Enhanced On–Off Ratio Photodetectors Based on Lead‐Free Cs3Bi2I9 Single Crystal Thin Films

Hybrid organic–inorganic lead halide perovskite single crystal thin film (SCTF) recently has attracted enormous interest in the field of optoelectronic devices, since it efficiently resolves the trade‐off between thickness and carrier diffusion length. However, the toxicity of lead element and the instability induced by organic component still hinder its future developments. In this work, lead‐free all‐inorganic Cs₃Bi₂I₉ SCTF with a high orientation along (00h) has been in situ grown on indium tin oxide (ITO) glass via a space‐limited solvent evaporation crystallization method. The trap density of Cs₃Bi₂I₉ SCTF (5.7 × 10¹² cm^?3) is 263 folds lower than that of the polycrystalline thin film (PCTF) counterpart, together with a 5‐order‐of‐magnitude higher carrier mobility. These superior charge transfer properties enable a photoresponse on–off ratio as high as 11 000, which far surpasses that of the PCTF device by 460 folds, comparable to the lead halide perovskite. Furthermore, the Cs₃Bi₂I₉ SCTF photodetector exhibits outstanding stability even without any encapsulation, whose initial performance is well maintained after aging 1000 h in humid air of 50% RH or continuous on–off light illumination for 20 h. This work will pave the way to produce new families of high‐performance, stable, and nontoxic perovskite SCTF for future optoelectronic applications.     

All‐Inorganic Bismuth‐Based Perovskite Quantum Dots with Bright Blue Photoluminescence and Excellent Stability

Lead halide perovskite quantum dots (QDs) possess color‐tunable and narrow‐band emissions and are very promising for lighting and display applications, but they suffer from lead toxicity and instability. Although lead‐free Bi‐based and Sn‐based perovskite QDs (CsSnX₃, Cs₂SnX₆, and (CH₃NH₃)₃Bi₂X₉) are reported, they all show low photoluminescence quantum yield (PLQY) and poor stability. Here, the synthesis of Cs₃Bi₂Br₉ perovskite QDs with high PLQY and excellent stability is reported. Via a green and facile process using ethanol as the antisolvent, as‐synthesized Cs₃Bi₂Br₉ QDs show a blue emission at 410 nm with a PLQY up to 19.4%. The whole series of Cs₃Bi₂X₉ (X = Cl, Br, and I) QDs by mixing precursors can cover the photoluminescence emission range from 393 to 545 nm. Furthermore, Cs₃Bi₂Br₉ QDs show excellent photostability and moisture stability due to the all‐inorganic nature and the surface passivation by BiOBr, which enables the one‐pot synthesis of Cs₃Bi₂Br₉ QD/silica composite. A lead‐free perovskite white light‐emitting diode is fabricated by simply combining the composite of Cs₃Bi₂Br₉ QD/silica with Y₃Al₅O₁₂ phosphor. As a new member of lead‐free perovskite QDs, Cs₃Bi₂Br₉ QDs open up a new route for the fabrication of optoelectronic devices due to their excellent stability and photophysical characteristics.     

Low‐Dimensional Lead‐Free Inorganic Perovskites for Resistive Switching with Ultralow Bias

3D organic–inorganic and all‐inorganic lead halide perovskites have been intensively pursued for resistive switching memories in recent years. Unfortunately, instability and lead toxicity are two foremost challenges for their large‐scale commercial applications. Dimensional reduction and composition engineering are effective means to overcome these challenges. Herein, low‐dimensional inorganic lead‐free Cs₃Bi₂I₉ and CsBi₃I₁₀ perovskite‐like films are exploited for resistive switching memory applications. Both devices demonstrate stable switching with ultrahigh on/off ratios (≈10⁶), ultralow operation voltages (as low as 0.12 V), and self‐compliance characteristics. 0D Cs₃Bi₂I₉‐based device shows better retention time and larger reset voltage than the 2D CsBi₃I₁₀‐based device. Multilevel resistive switching behavior is also observed by modulating the current compliance, contributing to the device tunability. The resistive switching mechanism is hinged on the formation and rupture of conductive filaments of halide vacancies in the perovskite films, which is correlated with the formation of AgI_x layers at the electrode/perovskite interface. This study enriches the library of switching materials with all‐inorganic lead‐free halide perovskites and offers new insights on tuning the operation of solution‐processed memory devices.     

