IDL formation and its oxide ion blocking effect is by alternatively fabricating the GDC interlayer using pulsed laser deposition (PLD), whereby dense layers prepared at a relatively lower deposition temperature without post-growth sintering can be obtained. Consequently, the cell's ohmic resistance is drastically lowered and a significant improvement in cell performance is achieved. These results have major implications for the selection and optimization of cell fabrication processes to mitigate degradation issues associated to heterointerfaces.

Interface Diffusion and Compatibility of (Ba,La)FeO3-δ Perovskite Electrodes in Contact with Barium Zirconate and Ceria.

Ba1-xLaxFeO3-δ perovskites (BLF) capable of conducting electrons, protons, and oxygen ions are promising oxygen electrodes for efficient solid oxide cells (fuel cells or electrolyzers), an integral part of prospected large-scale power-to-gas energy storage systems. We investigated the compatibility of BLF with lanthanum content between 5 and 50%, in contact with oxide-ion-conducting Ce0.8Gd0.2O2-δ and proton-conducting BaZr0.825Y0.175O3-δ electrolytes, annealing the electrode-electrolyte bilayers at high temperature to simulate thermal stresses of fabrication and prolonged operation. By employing both bulk X-ray diffraction and synchrotron X-ray microspectroscopy, we present a space-resolved picture of the interaction between electrode and electrolyte as what concerns cation interdiffusion, exsolution, and phase stability. We found that the phase stability of BLF in contact with other phases is correlated with the Goldschmidt tolerance factor, in turn determined by the La/Ba ratio, and appropriate doping strategies with oversized cations (Zn2+, Y3+) could improve structural stability. While extensive reactivity and/or interdiffusion was often observed, we put forward that most products of interfacial reactions, including proton-conducting Ba(Ce,Gd)O3-δ and mixed-conducting (Ba,La)(Fe,Zr,Y)O3-δ, may not be very detrimental for practical cell operation.

Heuristic Approach to Predict the Performance Degradation of a Solid Oxide Fuel Cell Cathode.

The present work aims to predict the degradation in the performance of a solid oxide fuel cell (SOFC) cathode owing to cation interdiffusion between the electrolyte and cathode and surface segregation. Cation migration in the (La0.60Sr0.40)0.95Co0.20Fe0.80O3-x (LSCF)-Gd0.10Ce0.90O1.95 (GDC) composite cathode is evaluated in relation to time up to 1000 h using scanning transmission electron microscopy (STEM)-energy-dispersive X-ray spectroscopy (EDXS). The resulting insulating phase formed within the GDC interlayer is quantified by means of the volume fraction using a two-dimensional (2D) image analysis technique. For the very first time, the amount of the insulating phase in the GDC interlayer is quantified, and the corresponding performance degradation of the LSCF cathode is predicted. Mathematical relationships are established for the estimation of degradation due to surface segregation of the cathode. The ohmic resistance between the cathode and the GDC interlayer/electrolyte interface and the polarization resistance of the cathode, characterized by electrochemical impedance spectroscopy (EIS), show an excellent match with the predicted results. The combined degradation analysis and modeling for the cathode lifetime prediction provide a systematic understanding of the time-dependent cation migration and segregation behavior.

Structural and magnetic properties of YIG thin films deposited by pulsed laser deposition and RF magnetron sputtering technique

Yttrium iron garnet (YIG) has been extensively explored for its potential avenues in spintronic applications. A majority of these studies employ thin films grown by PLD at high substrate temperature, which generally leads to an interfacial dead layer with cations interdiffusion hindering their technological implications. In this communication, we report the growth of YIG thin films at room temperature by PLD and RF sputtering techniques. Detailed structural investigation confirms the thin films’ single-phase growth and epitaxial nature. We have a further detailed investigation of magnetic properties by dc magnetization, magneto-optical Kerr effect and FMR techniques. Although our thin films exhibit a comparatively lower magnetic performance in terms of saturation magnetization and damping constant, we have obtained a significantly lower interfacial dead layer thickness of ∼1 nm, which is quite promising for spin transport applications. The present study, therefore, calls for future studies for simultaneous optimization of magnetic performance and interfacial dead layer with room temperature grown YIG thin films by both PLD and RF sputtering methods.

