Formation Of Perovskite Phase Research Articles

Synergistic effects of liquid phase sintering and B-site substitution to enhance proton conductivity of BaZr0.1Ce0.7Y0.1Yb0.1O3-δ for protonic ceramic fuel cell

This paper is dedicated to improving the sintering and conductivity of BaZr0.1Ce0.7Y0.1Yb0.1O3-δ (BZCYYb) by adding ZnO-CuO dual-sintering aids. The synergistic effects of liquid-sintering of Zn and B-site substitution of Cu on the sinterability and proton conductivity of BZCYYb are systematically investigated. X-ray diffraction (XRD) analysis of BZCYYb after addition of ZnO-CuO (BZCYYb-Zn-Cu) confirms the complete perovskite phase formation without any secondary phase. The substitution of Ce4+ (0.87 Å) with Zn2+ (0.74 Å) or Cu2+ (0.73 Å) induces a shift in XRD diffraction peak to higher angle due to a decrease in lattice constant. Energy dispersive X-ray spectroscopy analysis indicate a distinct distribution of Zn primarily at the grain boundaries, while Cu is predominantly located within the grains of BZCYYb-Zn-Cu. The addition of ZnO-CuO into BZCYYb results in a denser microstructure with larger average grain size. Furthermore, the substitution of Ce4+ by Cu2+ increases the concentration of oxygen vacancies and reduces activation energy. For BZCYYb-Zn-Cu, the proton conductivity reaches 4.52×10-2 S/cm at 750 °C, approximately 3 times higher than that of BZCYYb. This enhancement can be attributed to the synergistic effects of larger average grain size resulting from liquid phase sintering of Zn, low active energy, and high concentration of oxygen vacancies arising from Cu B-site substitution. BZCYYb-Zn-Cu is used as the electrolyte for anode support SOFC, and the single cell exhibits remarkable electrochemical performance and excellent stability in H2 fuel. This research establishes a crucial theoretical foundation for the preparation and performance evaluation for large-size protonic ceramic cell.

Understanding secondary order parameters in perovskites with tilted octahedra

In the family of perovskite materials, the tilts of BX 6 octahedra are the most common type of structural distortion. Conventionally, the formation of low-symmetry perovskite phases with tilted octahedra is analyzed by considering only primary order parameters. However, octahedral tilting also gives rise to secondary order parameters which contribute to additional atomic displacements, ordering and lattice distortions. Our study highlights the significant impact of secondary order parameters on the structural formation and emergent physical properties of perovskites. Through group-theoretical and crystallographic analyses, we have identified all secondary order parameters within Glazer-type tilt systems and clarified their physical manifestations. We explore the fundamental symmetry relationships among various structural degrees of freedom in perovskites, including tilt-induced ferroelasticity, correlations between displacements and ordering of atoms occupying different positions, and the potential for rigid unit rotations and unconventional octahedral tilts. Particular emphasis is placed on the emergence of secondary order parameters and their coupling with primary order parameters, as well as their symmetry-based hierarchy, illustrated through a modified Bärnighausen tree. We applied our theoretical insights to elucidate phase transitions in well known perovskites such as CaTiO3 and RMnO3 (where R = La and lanthanide ions), thereby demonstrating the significant influence of secondary order parameters on crystal structure formation. Our results serve as a symmetry-based guide for the design, identification and structural characterization of perovskites with tilted octahedra, and for understanding tilt-induced physical properties.

Precursor Ink Engineering to Implement Vacuum Extraction Method for Scalable Production of Perovskite Solar Cells.

Engineering perovskite precursor ink to widen the processing window is crucial to obtaining uniform, compact, and pinhole-free perovskite films at scale using industrially relevant solution coating techniques. Here, we introduce a ternary solvent system and systematically investigate the impacts of coordinating solvents, N-methyl-2-pyrrolidone (NMP) and N,N'-dimethylpropyleneurea (DMPU), on the physical properties of the slot-die-coated perovskite films and on the corresponding device performance. Tailoring NMP and DMPU concentrations in the precursor ink allows us to control the perovskite intermediate phase formation and widen the processing window, enabling the reproducible production of perovskite films with high photoelectrical quality at scale. Using the optimized precursor ink, we demonstrate slot-die-coated perovskite minimodules with power conversion efficiencies of 19 and 16% on 56 and 100 cm2 substrates, respectively.

