Defect Dipoles Research Articles

Self-powered visible light photodetector based on BixFeO3 film

In this study, the self-powered photodetector based on photovoltaic effect was obtained from Bi x FeO 3 (x = 1, 1.3, 1.5, 1.7) films. In order to study the origin of the photovoltaic effect, the self-polarized structure and defect distribution of the films were characterized by x-ray diffraction, x-ray photoelectron spectroscopy, and piezoelectric force microscopy. In addition, the responsivity (1515 μA/W) and detectivity (1.35Χ10 11 Jones) are achieved in the Bi 1.5 FeO 3 film at zero bias after receiving 0.2 mW/cm 2 of irradiation light in the wavelength of 500 nm. The rise and decay time of the photocurrent without bias reaches ∼6 ms and ∼15 ms respectively, and did not weaken after a 11 min cycling test. The self-polarized structure and defect dipoles play an important role in the photovoltaic effect of Bi x FeO 3 self-powered photodetector. This work lays a foundation for applications in Bi x FeO 3 self-powered photodetection.

Giant dielectric response and relaxation behavior in (Tm + Ta) co-doped TiO2 ceramics.

Dielectric materials with huge dielectric constants are attracting attention due to the growing demand for microelectronics and high energy-storage devices. In this work, Tm + Ta co-doped TiO2 ceramics were prepared by a solid-state reaction (SSR) method, and the microstructure and dielectric behavior were investigated. A ultrahigh permittivity (εr ∼ 2.26 × 104) and very low loss (tan δ ∼ 0.011) are achieved at 1 kHz for (Tm0.5Ta0.5)0.01Ti0.99O2 ceramics. XPS analysis confirms that the high dielectric constant and low dielectric loss are attributed to the electron pinned defect dipole (EPDD) response formed by the coupling of Ti3+ and oxygen vacancies. In addition, impedance analysis and frequency dependent dielectric constant under a DC bias indicate that the presence of the internal barrier layer capacitance (IBLC) response and electrode response at low to medium frequencies (<106 Hz) also contribute significantly to the dielectric constant. The findings reported in this work provide valuable insights into the simultaneous realization of a low dielectric loss and high permittivity in Tm + Ta co-doped TiO2 ceramics and other related dielectric ceramics.

Defect controlling of BaTiO3@ NiO double hysteresis loop ceramics with enhanced energy storage capability and stability

Dielectric capacitor with high energy storage density has become a pivotally enabling technology in electronic industry. The most critical factors affecting energy storage capacity are polarization and breakdown strength. Here the BaTiO3@ NiO double-hysteresis-loop ceramics with different polarization characteristics are prepared by changing the sintering atmosphere to control the defect structure. Results show that, the samples sintered in oxygen exhibit the obviously characteristics of double hysteresis loop, higher polarization and larger breakdown strength. In contrast, the samples sintered in nitrogen have lower polarization and breakdown strength and weaker double hysteresis loop. It is proved that the double hysteresis loop is caused by the defects of the inner layer and the outer layer by regulating the defect structure. Firstly, Low valence Ni ions replace Ti ions to form NiTi''−Vo•• defect dipoles. These charged defect dipoles could be pinned the domain wall, and the existence of oxygen vacancies restricts the movement of the domain wall, making the material appeared a pinched hysteresis loop similar to the double hysteresis loop as observed in antiferroelectrics. Secondly, the local electric field generated by the depletion layer at the interface may also trigger a new polarization features in the material. This double hysteresis loop helps to improve the polarization and energy storage capacity of the material.Finally, the excellent energy storage density of the oxygen samples reaches up to 2.48 J cm−3at 340 kV cm-1 with prominent cycle stability and temperature stability. This work provides a prospective method to fabricate material with high energy storage performance by the adjustment defect structure to control the polarization mechanism in the BaTiO3@1NiO ceramics.

