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Plasma etching is a crucial step in semiconductor manufacturing. High cleanliness and wafer‐to‐wafer reproducibility in the etching chamber are essential in order to successfully achieve nanometer‐sized integrated functions on the wafer. The trend toward the application of more aggressive plasma compositions leads to higher demands on the plasma resistance of the materials used in the etching chamber. Due to its excellent etch resistance, yttrium aluminum garnet Y3Al5O12 (YAG) is starting to replace established materials like SiO2 or Al2O3 in this kind of application. In this study, reactive spark plasma sintering (SPS) was used to manufacture highly dense YAG ceramics from the respective oxides. In addition, yttrium was replaced with heavier lanthanoids (Er, Lu), intending to investigate the role of the A‐site cation in the garnet type structure on the plasma erosion behavior. The produced materials were exposed to fluorine‐based etching plasmas mimicking the conditions in the semiconductor manufacturing apparatus and the erosion behavior was characterized by atomic force microscopy (AFM), secondary ion mass spectrometry (SIMS), transmission electron microscopy (TEM), and profilometry. The induced chemical gradient in the samples is limited to a few nanometers below the surface, which makes its characterization challenging. For advanced analysis, we developed a correlative characterization method combining SIMS and scanning TEM (STEM)–energy‐dispersive spectroscopy (EDS) enabling us to examine the structural and chemical changes in the reaction layer locally resolved. In the case of lanthanoid aluminates, an altered reaction layer and reduced fluorine penetration compared to YAG were found. However, a correlation between the characteristics of the induced chemical gradient and the determined physical erosion rates was not evident. [ABSTRACT FROM AUTHOR]

Using cost‐effective fabrication methods to manufacture a high‐performance solid oxide fuel cell (SOFC) is helpful to enhance the commercial viability. Here, we report an anode‐supported SOFC with a three‐layer Gd0.1Ce0.9O1.95 (gadolinia‐doped‐ceria [GDC])/Y0.148Zr0.852O1.926 (8YSZ)/GDC electrolyte system. The first dense GDC electrolyte is fabricated by co‐sintering a thin, screen‐printed GDC layer with the anode support (NiO–8YSZ substrate and NiO–GDC anode) at 1400°C for 5 h. Subsequently, two electrolyte layers are deposited via physical vapor deposition. The total electrolyte thickness is less than 5 μm in an area of 5 × 5 cm2, enabling an area‐specific ohmic resistance as low as 0.125 Ω cm−2 at 500°C (under open circuit voltage), and contributing to a power density as high as 1.2 W cm−2 at 650°C (at an operating cell voltage of 0.7 V, using humidified [10 vol.% H2O] H2 as fuel and air as oxidant). This work provides an effective strategy and shows the great potential of using GDC as an electrolyte for high‐performance SOFC at intermediate temperature. [ABSTRACT FROM AUTHOR]

Due to the increasing number of applications for ceramic components in reactive etching processes, the interest in the specific erosion behavior of highly etch‐resistant materials like yttrium oxide (Y2O3) has increased in the past years. Despite the large number of investigations already existing in this field, a more general understanding of the erosion mechanisms still lacks due to the limited comparability of these investigations. The huge difference in the kind of etching setups, processing parameters (bias voltage and plasma gas composition), and sample microstructures prevented consistent conclusions so far. To achieve a more general understanding, this study investigates the erosion behavior Y2O3 under a broad spectrum of plasma etching parameters. Therefore, the bias voltage is increased from 50 to 300 V and the plasma gas composition is gradually changed from Ar‐rich to CF4‐rich compositions. This systematic approach allows to directly correlate the morphology changes caused by plasma erosion with the related plasma etching parameters and enables to better understand their influence on the depth of physical and chemical interactions, surface damage, and etching rate. We discovered three distinct erosion regimes, which exhibit specific erosion characteristics. Using these observations, a schematic processing map for Y2O3 was developed, which could help to estimate the severity of the erosion attack dependent on the processing parameters. [ABSTRACT FROM AUTHOR]

