Lead-free Metal Halide Perovskites Research Articles

Machine-Learning-Assisted Discovery of Mechanosynthesized Lead-Free Metal Halide Perovskites for the Oxidative Photocatalytic Cleavage of Alkenes.

Lead-free metal halide perovskites can potentially be air- and water-stable photocatalysts for organic synthesis, but there are limited studies on them for this application. Separately, machine learning (ML), a critical subfield of artificial intelligence, has played a pivotal role in identifying correlations and formulating predictions based on extensive datasets. Herein, an iterative workflow by incorporating high-throughput experimental data with ML to discover new lead-free metal halide perovskite photocatalysts for the aerobic oxidation of styrene is described. Through six rounds of ML optimization guided by SHapley Additive exPlanations (SHAP) analysis, BA2CsAg0.95Na0.05BiBr7 as a photocatalyst that afforded an 80% yield of benzoic acid under the standard conditions is identified, which is a 13-fold improvement compared to the 6% with when using Cs2AgBiBr6 as the initial photocatalyst benchmark that is started. BA2CsAg0.95Na0.05BiBr7 can tolerate various functional groups with 22 styrene derivatives, highlighting the generality of the photocatalytic properties demonstrated. Radical scavenging studies and density functional theory calculations revealed that the formation of the reactive oxygen species superoxide and singlet oxygen in the presence of BA2CsAg0.95Na0.05BiBr7 are critical for photocatalysis.

Tuning Electronic and Structural Properties of Lead-Free Metal Halide Perovskites: A Comparative Study of 2D Ruddlesden-Popper and 3D Compositions.

In recent decades, two-dimensional (\num{2}D) perovskites have emerged as promising semiconductors for next-generation photovoltaics, showing notable advancements in solar energy conversion. Herein, we explore the impact of alternative inorganic lattice \ce{BX}-based compositions ($\ce{B} = \ce{Ge}$ or \ce{Sn}, $\ce{X} = \ce{Br}$ or \ce{I}) on the energy gap and stability. Our investigation encompasses \ce{BA$_2$MA$_{n-1}$B$_n$X$_{3n+1}$} \num{2}D Ruddlesden-Popper perovskites (for $n = \num{1} - \num{5}$ layers) and \num{3}D bulk \ce{(MA)BX$_3$} systems, employing first-principles calculations with spin-orbit coupling (SOC), DFT-1/2 quasiparticle, and D3 dispersion corrections. The study unveils how atoms with smaller ionic radii induce anisotropic internal and external distortions within the inorganic and organic lattices. Introducing the \ce{BA} spacers in the low-layer regime reduces local distortions but widens band gaps. Our calculation protocol provides deeper insights into the physics and chemistry underlying \num{2}D perovskite materials, paving the way for optimizing environmentally friendly alternatives that can efficiently replace \ce{Pb} with sustainable materials.

Enhancing CsSn0.5Ge0.5I3 Perovskite Solar Cell Performance via Cu2O Hole Transport Layer Integration

Perovskite solar cells (PSCs) have emerged as a promising alternative to traditional silicon solar cells due to their low cost of fabrication and high power conversion efficiency (PCE). The utilization of lead halide perovskites as absorber layers in perovskite solar cells has been impeded by two major issues: lead poisoning and stability concerns. These hindrances have greatly impeded the industrialization of this cutting-edge technology. In light of the harmful effects of lead in perovskite solar cells, researchers have shifted their attention to exploring lead-free metal halide perovskites. However, the present alternatives to lead-based perovskite exhibit poor performance, thus prompting further inquiry into this matter. The primary objective of this research is to investigate the use of Cu2O as a hole transport layer in combination with lead-free metal halide perovskite (CsSn0.5Ge0.5I3) to achieve superior performance. Through meticulous experimentation, the suggested model has achieved outstanding results by optimizing several key variables. These variables include the thickness of the absorber layer (CsSn0.5Ge0.5I3), defect density, and doping densities, as well as the back contact work function and the operating temperature associated with each layer. The proposed FTO/PC60BM/CsSn0.5Ge0.5I3/Cu2O/Au solar cell structure surpassed prior configurations by comprehensively examining key aspects such as absorber layer thickness and defect density, doping densities, and back contact work. The structure has been also compared with multiple electron transport elements and concluded that the proposed model functions superior due to the use of PC60BM as an electron transport layer and it has an improved electron extraction procedure. Finally, the proposed model has achieved the optimized values as Jsc of 31.56 mA/cm-2, Voc of 1.12 V, FF of 81.47%, and PCE of 27.72%. As a consequence of this research, the investigated structure may be an excellent contender for the eventual creation of lead-free solar power cells made from perovskite.