Point defect induced incommensurate dipole moments in the KCa2Nb3O10 Dion-Jacobson layered perovskite

Local structural distortions due to isolated atomic defects and defect complexes strongly affect the macroscopic properties of oxide ceramics. While the characterization of local defect structures is more common in simple $\mathrm{AB}{\mathrm{O}}_{3}$ perovskites, unambiguous determination of the same in layered perovskites is more difficult due to their complex crystal structures. Here, we combined x-ray pair distribution function and density functional theory calculations to characterize the structure of cation-oxygen divacancy pairs in a Dion-Jacobson (D-J) layered perovskite. Our results indicate that local incommensurate dipole moments with polarization density in the range of $\ensuremath{\sim}0.1--17\phantom{\rule{0.16em}{0ex}}\ensuremath{\mu}\mathrm{C}/\mathrm{c}{\mathrm{m}}^{2}$ are created due to divacancy-induced structural distortions in the D-J phase $\mathrm{K}{\mathrm{Ca}}_{2}{\mathrm{Nb}}_{3}{\mathrm{O}}_{10}$. This is comparable with defect dipole moments observed in well-known perovskite ferroelectrics. The current results imply that controlling the atomic defects can potentially lead to significant control of dielectric properties in D-J layered perovskites.

Enhancement of the electrocaloric effect in PbZr0.7Ti0.3O3 ceramics via La doping: Driven by phase co-existence or defect effects?

Lattice defects and their effects have been pivotal in studies of phase transitions in a wide range of materials. Introduction of such defects into a ferroelectric material through doping of secondary elements can be tailored towards specific applications but the mechanism through which the bulk properties change is seldom scrutinized. Here we study the effect of systematic La substitution into PbZr0.7Ti0.3O3 (PZT 70/30) ceramics whereby we analyzed the temperature dependent properties and estimated the temperature changes that could be induced upon application of an external electric field, namely the electrocaloric effect (ECE). Expecting the entropic changes to be maximal under an applied field, the suitability of the La doped PZT 70/30 system for EC applications had been a motivation to undertake the current task as this composition reportedly can host a rich variety of phases depending on La content including relaxor and antiferroelectric (AFE) states. An electrocaloric (EC) temperature change of 1.15 °C in a wide range of temperatures for 8% La doping at 45 kV/cm applied field was estimated from experimental data, the possible origins of which is discussed. We were able to explain the experimental results by adopting a Landau-Ginzburg based computational approach coupled with elasticity and electrostatics whereby La sites are treated as point defects in a PZT 70/30 lattice. The gradual slanting of the hystereses and reduction of the transition temperature in the samples with increasing La content is claimed to be a direct consequence of the electrical fields due to formation of dipolar defect complexes as backed by our simulations. The ECE is discussed in the light of the simulations and recent results for AFE ceramics.

Microwave absorbing property of gelcasting SiC-Si3N4 ceramics with hierarchical pore structures

In this work, X-band microwave absorbing properties of gelcasted SiC-Si3N4 ceramics with different hierarchical pore structures at both room temperature and high temperature were reported for the first time. Effects of pore structures, sample thickness and temperature on complex permittivity and microwave absorption performance of SiC-Si3N4 ceramics were investigated systemically. The results suggested that the introduction of appropriate hierarchical pore structure was beneficial to improve the absorbing performance of the material. The minimum reflection loss value can reach -59.2 dB for the 3.8 mm thick sample at 8.35 GHz and room temperature. By elevating the temperature, the effective absorption bandwidth of porous SiC-Si3N4 with a thickness of 3.0 mm covers the entire X-band. The excellent microwave absorbing property of porous SiC-Si3N4 ceramics was attributed to the multiple reflections brought about by the existence of hierarchical pores, interfacial polarization between SiC and Si3N4 grains, and defect dipole polarization in grains and grain boundaries. The good absorbing property and the clarification of absorbing mechanism of porous gelcasted SiC-Si3N4 ceramics will provide a solid foundation for the development of porous SiC-based absorbing parts.

Interplay of defect dipole and flexoelectricity in linear dielectrics

Flexoelectricity is apparently linearized with the dielectric permittivity and therefore regarded as an inherent dielectric response of solid dielectrics. Herein, we study the role of defect dipole to flexoelectricity by selecting several typical linear dielectrics, wherein the external factors including the surface piezoelectricity, ferroelectricity, and semiconducting interface are strictly eliminated. It is found that the defect dipoles could result in several times enhancement for both the flexoelectric coefficient and the flexocoupling coefficient of the linear dielectrics. The output of this work indicates that introducing defects was a general approach to improve the flexoelectric response.

Hole-Pinned Defect Clusters for a Large Dielectric Constant up to GHz in Zinc and Niobium Codoped Rutile SnO2.