Cation doping of Y2O3 is an established approach for tailoring densification and grain growth during sintering. However, the segregation of doped cations to the grain boundary and their impact on processing are still not completely understood. Segregation can be driven by electrostatic effects due to charge mismatch with the host lattice or elastic effects induced by ion size mismatch. While segregation is caused by thermodynamics, it impacts diffusion and the kinetics of grain boundaries during densification and microstructure evolution. In this study, we utilize two isovalent dopants (La3+ and Gd3+), that is we focus on the elastic component of segregation. We investigate the densification as well as the grain growth kinetics of both doped and undoped Y2O3 during field‐assisted sintering/spark plasma sintering (FAST/SPS). While Gd3+ is showing no significant effect on densification, La3+ resulted in a strongly reduced sintering activity. Furthermore, the analysis of the grain growth behavior during sintering and on predensified samples revealed a decrease in the grain growth coefficient, with La3+ having the strongest impact. The structure and chemistry at the grain boundary were observed by aberration‐corrected TEM. While no structural change was caused by doping, the chemical analysis showed a strong segregation of La3+ to the grain boundary, which could not be observed for Gd3+. The results indicate that segregated La3+ causes a drastic decrease in grain boundary migration rates through solute drag as well as much slower sintering kinetics, likely caused by a decrease in the grain boundary self‐diffusion due to segregation. This study further underlines the importance of the elastic contribution to cation segregation and establishes a clear relationship to grain growth and sintering kinetics, which are both decreased by segregation. [ABSTRACT FROM AUTHOR]

The proton conductive material BaCe0.65Zr0.2Y0.15O3−δ has great potential for the separation and purification of hydrogen. However, due to the demanding application conditions regarding both temperature and atmosphere, the elevated temperature structural stability needs to be characterized and warranted. Hence, in this research work, the elevated temperature compressive creep behavior of BaCe0.65Zr0.2Y0.15O3−δ in the temperature regime of 850°C to 1200°C was studied in both air and 4% H2/Ar as a function of the applied stress. The results indicate different creep mechanisms depending on atmosphere and temperature range. While dislocation creep was observed in 4% H2/Ar over the full range, a dislocation creep mechanism was observed in air at temperatures ≤1050°C and a diffusional creep mechanism at temperature ≥1100°C. A detailed microstructural analysis of the post‐creep test specimens revealed that the exposure to oxygen leads to localized stoichiometric changes and a decomposition at the surface. [ABSTRACT FROM AUTHOR]

Ce0.8Gd0.2O2−δ‐FeCo2O4 composites are attractive candidate materials for high‐purity oxygen generation providing robust chemical stability. Aiming for future industrial applications, a feasible solid‐state reaction process with one thermal processing step was used to synthesize 50 wt% Ce0.8Gd0.2O2−δ:50 wt% FeCo2O4 and 85 wt% Ce0.8Gd0.2O2−δ:15 wt% FeCo2O4 composites. Mechanical reliabilities of the sintered membranes were assessed based on the characterized mechanical properties and subcritical crack growth behavior. In general, the fracture strengths of as‐sintered membranes were reduced by tensile residual stresses and microcracks. In particular, the enhanced subcritical crack growth behavior, which leads to limited stress tolerance and high failure probability after a 10‐year operation, was evaluated in more detail. Further materials and processing improvements are needed to eliminate the tensile stress and microcracks to warrant a long‐term reliable operation of the composites. [ABSTRACT FROM AUTHOR]

Submicron Ti2AlC MAX phase powder was synthesized by molten salt shielded synthesis (MS3) using a Ti:Al:C molar ratio of 2:1:0.9 at a process temperature of 1000°C for 5 hours. The synthesized powder presented a mean particle size of ~0.9 µm and a purity of 91 wt. % Ti2AlC, containing 6 wt. % Ti3AlC2. The Ti2AlC powder was sintered by pressureless sintering, achieving a maximal relative density of 90%, hence field‐assisted sintering technology/spark plasma sintering was used to enhance densification. The fine‐grained microstructure was preserved, and phase purity of Ti2AlC was unaltered in the latter case, with a relative density of 98.5%. Oxidation was performed at 1200°C for 50 hours in static air of dense monolithic Ti2AlC with different surface finish, (polished, ground and sandblasted) which resulted in the formation of an approx. 8 µm thin aluminum oxide (Al2O3) layer decorated with titanium dioxide (rutile, TiO2) colonies. Surface quality had no influence on Al2O3 scale thickness, but the amount and size of TiO2 crystals increased with surface roughness. A phenomenon of rumpling of the thermally grown oxide (TGO) was observed and a model to estimate the extent of deformation is proposed. [ABSTRACT FROM AUTHOR]