Nanostructured LSC Thin Film Electrodes with Improved Electrochemical Performance and Long-Term Stability

Nanostructured La0.6Sr0.4CoO3-δ (LSC) thin film electrodes exhibit exceptionally high oxygen surface exchange properties, surpassing those of conventional microscale electrode structures, which are desirable for application in solid oxide cells (SOC) [1-2]. On the other hand, the LSC nanostructures also tend to undergo significant morphological changes at typically high temperatures required for SOC operation, leading to rapid degradation in performance. Here, towards the goal of improving the long-term stability of electrochemical performance of nanostructured LSC thin films, a systematic investigation of the effect of processing temperatures on long-term stability was carried out [3]. By varying the deposition temperature (500 °C to room temperature), the as-grown characteristic nanostructures of LSC thin films prepared using pulsed laser deposition can be tuned from highly dense nanocolumnar grains to nanofibrous structures with high porosity. Variations in the deposition temperature also resulted to differences in the proportion of surface-bound/lattice-bound Sr and Co2+/Co3+ at the surfaces of the as-grown LSC thin films; however, prolonged annealing at 700 °C in air essentially transforms the surfaces to a final state with mostly lattice-bound Sr and Co3+. Nevertheless, LSC films with initially nanofibrous structures are found to be less prone to the grain sintering effect occurring at high temperatures and exhibit less degradation of the electrode polarization resistance as compared to well-dense films. Using lower deposition temperatures, cation interdiffusion occurring at LSC/GDC interfaces is also significantly suppressed, thus leading to better interfacial stability as compared to those prepared at higher deposition temperatures. These results highlight the relationship between characteristic nanostructures of thin film electrodes and electrochemical performance and provide guidance on designing electrodes with improved long-term stability.[1] J. Januschewsky, M. Ahrens, A. Opitz, F. Kubel and J. Fleig, Adv. Funct. Mater., 2009, 19, 3151–3156.[2] J. Hayd, L. Dieterle, U. Guntow, D. Gerthsen and E. Ivers-Tiffee, J. Power Sources, 2011, 196, 7263–7270.[3] K. Develos-Bagarinao, O. Celikbilek, R. A. Budiman, G. Kerherve, S. Fearn, S. J. Skinner and H. Kishimoto, J. Mater. Chem. A, 10, 2445-2459 (2022).

Atomic-Layer Engineering of La2-xSrxCuO4-La2-xSrxZnO4 Heterostructures.

The fabrication of trilayer superconductor-insulator-superconductor (SIS) Josephson junctions with high-temperature superconductor (HTS) electrodes requires atomically perfect interfaces. Therefore, despite great interest and efforts, this remained a challenge for over three decades. Here, we report the discovery of a new family of metastable materials, La2-xSrxZnO4 (LSZO), synthesized by atomic-layer-by-layer molecular beam epitaxy (ALL-MBE). We show that LSZO is insulating and epitaxially compatible with an HTS compound, La2-xSrxCuO4 (LSCO). Since the "parent" compound La2ZnO4 (LZO) is easier to grow, here we focus on this material as our insulating layer. Growing LZO at very low temperatures to reduce cation interdiffusion makes LSCO/LZO interfaces atomically sharp. We show that in LSCO/LZO/LSCO trilayers, the superconducting properties of the LSCO electrodes remain undiminished, unlike in previous attempts with insulator barriers made of other materials. This opens prospects to produce high-quality HTS tunnel junctions.

Engineering Interface Defects and Interdiffusion at the Degenerate Conductive In2O3/Al2O3 Interface for Stable Electrodes in a Saline Solution.