Pressure-induced DFT evaluation of MSnI3 (M = K, Rb) perovskites for electronic phase transition and enhanced optoelectronic utilization

In optoelectronic device applications, perovskite materials have overtaken other compounds because of their exceptional power conversion efficiencies. Lead-based perovskites have found extensive use; however, their widespread adoption is hindered by the inherent toxicity associated with lead content. In contrast, lead-free metal halide perovskites have taken the dominant position in the commercialization of optoelectronic devices by offering high efficiency, affordability, flexibility, tunability, and environmental benefits. To better understand the structural, electronic, bonding, optical, elastic, and mechanical properties of the non-toxic MSnI3 (M = K, Rb) metal halides under different hydrostatic pressures, a first-principles simulation has been carried out with the use of density functional theory (DFT). Lattice parameters and electronic band structures have been computed using both the Generalized Gradient Approximation (GGA) and the non-local hybrid sX (Hartree-Fock screened exchange) functional. Utilizing the sX method results in enhanced band gap values for MSnI3 (M = K, Rb) perovskite compounds. The application of pressure has led to a decrease in both lattice parameters and band gaps, marking a transition from a semiconductor to a metallic state. The projection of the density of states and their electronic orbital contributions are also explored to evaluate the band structure tuning of MSnI3 (M = K, Rb) under pressure. The bond length calculation and the charge density mapping confirm the existence of both the ionic and covalent bonds in MSnI3 (M = K, Rb). Additionally, the pressure-induced calculation suggests that the bonds between both compounds will be stronger at high pressure. Increasing hydrostatic pressure causes a dramatic movement of the absorption edge of MSnI3 (M = K, Rb) perovskites into the low energy region (a red shift), which is revealed by the analysis of optical functions. The optical functions’ investigation indicates that the hydrostatic pressure allows the compounds even better for a number of possible uses. The mechanical qualities are a direct reflection of the ductile and anisotropic nature of the compounds, both of which are significantly influenced by the external pressure.

An all-inorganic lead-free metal halide double perovskite for the highly selective detection of norfloxacin in aqueous solution.

Lead-based perovskites are highly susceptible to environmental influences, and their application in analytical chemistry, especially in aqueous solution, has been reported rarely. All-inorganic lead-free metal halide perovskites have been considered as a substitute for lead-based perovskites. Herein, a Cs2RbTbCl6 perovskite microcrystal (PMCs), which emits strong yellow-green fluorescence with a maximum emission wavelength at 547nm, was for the first time synthesized and characterized. The Cs2RbTbCl6 PMCs could be well dispersed in N,N-dimethylacetamide (DMF), and its fluorescence could be significantly enhanced by the addition of norfloxacin (NOR) in the aqueous solution. We found that the Cs2RbTbCl6 PMCs can be used as fluorescent probes (excitation, 365nm; emission, 547nm) to selectively detect NOR in a concentration range from 10.0 to 200.0μM with the limit of detection (LOD) being 0.04μM. The Cs2RbTbCl6 PMCs could also be adsorbed on filter paper to fabricate as a fluorescent test paper for visual detection of NOR under 365-nm ultraviolet (UV) lamp irradiation. The proposed method has the potential to establish a new analytical method to visualize the detection of NOR in aqueous environments and also promotes the application of all-inorganic lead-free perovskites for analytical detection in aqueous environments.

Autonomous nanomanufacturing of lead-free metal halide perovskite nanocrystals using a self-driving fluidic lab.

Lead-based metal halide perovskite (MHP) nanocrystals (NCs) have emerged as a promising class of semiconducting nanomaterials for a wide range of optoelectronic and photoelectronic applications. However, the intrinsic lead toxicity of MHP NCs has significantly hampered their large-scale device applications. Copper-base MHP NCs with composition-tunable optical properties have emerged as a prominent lead-free MHP NC candidate. However, comprehensive synthesis space exploration, development, and synthesis science studies of copper-based MHP NCs have been limited by the manual nature of flask-based synthesis and characterization methods. In this study, we present an autonomous approach for the development of lead-free MHP NCs via seamless integration of a modular microfluidic platform with machine learning-assisted NC synthesis modeling and experiment selection to establish a self-driving fluidic lab for accelerated NC synthesis science studies. For the first time, a successful and reproducible in-flow synthesis of Cs3Cu2I5 NCs is presented. Autonomous experimentation is then employed for rapid in-flow synthesis science studies of Cs3Cu2I5 NCs. The autonomously generated experimental NC synthesis dataset is then utilized for fast-tracked synthetic route optimization of high-performing Cs3Cu2I5 NCs.