Unveiling the role of Cs ion in perovskite phase formation during solid–vapor reactions

The preparation of perovskite solar cells (PSCs) using a solid–vapor reaction has shown great potential due to its scalability and lack of organic solvent. The phase formation process in the solid–vapor reaction is crucial for the crystallization of perovskite films. Previous studies mainly introduced Cs into the solid–vapor reaction, but insufficient attention was paid to the role of Cs in purifying the phase formation path during the crystallization process. In this study, we investigated the effect of Cs on the phase formation process in the solid–vapor reaction and found that Cs can decrease the crystallinity of lead halide films, induce a purified phase formation process to prevent the formation of δ-phase and other impurity phases, regulate the crystallization rate of perovskite, and produce high-quality, low-defect perovskite films. The result was achieving a champion power conversion efficiency (PCE) of 21.54 % for a small area (0.148 cm2) and 18.65 % for larger mini-modules (5 × 5 cm2). Furthermore, the devices maintained over 80 % of their initial efficiencies after 450 h of continuous operation under AM 1.5 G irradiation. This work underscores the importance of purified phase formation paths in solid–vapor reactions for outstanding crystal quality in high-performance perovskite solar cells.

2D Phase Formation on 3D Perovskite: Insights from Molecular Stiffness.

Several studies have demonstrated that low-dimensional structures (e.g., two-dimensional (2D)) associated with three-dimensional (3D) perovskite films enhance the efficiency and stability of perovskite solar cells. Here, we aim to track the formation sites of the 2D phase on top of the 3D perovskite and to establish correlations between molecular stiffness and steric hindrance of the organic cations and their influence on the formation and crystallization of 2D/3D. Using cathodoluminescence combined with a scanning electron microscopy technique, we verified that the formation of the 2D phase occurs preferentially on the grain boundaries of the 3D perovskite. This helps explain some passivation mechanisms conferred by the 2D phase on 3D perovskite films. Furthermore, by employing in situ grazing-incidence wide-angle X-ray scattering, we monitored the formation and crystallization of the 2D/3D perovskite using three cations with varying molecular stiffness. In this series of molecules, the formation and crystallization of the 2D phase are found to be dependent on both steric hindrance around the ammonium group and molecular stiffness. Finally, we employed a 2D/3D perovskite heterointerface in a solar cell. The presence of the 2D phase, particularly those formed from flexible cations, resulted in a maximum power conversion efficiency of 21.5%. This study provides insight into critical aspects related to how bulky organic cations' stiffness and steric hindrance influence the formation, crystallization, and distribution of 2D perovskite phases.

Chemical Reaction Modulated Low-Dimensional Phase Toward Highly Efficient Sky-Blue Perovskite Light-Emitting Diodes.

Blue perovskite light-emitting diodes (PeLEDs) are crucial avenues for achieving full-color displays and lighting based on perovskite materials. However, the relatively low external quantum efficiency (EQE) has hindered their progression towards commercial applications. Quasi-two-dimensional (quasi-2D) perovskites stand out as promising candidates for blue PeLEDs, with optimized control over low-dimensional phases contributing to enhanced radiative properties of excitons. Herein, the impact of organic molecular dopants on the crystallization of various n-phase structures in quasi-2D perovskite films. The results reveal that the highly reactive bis(4-(trifluoromethyl)phenyl)phosphine oxide (BTF-PPO) molecule could effectively restrain the formation of organic spacer cation-ordered layered perovskite phases through chemical reactions, simultaneously passivate those uncoordinated Pb2+ defects. Consequently, the prepared PeLEDs exhibited a maximum EQE of 16.6 % (@ 490 nm). The finding provides a new route to design dopant molecules for phase modulation in quasi-2D PeLEDs.

Homogenizing The Low-Dimensional Phases for Stable 2D-3D Tin Perovskite Solar Cells.