Even though advanced ceramics are widely applied as consumables in semiconductor etching processes, the erosion mechanisms and connected surface phenomena are not fully understood. Through the interaction with reactive species and ion bombardment during the plasma exposure, oxide ceramic materials like Y2O3 are eroded by a physicochemical mechanism. In this study, fundamental phenomena of surface‐plasma interactions were investigated directly at the surface as well as in the near‐surface region after exposure to fluorine‐based etching plasmas. A straightforward re‐localization technique was used to investigate the microstructural features before and after the plasma exposure for up to 2 hours. Electron microscopy methods (scanning electron microscopy, electron backscatter diffraction) were coupled with atomic force microscopy, secondary ion mass spectroscopy, and transmission electron microscopy to study the surface topography and the corresponding reaction layer. Direct correlation of the microstructure before plasma exposure with the surface topography reveals a novel orientation‐dependent erosion mechanism that forms plateau‐like structures. Furthermore, the in‐depth analysis of the near‐surface area highlights the influence of the applied bias voltage on the physical damage and chemical gradient formation due to plasma exposure. The combined investigation of surface morphology and near‐surface properties reveals new fundamental aspects of the erosion behavior of polycrystalline yttria in CF4‐based etching plasmas. [ABSTRACT FROM AUTHOR]

Yttria‐stabilized zirconia (YSZ) has been for several decades the state of the art material for thermal barrier coating (TBC) applications in gas turbines. Although the material has unique properties, further efficiency improvement by increasing the temperature is limited due to its maximum temperature capability of about 1200°C. Above this temperature the deposited metastable tetragonal (t´) phase undergoes a detrimental phase transformation as well as enhanced sintering. Both processes promote the failure of the coatings at elevated temperatures and this early failure has been frequently observed in gradient tests. In this paper, we now experimentally shown for the first time that under typical cycling conditions not the time at elevated temperatures leads to the reduced lifetime but the transient cooling rates. If cooling rates were reduced to 10K/s, TBC systems could be operated in a burner rig at a surface temperature well above 1500°C without showing a lifetime reduction. The explanation of these astonishing findings is given by the evaluation of energy release rate peaks during fast transient cooling in combination with the phase evolution during cooling with the used cooling rates. [ABSTRACT FROM AUTHOR]

The compressive creep of silicon carbide fiber reinforced Ti3SiC2 MAX phase with both fine and coarse microstructure was investigated in the temperature range of 1000‐1300°C. Comparison of only steady‐state creep was done to understand the response of fabricated composite materials toward creep deformation. It was demonstrated that the fibers are more effective in reducing the creep rates for the coarse microstructure by an increase in activation energy compared to the variant with a finer microstructure, being partly a result of the enhanced creep rates for the microstructure with larger grain size. Grain boundary sliding along with fiber fracture appears to be the main creep mechanism for most of the tested temperature range. However, there are indications for a changed creep mechanism for the fine microstructure for the lowest testing temperature. Local pores are formed to accommodate differences in strain related to creeping matrix and predominantly elastically deformed fibers during creep. Microstructural analysis was done on the material before and after creep to understand the deformation mechanics. [ABSTRACT FROM AUTHOR]