Displacive Order–Disorder Behavior and Intrinsic Clustering of Lattice Distortions in Bi‐Substituted NaNbO3

Perovskite‐like NaNbO₃‐Bi_1/3NbO₃ solid solutions are studied to understand the interactions between octahedral rotations, which dominate the structural behavior of NaNbO₃ and displacive disorder of Bi present in Bi_1/3NbO₃. Models of instantaneous structures for representative compositions are obtained by refining atomic coordinates against X‐ray total scattering and extended X‐ray‐absorption fine structure data, with additional input obtained from transmission electron microscopy. A mixture of distinct cations and vacancies on the cuboctahedral A‐sites in Na_1?3xBi_xNbO₃ (x ≤ 0.2) results in 3D nanoscale modulations of structural distortions. This phenomenon is determined by the inevitable correlations in the chemical composition of adjacent unit cells according to the structure type—an intrinsic property of any nonmolecular crystals. Octahedral rotations become suppressed as x increases. Out‐of‐phase rotations vanish for x > 0.1, whereas in‐phase tilts persist up to x = 0.2, although for this composition their correlation length becomes limited to the nanoscale. The loss of out‐of‐phase tilting is accompanied by qualitative changes in the probability density distributions for Bi and Nb, with both species becoming disordered over loci offset from the centers of their respective oxygen cages. Symmetry arguments are used to attribute this effect to different strengths of the coupling between the cation displacements and out‐of‐phase versus in‐phase rotations. The displacive disorder of Bi and Nb combined with nanoscale clustering of lattice distortions are primarily responsible for the anomalous broadening of the temperature dependence of the dielectric constant.     

A New Phase Boundary in (Bi1/2Na1/2)TiO3−BaTiO3 Revealed via a Novel Method of Electron Diffraction Analysis

A new phase boundary is revealed in (1–x)(Bi_1/2Na_1/2)TiO₃?xBaTiO₃, the most extensively studied lead‐free piezoelectric solid solution. This discovery results from a novel method of electron diffraction analysis, which allows the precise determination of oxygen octahedra tilting in multi‐domain perovskite ferroelectrics. The study using this method supports the recently proposed Cc symmetry for pure (Bi_1/2Na_1/2)TiO₃, and, more importantly, indicates the crystal structure evolves into the R3c symmetry with the addition of BaTiO₃, forming a Cc/R3c phase boundary at x = 3–4%. In the poling field E_pol versus composition x phase diagram for polycrystalline ceramics, this phase boundary exists with E_pol below 5.5 kV mm^?1; the Cc phase is transformed to the R3c phase during poling at higher fields. The results reported here provide the microstructural origin for the previously unexplained strain behavior and clarify the low‐BaTiO₃‐content phase relationship in this popular lead‐free piezoelectric system.     

Inch‐Size Single Crystal of a Lead‐Free Organic–Inorganic Hybrid Perovskite for High‐Performance Photodetector

Large‐size crystals of organic–inorganic hybrid perovskites (e.g., CH₃NH₃PbX₃, X = Cl, Br, I) have gained wide attention since their spectacular progress on optoelectronic technologies. Although presenting brilliant semiconducting properties, a serious concern of the toxicity in these lead‐based hybrids has become a stumbling block that limits their wide‐scale applications. Exploring lead‐free hybrid perovskite is thus highly urgent for high‐performance optoelectronic devices. Here, a new lead‐free perovskite hybrid (TMHD)BiBr₅ (TMHD = N,N,N,N‐tetramethyl‐1,6‐hexanediammonium) is prepared from facile solution process. Emphatically, inch‐size high‐quality single crystals are successfully grown, the dimensions of which reach up to 32 × 24 × 12 mm³. Furthermore, the planar arrays of photodetectors based on bulk lead‐free (TMHD)BiBr₅ single crystals are first fabricated, which shows sizeable on/off current ratios (≈10³) and rapid response speed (τ_rise = 8.9 ms and τ_decay = 10.2 ms). The prominent device performance of (TMHD)BiBr₅ strongly underscores the lead‐free hybrid perovskite single crystals as promising material candidates for optoelectronic applications.     