High permittivity materials for a gigahertz (GHz) communication technology have been actively sought for some time. Unfortunately, in most materials, the dielectric constant starts to drop as frequencies increase through the megahertz (MHz) range. In this work, we report a large dielectric constant of ∼800 observed in defect-mediated rutile SnO2 ceramics, which is nearly frequency and temperature independent over the frequency range of 1 mHz to 35 GHz and temperature range of 50-450 K. Experimental and theoretical investigations demonstrate that the origin of the high dielectric constant can be attributed to the formation of locally well-defined Zn2+-Nb4+ defect clusters, which create hole-pinned defect dipoles. We believe that this work provides a promising strategy to advance dipole polarization theory and opens up a direction for the design and development of high frequency, broadband dielectric materials for use in future communication technology.

Anomalous Dielectric Behavior in Co-Doped TiO2 Nanotubes: Effect of Oxygen Vacancy Mediated Defect Dipole Pairs

Titanium dioxide (TiO2) nanotubes are considered to be unique in terms of their physical properties and high dielectric constant. The oxygen vacancies in TiO2 play a crucial role in the dielectric behavior, which can be tuned by doping with proper materials. Herein, the changes in the dielectric behavior, as well as defect concentration of TiO2 nanotubes by Cobalt (Co) doping, have been evaluated. For this purpose, Co-doped TiO2 nanotubes have been synthesized by using combined sol-gel and hydrothermal methods. By analyzing photoluminescence spectra, the intensities and positions of five emission peaks are clearly assigned. The PL peaks could be sensibly explained by various mechanisms, such as direct allowed transition, oxygen vacancies, and self-trapped excitons. The dielectric behavior of Co-doped TiO2 nanotubes with controlled oxygen vacancies is explained. The dielectric constant is particularly at its highest in higher Co-doped TiO2 nanotubes. The current investigation provides new insight into the mechanisms underlying the anomalous dielectric properties shown by Co-doped TiO2 nanotubes, as evident from the movement of oxygen vacancies. It demonstrates the influence of defect dipoles, 2CoTi—Vȯ••, in the anomalous dielectric behavior observed for Co-doped TiO2 nanotubes.

Multiple property enhancement in bismuth ferrite‐based ferroelectrics by balancing nanodomain and relaxor state

AbstractBismuth ferrite‐barium titanate (BF‐BT)‐based ferroelectrics have received widespread attention due to its adjustable structure features and multifunctional characteristics. Property optimization (ferroelectricity, piezoelectricity, electrostrain, electrostriction) for different application scenarios can be realized by increasing BT content gradually, while it is still difficult to integrate multiple performance advantages in the same component. To solve the problem and achieve the simultaneous enhancement of property parameters, defect engineering was adopted in this work to balance domain configuration and relaxor state via selective oxides modification strategy. Compared with the nanodomain engineered relaxor ferroelectrics with improved electrostrain and degraded ferroelectricity, the defect‐mediated ceramics doped with MnO2 present both enhanced electrostrain and ferroelectricity. Multiscale structure analysis (crystal structure, defect structure, and domain structure) and property characterization (ferroelectricity, strain property, and leakage current density) suggested that the defect dipoles induced by Mn substitution can effectively refine domain size and maintain ferroelectric state at room temperature, and the easier domain switching caused by weak‐correlated polar dipoles greatly improves both the strain and ferroelectricity. Especially, the defect dipoles‐mediated nanodomain and property enhancement can be only observed in BFO‐Mn ceramics, and infeasible for other oxides (e.g., CuO and CeO2). We believe that this work can provide some guidance to modify electrical properties in BF‐BT‐based ferroelectrics.

Investigation of the coupling effect of flexoelectricity and ferroelasticity on energy storage efficiency of relaxor ferroelectrics

The Ginzburg–Landau theory and dipole defect model have been employed to investigate the flexoelectric and ferroelastic effects on the ferroelectric and energy storage properties of relaxor ferroelectrics (RFs). The results obtained show that due to the existence of polar nanoregions (PNRs) in RFs, the elastic field of the material, which is induced by both the flexoelectric and ferroelastic effects, leads to the increase of the domain switching energy and coercive field and the decrease of the energy storage efficiency. In contrast, the short-range electric field induced by the dipole defects enhances the energy storage efficiency of the material by enhancing the material’s relaxor behavior. Hence, the energy storage efficiency of RFs can be effectively functionalized by modulating the composition ratio and the electric field of the RF materials.