The compressive creep of a SiC whisker (SiCw) reinforced Ti3SiC2 MAX phase‐based ceramic matrix composites (CMCs) was studied in the temperature range 1100‐1300°C in air for a stress range 20‐120 MPa. Ti3SiC2 containing 0, 10, and 20 vol% of SiCw was sintered by spark plasma sintering (SPS) for subsequent creep tests. The creep rate of Ti3SiC2 decreased by around two orders of magnitude with every additional 10 vol% of SiCw. The main creep mechanisms of monolithic Ti3SiC2 and the 10% CMCs appeared to be the same, whereas for the 20% material, a different mechanism is indicated by changes in stress exponents. The creep rates of 20% composites tend to converge to that of 10% at higher stress. Viscoplastic and viscoelastic creep is believed to be the deformation mechanism for the CMCs, whereas monolithic Ti3SiC2 might have undergone only dislocation‐based deformation. The rate controlling creep is believed to be dislocation based for all the materials which is also supported by similar activation energies in the range 650‐700 kJ/mol. [ABSTRACT FROM AUTHOR]

Gadolinium zirconate (Gd2Zr2O7, GZO) as an advanced thermal barrier coating (TBC) material, has lower thermal conductivity, better phase stability, sintering resistance, and calcium‐magnesium‐alumino‐silicates (CMAS) attack resistance than yttria‐stabilized zirconia (YSZ, 6‐8 wt%) at temperatures above 1200°C. However, the drawbacks of GZO, such as the low fracture toughness and the formation of deleterious interphases with thermally grown alumina have to be considered for the application as TBC. Using atmospheric plasma spraying (APS) and suspension plasma spraying (SPS), double‐layered YSZ/GZO TBCs, and triple‐layered YSZ/GZO TBCs were manufactured. In thermal cycling tests, both multilayered TBCs showed a significant longer lifetime than conventional single‐layered APS YSZ TBCs. The failure mechanism of TBCs in thermal cycling test was investigated. In addition, the CMAS attack resistance of both TBCs was also investigated in a modified burner rig facility. The triple‐layered TBCs had an extremely long lifetime under CMAS attack. The failure mechanism of TBCs under CMAS attack and the CMAS infiltration mechanism were investigated and discussed. [ABSTRACT FROM AUTHOR]

Weakly acceptor‐doped ceria ceramics were characterized structurally and compositionally with advanced transmission electron microscopy (TEM) techniques and electrically with electrochemical impedance spectroscopy (EIS). The grain boundaries studied with TEM were found to be free of second phases. The impedance spectra, acquired in the range 703 ≤ T/K ≤ 893 in air, showed several arcs that were analyzed in terms of bulk, grain‐boundary, and electrode responses. We ascribed the grain‐boundary resistance to the presence of space‐charge layers. Continuum‐level simulations were used to calculate charge‐carrier distributions (of acceptor cations, oxygen vacancies, and electrons) in these space‐charge layers. The acceptor cations were assumed to be mobile at high (sintering) temperatures but immobile at the temperatures of the EIS measurements. Space‐charge formation was assumed to be driven by the segregation of oxygen vacancies to the grain‐boundary core. Comparisons of data from the simulations and from the EIS measurements yielded space‐charge potentials and the segregation energy of vacancies to the grain‐boundary core. The space‐charge potentials from the simulations are compared with values obtained by applying the standard, analytical (Mott–Schottky and Gouy–Chapman) expressions. The importance of modelling space‐charge layers from the thermodynamic level is demonstrated. [ABSTRACT FROM AUTHOR]

In situ high‐temperature powder X‐ray diffraction analysis (HT‐XRD) was carried out in the temperature range from 25°C‐1430°C to investigate the crystal structure of double perovskites, La2(Al1/2MgTa1/2)O6 (LAMT) and its phase transitions. This complex perovskite is a promising candidate for application in thermal barrier coating systems. Rietveld analysis shows a rock‐salt type ordering of the B‐site cations in the monoclinic space group symmetry, P21/n at room temperature. Upon heating, a structural phase transition occurs at ~855°C, and the crystal structure becomes rhombohedral with the space group symmetry R3¯. On further heating, LAMT transforms to the ideal cubic phase at ~1390°C with the space group symmetry Fm3¯m. Both of the structural phase transitions are completely reversible, and were confirmed through complementary differential scanning calorimetry and thermogravimetry measurements. With increasing temperature, the degree of the octahedral tilting decreases and the variance of the different B–O bond lengths is reduced, until in the cubic phase, no tilting is present, and almost equal B–O bond lengths are obtained. [ABSTRACT FROM AUTHOR]