2D-3D tin-based perovskites are considered as promising candidates for achieving efficient lead-free perovskite solar cells (PSCs). However, the existence of multiple low-dimensional phases formed during the film preparation hinders the efficient transport of charge carriers. In addition, the non-homogeneous distribution of low-dimensional phases leads to lattice distortion and increases the defect density, which are undesirable for the stability of tin-based PSCs. Here, mixed spacer cations [diethylamine (DEA+) and phenethylamine (PEA+)] are introduced into tin perovskite films to modulate the distribution of the 2D phases. It is found that compared to the film with only PEA+, the combination of DEA+ and PEA+ favors the formation of homogeneous low-dimensional perovskite phases with three octahedral monolayers (n=3), especially near the bottom interface between perovskite and hole transport layer. The homogenization of 2D phases help improve the film quality with reduced lattice distortion and released strain. With these merits, the tin PSC shows significantly improved stability with 94% of its initial efficiency retained after storing in a nitrogen atmosphere for over 4600h, and over 80% efficiency maintained after continuous illumination for 400h.

Supported LaCoO3 perovskite-like oxides for N2O decomposition: The key role of the support nature and LaCoO3 content

In this work a detailed comparison of the N2O decomposition catalytic performance of LaCoO3 perovskite-like mixed oxides supported over different commercial materials was conducted. Zirconia-, silica- and γ-alumina-based supports were studied. Zirconia-based supports turned out to be the most applicable because of the formation of the pure LaCoO3 perovskite phase on their surface. Among these supports, ZrO2-La revealed to possess the best activity owing to the highest Co2+/Co3+ (0.82) and Oads./OL (0.67) ratios on its surface. The raw of activities was as follows: LaCoO3(20 %)/ZrO2-La > LaCoO3(20 %)/ZrO2 > LaCoO3(20 %)/ZrO2-W. When the LaCoO3 content in LaCoO3/ZrO2-La was 20 wt%, the maximum of activity was observed – 94.78 mmol(N2O)/[g(cat.)·h] at 450 °C. This fact was in accordance with the highest Co2+/Co3+ (0.82) and Oads./OL (0.67) ratios at the 20 wt% LaCoO3 content. Coordinatively unsaturated Co2+, forming Lewis acid-base pairs, were proposed to be the active sites of the zirconia-based LaCoO3 catalysts in the N2O decomposition.

Fabrication and characterization of methylammonium lead iodide-based perovskite solar cells under ambient conditions

<p>This study investigated the fabrication and characterization of CH<sub>3</sub>NH<sub>3</sub>PbI<sub>3</sub> based perovskite solar cells (PSCs) using the one-step spin coating technique under ambient conditions, eliminating the need for expensive glovebox and thermal evaporation equipment. The perovskite layer was annealed at 65 °C for 30 seconds and 100 °C for 30 seconds, 1 and 2 minutes. The scanning electron microscope (SEM) images show a smooth and uniform surface coverage for the ETL and CH<sub>3</sub>NH<sub>3</sub>PbI<sub>3</sub> layers. SEM results also show an average grain size of 397 nm for CH<sub>3</sub>NH<sub>3</sub>PbI<sub>3</sub> and an average particle size of ~17 nm for TiO<sub>2</sub> was confirmed by transmission electron microscopy (TEM). X-ray diffraction (XRD) results confirmed the formation of tetragonal perovskite (CH<sub>3</sub>NH<sub>3</sub>PbI<sub>3</sub>) phase with high crystallinity with a crystallite size of 19.99 nm for the samples annealed for 30 seconds at 65 °C and 1 min at 100 °C. FTIR results also confirmed the presence of anatase TiO2 at wavenumber 438 cm<sup>-1</sup> and the formation of the adduct of Pb<sub>2</sub> with dimethyl sulfoxide (DMSO) and MAI is confirmed at 1,015 cm<sup>-1</sup> . From the Tauc plot the bandgap energy of TiO2 and Perovskite layers was determined to be 3.52 eV and 2.06 eV respectively. An open-circuit voltage was 0.9057 V and short circuit current density was 12.2185 mA/cm<sup>2</sup> with a fill factor of 48.05 and power conversion efficiency (PCE) of 5.199%.</p>

Manganese-substituted strontium ferrite catalyst on honeycomb structured cordierite support for oxidation of diesel particulate matter