Nonvolatile voltage-controlled magnetization reversal in a spin-valve multiferroic heterostructure

Pure voltage-controlled magnetism, rather than a spin current or magnetic field, is the goal for next-generation ultralow power consumption spintronic devices. To advance toward this goal, we report a voltage-controlled nonvolatile 90° magnetization rotation and voltage-assisted 180° magnetization reversal in a spin-valve multiferroic heterostructure. Here, a spin valve with a synthetic antiferromagnetic structure was grown on a (110)-cut Pb(Mg1/3Nb2/3)0.7Ti0.3O3 (PMN-PT) substrate, in which only the magnetic moment of the free layer can be manipulated by an electric field (E-field) via the strain-mediated magnetoelectric coupling effect. As a result of selecting a specified PMN-PT substrate with defect dipoles, nonvolatile and stable magnetization switching was achieved by using voltage impulses. Accordingly, a giant, reversible and nonvolatile magnetoresistance modulation was achieved without the assistance of a magnetic field. In addition, by adopting a small voltage impulse, the critical magnetic field required for complete 180° magnetization reversal of the free layer can be tremendously reduced. A magnetoresistance ratio as large as that obtained by a magnetic field or spin current under normal conditions is achieved. These results indicate that E-field-assisted energy-efficient in-plane magnetization switching is a feasible strategy. This work is significant to the development of ultralow-power magnetoresistive memory and spintronic devices.

Coexistence of giant positive and large negative electrocaloric effects in lead-free ferroelectric thin film for continuous solid-state refrigeration

The solid-state cooling technique utilizing electrocaloric (EC) materials is an alternative approach to tackle the greenhouse effect caused by traditional vapor-compression refrigeration. However, such a promising technique is severely hampered by the lack of proper materials considering that most existing EC materials with a single positive/negative EC effect exhibit a limited cooling effect. Here, the coexistence of a positive and negative EC effects has been achieved in a lead-free Na0.5Bi0.5(Ti0.97W0.01Fe0.02)O3 ferroelectric film. A state-of-the-art positive adiabatic temperature change (ΔT) of ~56 K accompanied by an isothermal entropy change (ΔS) of ~64 J K−1 kg−1 at 143 °C and a large negative ΔT of ~ − 17 K with a ΔS of ~ − 24 J K−1 kg−1 at 55 °C are obtained under a strong electric field strength of 2692 kV cm−1. Oxygen vacancy-related defect dipoles play a critical role in the negative EC effect at lower temperatures, while the phase transition is responsible for the positive EC effect at higher temperatures. Meanwhile, the film exhibits a high EC strength with a maximum ΔT/ΔE of 0.021 K cm kV−1, together with a ΔS/ΔE of 0.024 J cm K−1 kg−1 kV−1. This work ensures a giant total temperature change by utilizing and combining both the negative and positive EC effects in a dual cooling process.

Outstanding enhanced breakdown field strength and energy storage properties in Na0.5Bi0.5TiO3-based thin film by the aging process

Aging behavior is usually perceived as a negative effect in application of ferroelectrics; however, we observe that the aging process has a unique role in improving the energy storage properties. Here, Na 0.5 Bi 0.47 La 0.03 TiO 3 (NBLT) and Na 0.5 Bi 0.5 Ti 0.97 Mn 0.03 O 3 (NBMT) thin films deposited on Pt/TiO 2 /SiO 2 /Si substrate are prepared by sol-gel method. There is a high growth rate of breakdown filed strengthen ( BDS ) and energy storage density ( W ) in aged NBMT thin film, its BDS and W are enhanced from 2175 kV cm −1 to 3492 kV cm −1 , and from 16.1 J cm −3 to 37.7 Jcm −3 , respectively. It is demonstrated that the aging process tends to exhibit various levels of sensitivity on doping sites due to the formation and orientation of the defect dipoles are different. Besides, (Na 0.5 Bi 0.5 Ti 0.97 Mn 0.03 O 3 /Na 0.5 Bi 0.47 La 0.03 TiO 3 ) 5 and 0.65 Pb (Mg 1/3 Nb 2/3 ) O 3 -0.35PbTiO 3 /(Na 0.5 Bi 0.5 Ti 0.97 Mn 0.03 O 3 /Na 0.5 Bi 0.47 La 0.03 TiO 3 ) 3 [(M/L) 5 and P/(M/L) 3 ] are constructed to introduce interface to enhance BDS , where an outstanding energy density of 56.8 J cm −3 under 3579 kV cm −1 is achieved in aged P/(M/L) 3 thin film. The aging process and introduction of interfaces are responsible for this improvement, and a possible mechanism for the aging process is proposed. It is concluded that the aging process combined with interface engineering is an effective strategy to improve energy storage properties. • NBT-based thin film with different doping sites were fabricated by sol-gel method. • The aging behavior and interface engineering enhance breakdown field strength. • Realizing energy density of 56.8 J cm −3 under 3579 kV cm −1 in aged P/(M/L) 3 thin film. • A possible mechanism for the aging process was proposed.