The ionic conductivity of solid electrolytes is dependent on synthesis and processing conditions, ie, powder properties, shaping parameters, sintering time (ts), and sintering temperature (Ts). In this study, Na3Zr2(SiO4)2(PO4) was sintered at 1200 and 1250°C for 0‐10 hours and its microstructure and electrical performance were investigated by means of scanning electron microscopy and impedance spectroscopy. After sintering under all conditions, the sodium super‐ionic conductor‐type structure was formed along with ZrO2 as a secondary phase. The microstructure investigation revealed a bimodal particle size distribution and grain growth at both Ts. The density of samples increased from 60% at 1200°C for 0 hours to 93% at 1250°C for 10 hours. The ionic conductivity of the samples increased with ts due to densification and grain growth, ranging from 0.13 to 0.71 mS/cm, respectively. The corresponding equivalent circuit fitting for the impedance spectra revealed that grain boundary resistance is the prime factor contributing to the changing conductivity after sintering. The activation energy of the bulk conductivity (Ea,bulk) remained almost constant (0.26 eV) whereas the activation energy of the total conductivity (Ea) exhibited a decreasing trend from 0.37 to 0.30 eV for the samples with ts = 0 and 10 hours, respectively—both sintered at 1250°C. In this study, the control of the grain boundaries improved the electrical conductivity by a factor of 6. [ABSTRACT FROM AUTHOR]

The microstructural evolution during sintering involves the formation and pinch-off of pore channels. The sintering of 3 particles in 3 dimensions is a simple model for studying the pinch-off of a pore channel. We simulate the solid-state sintering of 3 particles by using Brakke’s Surface Evolver program, which incorporates coupled grain-boundary diffusion and surface diffusion. The pinch-off of pore channel divides the sintering process into 2 stages; the initial stage and the later stage. The contact area has a noncircular shape bounded by both surface triple junction and triple junction in the later stage. A general method is presented to determine the sintering force acting on the noncircular contact. The mechanical approach of densification, where the relative motion of particles is driven by both sintering force and applied force, is applicable not only for the initial stage, but also for the later stage. [ABSTRACT FROM AUTHOR]

Cr2AlC foams have been processed for the first time containing low (35 vol%), intermediate (53 vol%), and high (75 vol%) content of porosity and three ranges of pore size, 90-180 μm, 180-250 μm, and 250-400 μm. Sacrificial template technique was used as the processing method, utilizing NH4HCO3 as a temporary pore former. Cr2AlC foams exhibited negligible oxidation up to 800°C and excellent response up to 1300°C due to the in-situ formation of an outer thin continuous protective layer of α-Al2O3. The in-situ α-Al2O3 protective layer covered seamlessly all the external surface of the pores, even when they present sharp angles and tight corners, reducing significantly the further oxidation of the foams. The compressive strength of the foams was 73 and 13 MPa for 53 vol% and 75 vol% porosity, respectively, which increased up to 128 and 24 MPa after their oxidation at 1200°C for 1 hour. The increase in the compressive strength after the oxidation was caused by the switch from inter- to transgranular fracture mode. According to the excellent high-temperature response, heat exchangers and catalyst supports are the potential application of these foams. [ABSTRACT FROM AUTHOR]

We report on the materials interaction of gadolinium-doped ceria (GDC) and yttria-stabilized zirconia (YSZ) in the context of high-temperature sintering during manufacturing of anode supported solid oxide fuel cells (AS-SOFC). While ceriabased anodes are expected to show superior electrochemical performance and enhanced sulfur and coking tolerance in comparison to zirconia-based anodes, we demonstrate that the incorporation of a Ni-GDC anode into an ASC with YSZ electrolyte decreases the performance of the ASC by approximately 50% compared to the standard Ni-YSZ cell. The performance loss is attributed to interdiffusion of ceria and zirconia during cell fabrication, which is investigated using powder mixtures and demonstrated to be more severe in the presence of NiO. We examine the physical properties of a GDC-YSZ mixed phase under reducing conditions in detail regarding ionic and electronic conductivity as well as reducibility, and discuss the expected impact of cation intermixing between anode and electrolyte. [ABSTRACT FROM AUTHOR]