Perovskite-based catalysts have been explored as low-cost substitutes for platinum (Pt)- based catalysts for diesel particulate matter (DPM) oxidation. In this work, manganese (Mn)-substituted strontium ferrite (SrFeMnO3-δ) (SFM) as a catalyst was coated on the honeycomb structure of cordierite support and tested for its catalytic performance for DPM oxidation using a real-world engine. The characteristic diffraction peaks due to the presence of the perovskite structure of SFM were observed for the cordierite-supported SFM. Mn was substituted in the lattice of un-substituted strontium ferrite and no other impurities were formed upon the Mn-substitution. Highly agglomerated SFM particles were formed solely due to the perovskite phase formation temperature (900 °C). The SFM catalyst enhanced catalytic Printex-V oxidation performance compared to its oxidation without the catalyst, where Printex V was used as the model DPM. The SFM catalyst showed high CO2 selectivity upon the oxidation of DPM. These results infer that the SFM catalyst possesses promise as an alternative to commercially available DOC catalysts based on PGM for DPM oxidation. SFM-coated cordierite support performed much better in terms of particle number, mass and surface area than commercial diesel oxidation catalyst (DOC) or without DOC at no engine load. The performance is substantially higher even at moderate engine loads of up to 40% and comparable at very high engine loads of 100%. Detailed investigations on a real engine exhaust and measurement of crucial parameters like particle number, mass and surface area suggest convincing and relatively rare evidence for its potential as a catalyst for diesel exhaust emission control catalyst.

Accelerated formation of photoactive formamidinium-based lead triiodide perovskite crystals by the addition of copper iodide

Additions of copper iodide (CuI), rubidium iodide, or cesium iodide to perovskite precursor solutions accelerated the formation of the photoactive α-phase of formamidinium lead triiodide (FAPbI3) perovskite crystals. In particular, the addition of CuI suppresses the formation of low-dimensional perovskite phases, thereby reducing carrier transport. The first-principles calculations revealed that substituting Cu at the formamidinium site could maintain the effective mass ratios of the α-phase. The CuI addition to FAPbI3 is expected to enhance its photovoltaic properties. Moreover, introducing CuI into perovskite precursor solutions is suggested as a new approach to accelerate the formation of the photoactive α-FAPbI3 phase.

Transient Ruddlesden-Popper-Type Defects and Their Influence on Grain Growth and Properties of Lithium Lanthanum Titanate Solid Electrolyte.

Lithium lanthanum titanate (LLTO) perovskite is one of the most promising electrolytes for all-solid-state batteries, but its performance is limited by the presence of grain boundaries (GBs). The fraction of GBs can be significantly reduced by the preparation of coarse-grained LLTO ceramics. In this work, we describe an alternative approach to the fabrication of ceramics with large LLTO grains based on self-seeded grain growth. In compositions with the starting stoichiometry for the Li0.20La0.60TiO3 phase and with a high excess addition of Li (Li:La:Ti = 11:15:25), microstructure development starts with the formation of the layered RP-type Li2La2Ti3O10 phase. Grains with many RP-type defects initially develop into large platelets with thicknesses of up to 10 μm and lengths over 100 μm. Microstructure development continues with the crystallization of LLTO perovskite, epitaxially on the platelets and as smaller grains with thinner in-grain RP-lamellae. Theoretical calculations confirmed that the formation of RP-type sequences is energetically favored and precedes the formation of the LLTO perovskite phase. At around 1250 °C, the RP-type sequences become thermally unstable and gradually recrystallize to LLTO via the ionic exchange between the Li-rich RP-layers and the neighboring Ti and La layers as shown by quantitative HAADF-STEM. At higher sintering temperatures, LLTO grains become free of RP-type defects and the small grains recrystallize onto the large platelike seed grains via Ostwald ripening. The final microstructure is coarse-grained LLTO with total ionic conductivity in the range of 1 × 10-4 S/cm.

Realizing Phase‐Pure (PEA)2FAPb2I7 Perovskite Films by Inhibiting 3D Phase Formation

Abstract2D Ruddlesden–Popper (RP) layered metal‐halide perovskites have garnered significant interest due to their unique photoelectric properties and excellent stability. However, 2D perovskite films prepared via solution process generally exhibit multi‐quantum well structure with random well width distribution, which significantly impedes the carrier transportation. Herein, the synthesis of phase‐pure 2D (PEA)2FAPb2I7 (PEA = C8H11N, FA = CH4N2) perovskite thin films is reported in ambient environment achieved by suppressing the formation of the 3D perovskite phase. First, incorporation of MACl additive can effectively regulate the intermediate during crystallization, facilitating the formation of a metastable 3D MAxFA1‐xPbIyCl3‐y phase. Second, precise control of environmental humidity is employed to further inhibit the formation of α‐FAPbI3 phase. As a result, the perovskite intermediate composed of predominantly metastable 3D phase and 2D n = 2 phase is achieved, which is eventually transformed into 2D n = 2 perovskite during annealing, leading to markedly enhanced phase purity. Photoconductive‐type photodetectors based on the phase‐pure 2D RP perovskite films are fabricated, demonstrating a high detectivity of over 9.4 × 1012 Jones due to the improved carrier transportation. This study provides a comprehensive insight into the crystallization process of phase‐pure 2D perovskites.