Structural evolution and dielectric properties of (Bi, Mg, Zr)-doped BaTiO3 ceramics for X8R-MLCC application

The (1-x) BaTiO3-x (0.5Bi2O3-0.67MgO-0.33ZrO2) ceramics (x = 5, 10, 15 and 20 mol%) are fabricated by a conventional solid-state method in a reducing atmosphere. All ceramics display a pure perovskite phase without any trace of secondary phase, and a phase transition from tetragonal phase to pseudo-cubic phase occurs between x = 0.1 and x = 0.15. The dielectric analysis manifests that both the dielectric constant and insulation resistivity at room temperature decrease with increasing dopants, which is mainly related to the reduction of grain boundaries. Meanwhile, high dielectric constant (∼2020) and excellent insulation resistivity (∼4.81 × 1013 ΩΩ ·cm) are obtained when x = 0.05. Besides, the temperature stability of ceramics in the high temperature region is improved with little BMZ-doping, and BMZ05 ceramic satisfies the EIA X8R standard. The complex impedance demonstrates that obvious heterogeneous interfaces and strong interface polarization are existed in ceramics. The fitted activation energy of grain boundary reflects that the long-range hopping polarization of oxygen vacancies dominates in the dielectric constant of ceramics when x < 0.1, while the short-range hopping polarization of defect dipoles dominates when x > 0.15.

One simple approach, two remarkable enhancements: Manipulating defect dipoles and local stress of (K, Na)NbO3-based ceramics

Although the composition-driven multi-phase coexistence strategy has been widely used to modify the piezoelectric properties of potassium sodium niobate ((K, Na)NbO3, KNN) based ceramics, the trade-off between long-range ferroelectric ordering and chemical additives-induced disorder hinders the further improvement of piezoelectricity and makes the electric field-induced strain temperature-dependent. Herein, to resolve two issues, we proposed a new concept, that is, manipulating defect dipoles and local stress of a pre-constructed multi-phase coexistence through controlling zirconium (Zr) content. We validated the new concept by designing 0.96(K0.4Na0.6)Nb0.955Sb0.045O3-0.04(Bi0.5Na0.5)Zr(1+x)O3 ceramics. In samples with Zr deficiency (i.e., x=-0.1), we obtained high retention of 91% in normalized unipolar strain (Suni) over the temperature range of 30-160 °C, even under low electric fields of 10-20 kV/cm, superior to those of other representative KNN-based ceramics. In samples with slight Zr excess (i.e., x=0.07), we achieved an increase in direct piezoelectric coefficient (d33) and converse piezoelectric coefficient (d33*) by 12% and 25%, respectively, in comparison with that at x=0. The enhanced temperature stability stems from the released domain walls that are pinned by defect dipoles, and the increased d33 (and d33*) originates from the synergetic contributions of the multi-phase coexistence, increased grain size, and stabilization of the ZrO2 secondary phase. Therefore, our new concept would benefit the composition design and performance improvement of KNN-based ceramics in the future.

Interplay between polarization, strain, and defect pairs in Fe-doped SrMnO3−δ

Defect chemistry, strain, and structural, magnetic and electronic degrees of freedom constitute a rich space for the design of functional properties in transition metal oxides. Here, we show that it is possible to engineer polarity and ferroelectricity in non-polar perovskite oxides via polar defect pairs formed by anion vacancies coupled to substitutional cations. We use a self-consistent site-dependent DFT+$U$ approach that accounts for local structural and chemical changes upon defect creation and which is crucial to reconcile predictions with the available experimental data. Our results for Fe-doped oxygen-deficient SrMnO$_3$ show that substitutional Fe and oxygen vacancies can promote polarity due to an off-center displacement of the defect charge resulting in a net electric dipole moment, which polarizes the lattice in the defect neighborhood. The formation of these defects and the resulting polarization can be tuned by epitaxial strain, resulting in enhanced polarization also for strain values lower than the ones necessary to induce a polar phase transition in undoped SrMnO$_3$. For high enough defect concentrations, these defect dipoles couple in a parallel fashion, thus enabling defect- and strain-based engineering of ferroelectricity in SrMnO$_3$.