Achieving Multicolor Emitting of Antimony-Doped Indium-Based Halide Perovskite via Monovalent Metal Induced Phase Engineering.

Lead-free metal halide perovskites have attracted attention because of their excellent optical properties and nontoxicity. Here, we report the synthesis of Sb3+-doped indium halide perovskite Cs2InCl5·H2O:Sb3+ by an improved solution coprecipitation method. The treatment of the Sb3+-doped indium halide perovskite with selected monovalent cation halides led to Cs2MInCl6 (Ag+, K+, Na+) in different crystal structures or phases. Sb3+ has an isolated ns2 electron, and Sb3+-doped metal halide acts as the luminescence center and exhibits bright broadband emission that originated from self-trapped excitons. Under UV light excitation, these phosphors with different crystal structures emitted multicolored luminescence ranging from blue, green, yellow, and red depending on whether or not or which monovalent metal ion was used. The phosphor samples were used to print high-resolution 2D color barcodes for security and anticounterfeiting applications. The study presented here provides a new approach for the design and synthesis of lead-free metal halide perovskites with different crystal structures and unique optical properties.

Photoimaging with Color-Sensing Abilities by Tuning the Band Gap of a Single-Crystal Lead-Free Perovskite.

Photodetectors (PDs) composed of lead-free metal halide perovskites have been a shining topic in optoelectronics. However, it is debatable whether perovskites are an n-type or p-type semiconductor with a direct or indirect band gap. Furthermore, to date, little research has been conducted on lead-free metal halide perovskites with color-sensing abilities. Herein, for the first time, single-crystal MA3Bi2I3xBr9-3x (x = 0, 1, 2, and 3) perovskites were systematically studied, and the results showed that MA3Bi2I9 is a p-type direct-band-gap semiconductor, whereas MA3Bi2Br9 is an n-type indirect-band-gap semiconductor. Furthermore, the band gap of MA3Bi2I3xBr9-3x (x = 0, 1, 2, and 3) perovskites can be systematically tuned from 2.06 to 2.55 eV, affording it with color-sensing abilities from 450 to 580 nm, respectively. The representative Au-MA3Bi2I9-ITO (ITO = indium tin oxide) PD exhibits a superior self-powered photodetecting performance with a high responsivity (15.8 mA W-1; 580 nm, 1.0 mW cm-2), detectivity (8.1 × 1011 Jones), an on/off ratio (4231), LDR (72.5 dB) and a fast response speed (rise time of 2 μs and decay time of 29 μs). This study not only facilitates the theoretical understanding of the band gap of perovskite materials but also sheds light on the application of lead-free perovskites in object interaction and color perception.

Structural Transformation and Photoluminescent Property of Manganese-Doped Bismuth-Based Perovskites.

Here, we synthesized pure Cs3Bi2Cl9 (CBC) and manganese (Mn)-doped crystals with different feeding ratios, leading to changes in structure and luminescence. The crystals Cs3Bi2Cl9-Mn (CBCM) formed by doping a minor amount of Mn2+ (Bi/Mn = 8:1) maintain the orthorhombic phase structure of the host, but when Bi/Mn = 2:1, the crystal structure is more inclined to form Cs4MnBi2Cl12 (CMBC) of a trigonal phase. Combined with density functional theory (DFT) calculation, the results demonstrate that a moderate amount of Mn2+ doping can create impurity energy levels in the forbidden band. However, as the structure transitions, the type of energy band structure changes from indirect to direct, with completely different electronic orbital features. Temperature-dependent time-resolved and steady-state photoluminescence spectroscopies are used to explore the structure-related thermal properties and transitional process. Differences energy transfer routes are revealed, with CBCM relying on intersystem energy transfer and CMBC mainly depending on direct excitation of Mn2+ to produce d-d transitions. Furthermore, since CMBC is temperature-sensitive, we perform the first photoluminescent (PL) lifetime temperature measurement using CBMC and obtain a maximum relative sensitivity of 1.7 %K-1 and an absolute sensitivity of 0.0099 K-1. Our work provides insight into the mechanism of Mn2+ doping-induced luminescence and offers a potentially effective doping strategy for improving the PL properties of lead-free metal halide perovskites.