Understanding Bulk Defects in Topological Insulators from Nuclear‐Spin Interactions

Non‐invasive local probes are needed to characterize bulk defects in binary and ternary chalcogenides. These defects contribute to the non‐ideal behavior of topological insulators. The bulk electronic properties are studied via ¹²⁵Te NMR in Bi₂Te₃, Sb₂Te₃, Bi_0.5Sb_1.5Te₃, Bi₂Te₂Se, and Bi₂Te₂S. A distribution of defects gives rise to asymmetry in the powder lineshapes. The Knight shift, line shape, and spin‐lattice relaxation are investigated in terms of how they affect carrier density, spin‐orbit coupling, and phase separation in the bulk. The present study confirms that the ordered ternary compound Bi₂Te₂Se is the best topological insulator candidate material at the present time. These results, which are in good agreement with transport and angle‐resolved photoemission spectroscopy studies, help establish the NMR probe as a valuable method to characterize the bulk properties of these materials.     

Defect‐Driven Structural Distortions at the Surface of Relaxor Ferroelectrics

Relaxor‐ferroelectric materials find application in a broad range of technological devices, including ultrasonic imaging transducers, nanopositioning, and high‐performance capacitors. They generally exhibit occupationally disordered structures creating local polar fluctuations that are highly sensitive to applied electric or stress fields. The sensitivity of the material structure to external field and stress conditions also makes them likely to develop skin or surface phases that are unique from the bulk. Surface layers can adjust the material response and also lead to ambiguity in structural characterization. Here, using a combination of X‐ray diffraction methods, it is shown that a ≈20 µm skin structure commonly exists in the lead‐free relaxor‐ferroelectric ceramic (Na_1/2Bi_1/2)TiO₃–BaTiO₃. Using experiments and density functional theory calculations, it is shown that the combined action of oxygen vacancies providing internal chemical pressure and the surface plane stress state dictates the stability and structure of the skin layer. This work can be extended to all perovskite relaxor ferroelectrics and provides new insights into the origin of skin layers in these materials. The opportunity exists to further enhance the functionality of these materials through engineering of surface structures using the methods outlined here.     

Dual‐Phase All‐Inorganic Cesium Halide Perovskites for Conducting‐Bridge Memory‐Based Artificial Synapses

Neuromorphic computing, which mimics biological neural networks, can overcome the high‐power and large‐throughput problems of current von Neumann computing. Two‐terminal memristors are regarded as promising candidates for artificial synapses, which are the fundamental functional units of neuromorphic computing systems. All‐inorganic CsPbI₃ perovskite‐based memristors are feasible to use in resistive switching memory and artificial synapses due to their fast ion migration. However, the ideal perovskite phase α‐CsPbI₃ is structurally unstable at ambient temperature and rapidly degrades to a non‐perovskite δ‐CsPbI₃ phase. Here, dual‐phase (Cs₃Bi₂I₉)_0.4?(CsPbI₃)_0.6 is successfully fabricated to achieve improved air stability and surface morphology compared to each single phase. Notably, the Ag/polymethylmethacrylate/(Cs₃Bi₂I₉)_0.4?(CsPbI₃)_0.6/Pt device exhibits non‐volatile memory functions with an endurance of ≈10³ cycles and retention of ≈10⁴ s with low operation voltages. Moreover, the device successfully emulates synaptic behavior such as long‐term potentiation/depression and spike timing/width‐dependent plasticity. This study will contribute to improving the structural and mechanical stability of all‐inorganic halide perovskites (IHPs) via the formation of dual phase. In addition, it proves the great potential of IHPs for use in low‐power non‐volatile memory devices and electronic synapses.     

Photoresponsive Transistors Based on Lead‐Free Perovskite and Carbon Nanotubes

Lead‐free perovskite materials are exhibiting bright application prospects in photodetectors (PDs) owing to their low toxicity compared with traditional lead perovskites. Unfortunately, their photoelectric performance is constrained by the relatively low charge conductivity and poor stability. In this work, photoresponsive transistors based on stable lead‐free bismuth perovskites CsBi₃I₁₀ and single‐walled carbon nanotubes (SWCNTs) are first reported. The SWCNTs significantly strengthen the dissociation and transportation of the photogenerated charge carriers, which lead to dramatically improved photoresponsivity, while a decent I_light/I_dark ratio over 10² can be maintained with gate modulation. The devices exhibit high photoresponsivity (6.0 × 10⁴ A W^?1), photodetectivity (2.46 × 10¹⁴ jones), and external quantum efficiency (1.66 × 10⁵%), which are among the best reported results in lead‐free perovskite PDs. Furthermore, the excellent stability over many other lead‐free perovskite PDs is demonstrated over 500 h of testing. More interestingly, the device also shows the application potential as a light‐stimulated synapse and its synaptic behaviors are demonstrated. In summary, the lead‐free bismuth perovskite‐based hybrid phototransistors with multifunctional performance of photodetection and light‐stimulated synapse are first demonstrated in this work.     