Polarization enhancement in Fe doped BNT based relaxors using Bi compensation

Pseudocubic structural BNT-BT-BST based ergodic relaxors are investigated through Bi3+ and Fe3+ modulation in A and B sites of perovskite. High recoverable energy storage density and efficiency with excellent thermal stability, and large electrostrictive strain (0.24%) with ultralow hysteresis (2.8%) are achieved under a relatively low electric field. Slim polarization hysteresis (P-E) loops and strain curves are attributed to the absence of long-range ferroelectric domain as the introduction of BST. The incremental dopants that can restrain oxygen vacancies induced by A-site cationic vacancy (VA′′), will promote polarization, strengthen relaxor characteristics and suppress the reduction of Ti4+. A detailed mechanism of relaxor-ferroelectric phase transition and defect dipole of (FeTi′−VO••)• on polarization and electrostrictive strain is discussed. The work provides a new route in designing low-hysteresis BNT based relaxors for practical energy storage and actuator applications.

High energy storage density and temperature-stable dielectric properties for (1-x)Bi0.38Na0.38Sr0.24TiO3-xBaSnO3 lead-free relaxor ceramics

Relaxor ferroelectrics are promising candidates for energy storage equipment due to their excellent energy-storage properties. Lead-free (1-x)Bi0.38Na0.38Sr0.24TiO3-xBaSnO3 (abbreviated as BNST-100xBS) relaxor ceramics were synthesized by a traditional solid-phase sintering method. The influences of the addition of BaSnO3 dopants for the energy storage and dielectric temperature-stable properties of BNST-100xBS ceramics were systemically investigated. All samples exhibited a typical pseudo-cubic symmetry structure and obtained the dense microstructure. The ergodic relaxor behavior of all ceramics was observed and revealed a trend of increase as a function of composition. All samples showed a single grain conduction mechanism and the activation energy decreased with the addition of composition. It is related to the generation of oxygen vacancies induced by the defect dipoles. BNST-2.5BS ceramic exhibited an outstanding recoverable energy density of ~1.42 J/cm3 with the corresponding efficiency of ~79.7% at 115 kV/cm field. In addition, excellent temperature-stable permittivity (43–255 °C) was obtained for BNST-7.5BS ceramic. Hence, BNST-2.5BS ceramic revealed excellent energy density properties and BNST-7.5BS exhibited outstanding temperature-stable dielectric permittivity, which was beneficial to use in energy storage equipment and other device applications.

Structural, optical and electrical properties of Mn-doped ZnFe2O4 synthesized using sol–gel method

The system Zn1-xMnxFe2O4 (x = 0, 2, and 4%) was prepared by sol–gel chemical route at 80 °C. X-Ray powder diffraction and Raman spectrum analysis were used to determine the preliminary phase of obtained samples. W–H and SSP plots were used to determine the crystallite size and micro-strain of samples. The surface charge and morphology of the samples were studied using zeta potential and scanning electron microscope analysis, respectively. The optical bandgap of the samples suggested that they were semiconducting. The dielectric characteristics of samples were examined as a function of temperature (60–600 °C) at various frequencies (1 kHz, 10 kHz, 100 kHz, and 1 MHz). The presence of interfacial and orientational polarization was indicated by dielectric constant and dissipation factor studies, which ranged from (0.7–460) to (0.3–0.8) with Mn and were found thermally stable up to 300 °C. The thermal dependence of DC conductivity demonstrates Arrhenius type transport with one, two, and three regions of conduction in sample ZF-0, ZF-2, and ZF-4 respectively. The sources of charge carriers in samples were $${V}_{o}^{\cdot \cdot }$$ , $$e^{\prime}$$ and dipole defects $$\left( {V_{o}^{{ \cdot \cdot }} - 2{Fe_{{Fe^{{3 + }} }}^{{2 + }}} ^{\prime } } \right)$$ / $$\left( {{2Mn^{{3 + }} _{Zn^{{2 + }} }}^.- 2{Fe_{{Fe^{{3 + }} }}^{{2 + }}} ^{\prime } } \right)$$ . The current work could help to identify the possible applications in semiconductor devices, thermally stable capacitors, and as mixed ionic electronic conductors in solid oxide fuel cells.