Opportunity of lead-free metal halide perovskites for electroluminescence

<p>Lead halide perovskites (LHPs), which have demonstrated exceptional optical and electrical properties are promising candidates for electroluminescent light-emitting diodes (LEDs). However, concerns about the toxicity and stability have hindered their commercialization. In recent years, lead-free metal halide perovskites (LFMHPs) have emerged as promising alternatives, and significant progress has already been made in developing LFMHP-based LEDs. Nevertheless, their device performance is still inferior to that of well-developed LHP-based counterparts. To fully exploit LED applications and boost device performance, in this review, we provide a comprehensive overview of the currently explored different metal-based LFMHPs. We mainly focus on the preparation methods, crystal structure, optical properties, and LED applications of these materials. Furthermore, we conclude with a discussion regarding the key challenges and potential prospects in this field. We hope that this review will inspire more extensive research on LFMHPs from a new perspective and promote practical applications of LFMHP-based LEDs in multiple directions of current and future research.</p>

Bismuth-Based Halide Perovskites for Photocatalytic H2 Evolution Application.

Metal halide perovskites (MHPs), in particular lead-based perovskites, have earned recognized fame in several fields for their outstanding optoelectronic properties, including direct generation of free charge carriers, optimal ambipolar charge carrier transport properties, high absorption coefficient, point-defect tolerance, and compositional versatility. Nowadays, this class of materials represents a real and promising alternative to silicon for photovoltaic technologies. This worthy success led to a growing interest in the exploration of MHPs in other hot research fields, such as solar-driven photocatalytic water splitting towards hydrogen production. Nevertheless, many of these perovskites show air and moisture instability problems that considerably hinder their practical application for photocatalytic water splitting. Moreover, if chemical instability is a problem that can be in part mitigated by the optimization of the chemical composition and crystal structure, the presence of lead represents a real problem for the practical application of MHPs in commercial devices due to environmental and healthcare issues. To successfully overcome these problems, lead-free metal halide perovskites (LFMHPs) have gained increasing interest thanks to their optoelectronic properties, comparable to lead-based materials, and their more eco-friendly nature. Among all the lead-free perovskite alternatives, this mini-review considers bismuth-based perovskites and perovskite derivatives with a specific focus on solar-driven photocatalysis application for H2 evolution. Special attention is dedicated to the structure and composition of the different materials and to the advantage of heterojunction engineering and the relative impact on the photocatalytic process.

Green and cost-effective morter grinding synthesis of bismuth-doped halide perovskites as efficient absorber materials

Due to the instability and toxicity issues of lead/tin-based halide perovskites, lead-free metal halide perovskites have emerged as an attractive lead replacement for several semiconductor applications. Here, we present a bismuth (Bi)-based perovskite structure as a low-toxic and potentially substitutable alternative to lead-based perovskite solar cells. The synthesis and optical performance of MAPbI3, MA3Bi2I9Clx, and (MAPbI3:BiCl3) with ratios (of 10, 30, 50, 70)% as lead-free and low lead perovskite are prepared. The grinding technique is used as a green chemistry method compared to a typical reaction for scaling up production. The phase identification, crystallinity, thermal stability, optoelectronic properties, and nanoscale composition are comprised. The results showed that the prepared samples are enhanced in the visible absorption region and aligned well with previous literature. Besides, the bandgap energy for the mixed-structured perovskite, at a molar ratio of 10%, was reduced to 1.52 eV compared to 1.55 and 1.80 eV for MAPbI3, MA3Bi2I9Clx, respectively. At room temperature, the samples emitted intense photoluminescence in the 680–700 nm region. Our findings demonstrate the processability of bismuth perovskites, aiding in the development of high-performance low toxic perovskites by assisting in the refinement of materials and processing methods.

Tenability and improvement of the structural, electronic, and optical properties of lead-free CsSnCl3perovskite by incorporating reduced graphene oxide (rGO) for optoelectronic applications

The lead-free metal halide perovskite materials are a potential candidate for optoelectronics and photovoltaic applications due to their promising and outstanding properties.