A low-temperature Al2O3 deposition process provides a simplified method to form a conductive two-dimensional electron gas (2DEG) at the metal oxide/Al2O3 heterointerface. However, the impact of key factors of the interface defects and cation interdiffusion on the interface is still not well understood. Furthermore, there is still a blank space in terms of applications that go beyond the understanding of the interface's electrical conductivity. In this work, we carried out a systematic experimental study by oxygen plasma pretreatment and thermal annealing post-treatment to study the impact of interface defects and cation interdiffusion at the In2O3/Al2O3 interface on the electrical conductance, respectively. Combining the trends in electrical conductance with the structural characteristics, we found that building a sharp interface with a high concentration of interface defects provides a reliable approach to producing such a conductive interface. After applying this conductive interface as electrodes for fabricating a field-effect transistor (FET) device, we found that this interface electrode exhibited ultrastability in phosphate-buffered saline (PBS), a commonly used biological saline solution. This study provides new insights into the formation of conductive 2DEGs at metal oxide/Al2O3 interfaces and lays the foundation for further applications as electrodes in bioelectronic devices.

Combined effect of temperature difference across interface and finite size of the ions on interdiffusion in SOFC

In the present study, the combined effect of the temperature difference across the electrode-electrolyte interface and the finite size of ions non-idealities on the cation interdiffusion is investigated using a mathematical model. Here, we build on and add significantly to our previous work 1 where the study was limited only to the finite effect of ions. Considering each non-ideality/effect separately, the diffusion of manganese (Mn3+) ions decreases about 50 nm for a temperature difference (∆ T) of 50 K, and 31 nm for a finite size parameter ( ν) of 1.826. However, it is decreased by 54 nm considering both effects combindly for ∆ T = 50 K and ν = 1.75. Further, under individual effects, the highest electric potential drop is 0.32 for a ∆ T = 50 K and 0.27 for a ν = 1.75. Under combined effects, the electric potential drop is about 0.85 for ∆ T = 50 K and ν = 1.75. A significant variation is observed in the diffusion of Zr4+, Y3+ and Mn3+ ions and the overall electric potential. It is anticipated that the consideration of these effects/non-idealities will help in the better understanding of cation interdiffusion, and contribute towards performance enhancement of SOFCs.

Perspective and control of cation interdiffusion and interface reactions in solid oxide fuel cells (SOFCs)

Perspective and control of cation interdiffusion and interface reactions in solid oxide fuel cells (SOFCs)

Failure Mechanism and Optimization of Metal-Supported Solid Oxide Fuel Cells.

A solid oxide fuel cell (SOFC) is a clean, efficient energy conversion device with wide fuel applicability. Metal-supported solid oxide fuel cells (MS-SOFCs) exhibit better thermal shock resistance, better machinability, and faster startup than traditional SOFCs, making them more suitable for commercial applications, especially in mobile transportation. However, many challenges remain that hinder the development and application of MS-SOFCs. High temperature may accelerate these challenges. In this paper, the existing problems in MS-SOFCs, including high-temperature oxidation, cationic interdiffusion, thermal matching, and electrolyte defects, as well as lower temperature preparation technologies, including the infiltration method, spraying method, and sintering aids method, are summarized from different perspectives, and the improvement strategy of existing material structure optimization and technology integration is put forward.

Nanostructured LSC Thin Film Electrodes with Improved Electrochemical Performance and Long-Term Stability

Nanostructured La0.6Sr0.4CoO3- δ (LSC) thin film electrodes exhibit exceptionally high oxygen surface exchange properties, surpassing those of conventional microscale electrode structures, which are desirable for application in solid oxide cells (SOCs). Here, towards the goal of improving the long-term stability of electrochemical performance of nanostructured LSC thin films, a systematic investigation of the effect of processing temperatures on long-term stability was carried out. By varying the deposition temperature (from 500 °C to room temperature), the as-grown characteristic nanostructures of LSC thin films prepared using pulsed laser deposition can be tuned from highly dense nanocolumnar grains to nanofibrous structures with high porosity. From the comparison of the properties of the as-grown films and those annealed at 700 °C for 300 h, it was revealed that LSC thin films prepared at lower deposition temperatures are less prone to the grain sintering effect and cation interdiffusion and exhibit better interfacial stability and improved long-term performance.