Variations of Infiltration and Electronic Contact in Mesoscopic Perovskite Solar Cells Revealed by High‐Resolution Multi‐Mapping Techniques

A combination of high‐resolution mapping techniques is developed to probe the homogeneity and defects of mesoscopic perovskite solar cells. Three types of cells using a one‐step infiltration process with methylammonium lead iodide (MAPbI₃) or 5‐ammoniumvaleric acid‐MAPbI₃ solutions, or two‐step process with MAPbI₃ solution are investigated. The correlation between photoluminescence, photocurrent, electroluminescence, and Raman maps gives a detailed understanding of the different infiltration mechanisms, electronic contact at interfaces, and effect on local photocurrent for the cells. The one‐step MAPbI₃ cell has very limited infiltration of the perovskite solution which results in poor device performance. High loading of the mesopores of the TiO₂ and ZrO₂ scaffold is observed when using 5‐ammoniumvaleric acid, but some micrometer‐sized non‐infiltrated areas remain due to dense carbon flakes hindering perovskite infiltration. The two‐step cell has a complex morphology with features having either beneficial or detrimental effects on the local photocurrent. The results not only provide key insights to achieving better infiltration and homogeneity of the perovskite film in mesoporous devices but can also aid further work on planar devices to develop efficient extraction layers. Moreover, this multi‐mapping approach allows the correlation of the local photophysical properties of full perovskite devices, which would be challenging to obtain by other techniques.     

Criticality: Concept to Enhance the Piezoelectric and Electrocaloric Properties of Ferroelectrics

Compositional engineering with a focus on structural phase transitions has been considered as the most important approach for enhancement of the functional properties of ferroelectric materials due to the critical fluctuation of physical properties. Of special interest are electric‐field‐induced phase transitions, which can terminate in a liquid–vapor‐type critical point with a strong enhancement of functional properties. Whereas the critical point in liquid–vapor space considers changes in temperature and pressure, the critical point in this study is placed in electric field–temperature diagrams. In single crystals, temperature and electric field of a critical point are sharply defined and therefore not appealing for practical applications. However, in ceramics, it is demonstrated that the orientational dependence of the critical point leads to a broadened temperature and electric field range. The presence of a diffuse critical point in ceramics provides a conceptually novel approach for the enhancement of functional properties, such as piezoelectric and electrocaloric (EC) responses, as validated here on the example of the 0.75Bi_1/2Na_1/2TiO₃‐0.25SrTiO₃ lead‐free relaxor ferroelectric ceramics. The realization of a broad criticality range will further facilitate the development of the piezoelectric and EC materials and provide an alternative concept to manipulate the functional properties by application of an electric field.     

Materials Discovery of Stable and Nontoxic Halide Perovskite Materials for High‐Efficiency Solar Cells

Two critical limitations of organic–inorganic lead halide perovskite materials for solar cells are their poor stability in humid environments and inclusion of toxic lead. In this study, high‐throughput density functional theory (DFT) methods are used to computationally model and screen 1845 halide perovskites in search of new materials without these limitations that are promising for solar cell applications. This study focuses on finding materials that are comprised of nontoxic elements, stable in a humid operating environment, and have an optimal bandgap for one of single junction, tandem Si‐perovskite, or quantum dot–based solar cells. Single junction materials are also screened on predicted single junction photovoltaic (PV) efficiencies exceeding 22.7%, which is the current highest reported PV efficiency for halide perovskites. Generally, these methods qualitatively reproduce the properties of known promising nontoxic halide perovskites that are either experimentally evaluated or predicted from theory. From a set of 1845 materials, 15 materials pass all screening criteria for single junction cell applications, 13 of which are not previously investigated, such as (CH₃NH₃)_0.75Cs_0.25SnI₃, ((NH₂)₂CH)Ag_0.5Sb_0.5Br₃, CsMn_0.875Fe_0.125I₃, ((CH₃)₂NH₂)Ag_0.5Bi_0.5I₃, and ((NH₂)₂CH)_0.5Rb_0.5SnI₃. These materials, together with others predicted in this study, may be promising candidate materials for stable, highly efficient, and nontoxic perovskite‐based solar cells.     