2D Perovskite Capping Layer Enabling Stable Perovskite Photovoltaics

Interfacial passivation plays a pivotal role in achieving efficient and stable perovskite solar cells. Meanwhile, the introduction of 2D perovskites has also been widely reported to be beneficial for enhancing the performance and stability of devices. Herein, DEAI is used as an ammonium salt, which is spin coated onto the surface of the perovskite film, resulting in the formation of a 2D perovskite phase. This alteration increases the film's hydrophobicity, holding the promise of enhancing its humidity stability. Furthermore, DEAI effectively reduces trap density in the perovskite layer, suppressing nonradiative recombination and optimizing the surface potential, thereby improving the efficiency of devices. As a result, the inverted perovskite devices passivated with DEAI achieve a champion power conversion efficiency of 24.26%. Additionally, the unencapsulated DEAI‐passivated perovskite solar cells demonstrate enhanced stability.

The effect of ZnO and MnO2 as sintering aids in the preparation of potassium sodium niobate ceramics and electrical characterizations

Potassium sodium niobate (KNN) is an environmentally compatible piezoelectric material for substituting harmful lead-based ceramics. KNN-based ceramics have excellent piezoelectric properties with high Curie temperature. But, KNN faces difficulties during the processing like volatilization of alkali elements, chemical inhomogeneity, low densification, etc. The objective of this research is to investigate the impact of certain metal oxides additions like ZnO and MnO2 as sintering aids to solve the problems of the preparation and hence study the structural and electric properties of K0.5N0.5NbO3 (KNN) ceramics. ZnO and MnO2 added potassium sodium niobate, K0.5N0.5NbO3 was prepared by using the ceramic method. The prepared samples were sintered at 1000 °C for 2h conventionally. The structural properties of the ceramics have been analyzed by using X-Ray Diffractometer. The study demonstrates the formation of the orthorhombic-symmetric perovskite phase in all the prepared samples. The microstructural behavior of the ceramics has been characterized by techniques such as scanning electron microscopy (SEM) and compositional properties were studied by energy dispersive x-ray (EDAX). The effects of metal oxide additions on the electronic properties such as dielectric constant, dielectric loss, impedance properties, Nyquist plot, etc., were studied. The results have been analyzed and discussed in the paper.

Thermoelectric behavior of (Ba0.2Sr0.2Ca0.2La0.2Na0.2)CoO3 high entropy cobaltate-based perovskite.

Oxides are considered as promising thermoelectric materials due to their excellent thermal and chemical stability at elevated temperatures. However, their thermoelectric performances are hindered by high thermal conductivity due to the relatively simple structure compared to the layered or cage-like structure of intermetallics and chalcogenides. In this study, we have successfully crafted a novel cobaltate-based high-entropy oxide perovskite, (Ba0.2Sr0.2Ca0.2La0.2Na0.2)CoO3 (BSCLN), based on detailed thermodynamic calculation. XRD analysis of the as-synthesized ceramics confirms the formation of a cubic perovskite phase, while SEM-EDXS data reveals a dense microstructure with a uniform distribution of all the constituent elements. By employing high-entropy engineering in this cobaltate-based ceramic, we have managed to reduce thermal conductivity significantly while optimizing electrical conductivity. Five different elements populating the A-site induce extensive structural defects and disorder causing enhanced phonon scattering. This results in a glass-like low thermal conductivity of 1.43 W m-1 K-1 at 1023 K for the high-entropy cobaltate. Moreover, we have achieved a comparatively high electrical conductivity on the order of 104 S m-1. This study illustrates the effectiveness of introducing structural disorder through high-entropy engineering to enhance the overall thermoelectric performance of the material.