Spinodal decomposition-derived giant polarization in TiO2–SnO2 generated from a metastable phase

Spinodal decomposition (SD) was incorporated into Nb-doped metastable TiO2–SnO2 to achieve giant interfacial polarization. The dielectric characteristics were analyzed using an equivalent circuit involving electron migration, where the SD bulk is given by the universal dielectric response relation. Both the Nb–TiO2 and the Nb–SnO2 layers showed semiconductive behaviors. With increasing SD treatment temperature, the SD volume fraction increased, as did cation interdiffusion at the SD interface, resulting in a large dielectric loss. The optimal SD temperature was determined as 1100 °C, where the Maxwell–Wagner capacitance showed a very high value of 44.6 μF corresponding to the permittivity at the lowest frequency exceeding 106. Such colossal polarization was considered due to an accumulation of trapped electrons at the Schottky barrier at SD layers with different conductivities.

Facile Dimension Transformation Strategy for Fabrication of Efficient and Stable CsPbI3 Perovskite Solar Cells.

All-inorganic cesium lead triiodide (CsPbI3) perovskite has received increasing attention due to its intrinsic thermal stability and suitable band gap for photovoltaic applications. However, it is difficult to deposit high-quality pure-phase CsPbI3 films using CsI and PbI2 as precursors due to the rapid nucleation and crystal growth by the solution coating method. Here, a simple cation-exchange approach is employed to fabricate all-inorganic 3D CsPbI3 perovskite, where 1D ethylammonium lead (EAPbI3) perovskite is first solution-deposited and then transformed to 3D CsPbI3 via ion exchange between EA+ and Cs+ during thermal annealing. The large space between the PbI3- skeletons in 1D EAPbI3 favors the cation interdiffusion and exchange for the formation of pure-phase 3D CsPbI3 with full compactness and high crystallinity and orientation. The resulting CsPbI3 film exhibits a low trap density of state and high charge mobility, and the perovskite solar cell shows a power-conversion efficiency of 18.2% with enhanced stability. This strategy provides an alternative and promising fabrication route for the fabrication of high-quality all-inorganic perovskite devices.

Implications of Cation Interdiffusion between Double Perovskite Cathode and Proton-Conducting Electrolyte for Performance of Solid Oxide Fuel Cells

Chemical compatibility and cation interdiffusion between the double perovskite cobaltites RBaCo2O6−δ (R = Gd, Pr) and proton-conducting electrolyte BaZr0.8Y0.2O3−δ were studied. Chemical interaction was found to occur already at 1100 °C as a result of the partial dissolution of RBaCo2O6−δ (R = Gd, Pr) in BaZr0.8Y0.2O3−δ. Analysis of the element distribution along the cross sections of diffusion couples RBaCo2O6−δ(R = Gd, Pr)|BaZr0.8Y0.2O3−δ showed strong interdiffusion of cations, with cobalt being the most mobile one. Its diffusion depth in the electrolyte reaches up to several hundreds of micrometers. The addition of NiO as a sintering aid to BaZr0.8Y0.2O3−δ promotes cation diffusion especially through the grain boundary mechanism, increasing the diffusion depth of Co. The possible implications of cation interdiffusion on the performance of proton-conducting SOFCs are discussed based on the results obtained.

Antisite Defects and Chemical Expansion in Low‐damping, High‐magnetization Yttrium Iron Garnet Films

AbstractYttrium iron garnet is widely investigated for its suitability in applications ranging from magneto‐optical and microwave devices to magnonics. However, in the few‐nanometer thickness range, epitaxial films exhibit a strong variability in magnetic behavior that hinders their implementation in technological devices. Here, direct visualization and spectroscopy of the atomic structure of a nominally stoichiometric thin film, exhibiting a small damping factor of 3.0 ⋅ 10−4, reveals the occurrence of Y‐excess octahedral antisite defects. The two‐magnon strength is very small, Γ0≈10−6 Oe, indicating a very low occurrence of scattering centers. Notably, the saturation magnetization, 4πMs=2.10 (±0.01) kOe, is higher than the bulk value, in consistency with the suppression of magnetic moment in the minority octahedral sublattice by the observed antisite defects. Analysis of elemental concentration profiles across the substrate‐film interface suggests that the Y‐excess is originated from unbalanced cationic interdiffusion during the early growth stages.