Room‐Temperature AFM Electric‐Field‐Induced Topotactic Transformation between Perovskite and Brownmillerite SrFeOx with Sub‐Micrometer Spatial Resolution

Reversible structural transformations between perovskite (PV) ABO_3?δ and brownmillerite (BM) ABO_2.5 (A = Ca²⁺, Sr²⁺; B = Fe^4+/3, Co^4+/3+) oxides can be induced by topotactic oxygen exchange at moderate temperatures under reducing/oxidizing conditions. The combination of a large oxide‐ion conductivity and a small free energy difference between the 4+/3+ oxidation states of many 3d transition metal ions enables these topotactic transformations. Herein, it is demonstrated that the electric field produced by a voltage‐biased atomic force microscopy tip can induce such transformation between PV SrFeO_3?δ and BM SrFeO_2.5 at room temperature and with sub‐micrometer spatial resolution. Interestingly, the structural transformation is kept after the electric field is removed, allowing a nonvolatile control of the local chemical, electrical, optical, and magnetic properties. Thus, the results presented in this paper open the door for the fabrication of stable ionic‐based devices through the electric field patterning of different crystallographic phases.     

Resistance reduction effect of potassium bismuth titanate doping in yttrium–manganese co-doped medium Curie temperature barium titanate lead free ceramics through improved synthesis process

Through improved synthesis process, resistance reduction effect of (K_0.5Bi_0.5)TiO₃ (KBT) doping in Y–Mn co-doped BaTiO₃ (BT) lead free ceramics was investigated. By different doping methods (doping K₂O, Bi₂O₃ and TiO₂ or synthesized KBT), medium Curie temperature (around 130 °C) lead free BT ceramics were obtained with ultra-low resistivity (13.84 Ωcm) with a temperature maintaining process at 700 °C. In this contribution, effect of sintering process and doping methods is discussed in detail.     

Ultrahigh Energy‐Storage Density in NaNbO3‐Based Lead‐Free Relaxor Antiferroelectric Ceramics with Nanoscale Domains

Dielectric energy‐storage capacitors have received increasing attention in recent years due to the advantages of high voltage, high power density, and fast charge/discharge rates. Here, a new environment‐friendly 0.76NaNbO₃–0.24(Bi_0.5Na_0.5)TiO₃ relaxor antiferroelectric (AFE) bulk ceramic is studied, where local orthorhombic Pnma symmetry (R phase) and nanodomains are observed based on high‐resolution transmission electron microscopy, selected area electron diffraction, and in/ex situ synchrotron X‐ray diffraction. The orthorhombic AFE R phase and relaxor characteristics synergistically contribute to the record‐high energy‐storage density W_rec of ≈12.2 J cm^?3 and acceptable energy efficiency η ≈ 69% at 68 kV mm^?1, showing great advantages over currently reported bulk dielectric ceramics. In comparison with normal AFEs, the existence of large random fields in the relaxor AFE matrix and intrinsically high breakdown strength of NaNbO₃‐based compositions are thought to be responsible for the observed energy‐storage performances. Together with the good thermal stability of W_rec (>7.4 J cm^?3) and η (>73%) values at 45 kV mm^?1 up to temperature of 200 °C, it is demonstrated that NaNbO₃‐based relaxor AFE ceramics will be potential lead‐free dielectric materials for next‐generation pulsed power capacitor applications.     

Preparation and Thermoelectric Properties of Doped Bi2Te3-Bi2Se3 Solid Solutions

Since Bi₂Te₃ and Bi₂Se₃ have the same crystal structure, they form a homogeneous solid solution. Therefore, the thermal conductivity of the solid solution can be reduced by phonon scattering. The thermoelectric figure of merit can be improved by controlling the carrier concentration through doping. In this study, Bi₂Te_2.85Se_0.15:D _m (D: dopants such as I, Cu, Ag, Ni, Zn) solid solutions were prepared by encapsulated melting and hot pressing. All specimens exhibited n-type conduction in the measured temperature range (323 K to 523 K), and their electrical conductivities decreased slightly with increasing temperature. The undoped solid solution showed a carrier concentration of 7.37 × 10¹⁹ cm^?3, power factor of 2.1 mW m^?1 K^?1, and figure of merit of 0.56 at 323 K. The figure of merit (ZT) was improved due to the increased power factor by I, Cu, and Ag dopings, and maximum ZT values were obtained as 0.76 at 323 K for Bi₂Te_2.85Se_0.15:Cu_0.01 and 0.90 at 423 K for Bi₂Te_2.85Se_0.15:I_0.005. However, the thermoelectric properties of Ni- and Zn-doped solid solutions were not enhanced.     