An energy-efficient tellurium electrode enabled by a Cs2TeI6 perovskite structure for durable aqueous Zn–Te batteries

CsI in 2 M ZnSO4 aqueous electrolyte facilitates the formation of Cs2TeI6 perovskite phase for Te electrode, effectively suppressing Te4+ hydrolysis and sustaining fast redox kinetics in multi-electron transfer Zn–Te aqueous batteries.

2D Halide Perovskite Phase Formation Dynamics and Their Regulation by Co‐Additives for Efficient Solar Cells

AbstractThe incorporation of large organic ammonium ions renders the crystallization dynamics and layer formation process of halide perovskites complex, difficult to control, and leads to problems of suppressed charge transport with the formation of tiny‐sized grains. In this paper, the use of methylammonium chloride (MACl) and an excess of PbI2 is introduced as a co‐additives in the precursor solution for the control of phenylmethylammonium or benzylammonium (PMA+ spacer) and formamidinium (FA+)‐based quasi‐2D PMA2FAn−1PbnI3n+1 (n = 5) perovskite layers formation. By this method, the morphology of the layer, the inner phase distribution, and the charge transport properties are improved. By employing glow discharge‐optical emission spectroscopy (GD‐OES) and other techniques, it is revealed that the quasi‐2D perovskites prepared in the presence of co‐additives exhibit uniform removal dynamics of the solvent across the film. Furthermore, the grain growth mode, upon thermal annealing, is lateral. It results in large, monolithic grains with low‐trap state density and excellent substrate coverage. Particularly, co‐additives improve the cations dispersion upon the crystallization process, thus suppressing the low‐n phase formed through the aggregation of spacer cations and accelerating the formation of the high‐n phase.

Successful synthesis of LaFeO3 nanoporous powders with high catalytic and photocatalytic performances: Investigation of precursor effect

Porous LaFeO3 powders with high catalytic and photocatalytic activities were successfully synthesized by sol-gel method using nitrate and chloride precursors. The precursor effect on the crystal structure, morphology, specific surface area and optical properties of the prepared powders was fully determined. Thermogravimetric and X-ray diffraction analyzes showed the formation of the orthorhombic perovskite phase (Pnma, #62) at annealing temperature of 800 and 1000 °C for powder prepared by nitride and chloride salts, respectively. The scanning electron microscopy images revealed a significant effect of precursor type on nanoparticles morphology. It was found that powder prepared from chloride salts is more porous than that prepared with nitrate salts. The estimated surface area of LaFeO3 nanoparticles ranges between 5.94 and 11.56 m2/g and the band gap varies from 2.19 to 2.27 eV. Methylene blue (MB) dye was used to investigate the catalytic and photocatalytic properties of LaFeO3 powders. Both prepared powder types showed good catalytic activity and high photocatalytic performance under visible irradiation in removing MB dye. The adsorption kinetics data of MB molecules on LaFeO3 nanoparticles are well fitted to the pseudo-first order model. Powder synthesized with chloride salts demonstrated high photodegradation efficiency of MB dye compared to that prepared by nitrate salts, which can be attributed to its relatively small band gap and high porosity. These two factors ensure a greater number of photogenerated electrons and more sites for photocatalytic reactions.

Stabilizing perovskite precursors with the reductive natural amino acid for printable mesoscopic perovskite solar cells

Solution processability significantly advances the development of highly-efficient perovskite solar cells. However, the precursor solution tends to undergo irreversible degradation reactions, impairing the device performance and reproducibility. Here, we utilize a reductive natural amino acid, N-acetylcysteine (NALC), to stabilize the precursor solution for printable carbon-based hole-conductor-free mesoscopic perovskite solar cells. We find that I2 can be generated in the aged solution containing methylammonium iodide (MAI) in an inert atmosphere and speed up the MA-FA+ (formamidinium) reaction which produces large-size cations and hinders the formation of perovskite phase. NALC effectively stabilizes the precursor via its sulfhydryl group which reduces I2 back to I− and provides H+. The NALC-stabilized precursor which is aged for 1440 h leads to devices with a power conversion efficiency equivalent to 98% of that for devices prepared with the fresh precursor. Furthermore, NALC improves the device power conversion efficiency from 16.16% to 18.41% along with enhanced stability under atmospheric conditions by modifying grain boundaries in perovskite films and reducing associated defects.