Self‐Assembled Room Temperature Multiferroic BiFeO3‐LiFe5O8 Nanocomposites

Multiferroic materials have driven significant research interest due to their promising technological potential. Developing new room‐temperature multiferroics and understanding their fundamental properties are important to reveal unanticipated physical phenomena and potential applications. Here, a new room temperature multiferroic nanocomposite comprised of an ordered ferrimagnetic spinel α‐LiFe₅O₈ (LFO) and a ferroelectric perovskite BiFeO₃ (BFO) is presented. It is observed that lithium (Li)‐doping in BFO favors the formation of LFO spinel as a secondary phase during the synthesis of Li_xBi_1?xFeO₃ ceramics. Multimodal functional and chemical imaging methods are used to map the relationship between doping‐induced phase separation and local ferroic properties in both the BFO‐LFO composite ceramics and self‐assembled nanocomposite thin films. The energetics of phase separation in Li doped BFO and the formation of BFO‐LFO composites are supported by first principles calculations. These findings shed light on Li's role in the formation of a functionally important room temperature multiferroic and open a new approach in the synthesis of light element doped nanocomposites for future energy, sensing, and memory applications.     

Interplay of Structural and Optoelectronic Properties in Formamidinium Mixed Tin–Lead Triiodide Perovskites

Mixed lead–tin triiodide perovskites are promising absorber materials for low bandgap bottom cells in all‐perovskite tandem photovoltaic devices. Key structural and electronic properties of the FAPb_1−xSn_xI₃ perovskite are presented here as a function of lead:tin content across the alloy series. Temperature‐dependent photoluminescence and optical absorption measurements are used to identify changes in the bandgap and phase transition temperature. The large bandgap bowing parameter, a crucial element for the attainment of low bandgaps in this system, is shown to depend on the structural phase, reaching a value of 0.84 eV in the low‐temperature phase and 0.73 eV at room temperature. The parabolic nature of the bowing at all temperatures is compatible with a mechanism arising from bond bending to accommodate the random placement of unevenly sized lead and tin ions. Charge‐carrier recombination dynamics are shown to fall into two regimes. Tin‐rich compositions exhibit fast, monoexponential recombination that is almost temperature‐independent, in accordance with high levels of electrical doping. Lead‐rich compositions show slower, stretched‐exponential charge‐carrier recombination that is strongly temperature‐dependent, in accordance with a multiphonon assisted process. These results highlight the importance of structure and composition for control of bandgap bowing and charge‐carrier recombination mechanisms in low bandgap absorbers for all‐perovskite tandem solar cells.     

The Polar/Antipolar Phase Boundary of BiMnO3–BiFeO3–PbTiO3: Interplay among Crystal Structure,Point Defects,and Multiferroism

The ferromagnetic perovskite oxide BiMnO₃ is a highly topical material, and the solid solutions it forms with antiferromagnetic/ferroelectric BiFeO₃ and with ferroelectric PbTiO₃ result in distinctive polar/nonpolar morphotropic phase boundaries (MPBs). The exploitation of such a type of MPBs could be a novel approach to engineer novel multiferroics with phase‐change magnetoelectric responses, in addition to ferroelectrics with enhanced electromechanical performance. Here, the interplay among crystal structure, point defects, and multiferroic properties of the BiMnO₃–BiFeO₃–PbTiO₃ ternary system at its line of MPBs between polymorphs of tetragonal P4mm (polar) and orthorhombic Pnma (antipolar) symmetries is reported. A strong dependence of the phase coexistence on thermal history is found: phase percentage significantly changes whether the material is quenched or slowly cooled from high temperature. The origin of this phenomenon is investigated with temperature‐dependent structural and physical property characterizations. A major role of the complex defect chemistry, where a Bi/Pb‐deficiency allows Mn and Fe ions to have a mixed‐valence state, in the delicate balance between polymorphs is proposed, and its influence in the magnetic and electric ferroic orders is defined.