High Ionic Conduction and Polarity-Induced Piezoresponse in Layered Bimetallic Rb4Ag2BiBr9 Single Crystals

The emergence of lead-free metal-halide perovskites in modern-day energy research is primarily due to their competent semiconducting and optoelectronic properties, as well as their nontoxicity and improved stability in ambient operating conditions. However, a detailed understanding of ion transport dynamics and the relaxation behavior of these materials is still elusive. In this article, we report on the single-crystal (SC) growth of a bimetallic two-dimensional layered Rb4Ag2BiBr9 and explore its dielectric, piezoelectric, and ferroelectric properties. The dielectric attributes are investigated by studying the temperature-dependent complex impedance, complex electric modulus, and AC conductivity over an extensive frequency range from 4 Hz to 8 MHz. The role of grain and grain boundaries in the effective impedance is established using the Maxwell–Wagner equivalent circuit model from the Nyquist plots. The observed electric modulus spectra are studied using the Havriliak–Nigami and the Kohlrausch–Williams–Watts formalisms to understand the ionic transport and relaxation mechanisms in Rb4Ag2BiBr9. The DC conductivity and relaxation time show Arrhenius-like behavior with the inverse temperature validating the hopping motion of ions. The values of the activation energy required for ion hopping are calculated independently from the relaxation time, hopping frequency, and DC conductivity Arrhenius plots and are in good agreement with a value of 0.47 eV. The scaling of the temperature-dependent conductivity and electric modulus spectra into a single master curve demonstrates the congruence of the ionic conduction and the relaxation phenomena at different temperatures for Rb4Ag2BiBr9. This SC demonstrates decent thermal and ambient stability up to 500 °C and 12 months, respectively. The pristine orthorhombic Rb4Ag2BiBr9 SC shows a piezoelectric amplitude value of ∼564 pm at the maximum applied bias (±10 V), and a saturation polarization of ∼0.14 nC/cm2 estimated from the piezoelectric force microscopy and polarization hysteresis loop measurement, respectively. The ferroelectric and semiconducting attributes of this material can be harnessed for prospective applications as a thin film in designing mechanical energy harvesters as well as functional photoferroelectrics, such as optical switches and ferroelectric photovoltaics.

Pressure-Induced Emission from All-Inorganic Two-Dimensional Vacancy-Ordered Lead-Free Metal Halide Perovskite Nanocrystals

Although seeking an effective strategy for further improving their optical properties is a great challenge, two-dimensional (2D) halide perovskites have attracted a significant amount of attention because of their performance. In this regard, the pressure-induced emission accompanied by a remarkable pressure-enhanced emission is achieved without a phase transition in 2D vacancy-ordered perovskite Cs3Bi2Cl9 nanocrystals (NCs). Note that the initial Cs3Bi2Cl9 NCs possess extremely strong electron-phonon coupling, leading to the easy annihilation of trapped excitons by the phonon. Upon compression, pressure could effectively suppress phonon-assisted nonradiative decay and give rise to an intriguing emission from "0" to "1". Both the weakened electron-phonon coupling and the relaxed halide octahedral distortion benefiting from the vacancy-ordered structure contributed to the subsequent enhanced emission. This work not only elucidates the underlying photophysical mechanism but also identifies pressure engineering as a robust means for improving their potential applications in environmentally friendly solid-state lighting at extremes.

Facile synthesis of Cs3Bi2Br9 perovskite nanoplates with low-polarity antisolvents for photodetection applications

Lead-free metal-halide perovskites have garnered tremendous attention in recent times for their excellent properties, such as high light absorption coefficient and high charge-carrier diffusion length. Herein, we report the synthesis and investigation of lead-free Cs3Bi2Br9 perovskite nanoplates for visible light photodetection applications. The Cs3Bi2Br9 nanoplates were synthesized by a facile reprecipitation method based on the selection of antisolvents. The synthesized nanoplates present phase-pure crystal quality and exhibit reduced trap states, resulting in a high on/off current ratio of ∼103 under illumination at a wavelength of 405 nm in ambient air. This study thus hints at new opportunities for stable and low-toxicity perovskite-based optoelectronic applications.

A Review on Recent Advances in Materials of Hybrid Organic–Inorganic Perovskite Solar Cells

This study is an emphasis on the metal halide perovskite solar cells that are susceptible to factors that influence their power conversion efficiency (PCE). Perovskite solar cells, also known as PSCs, have been shown to have a high power conversion efficiency (PCE) due to a number of various factors. As they reached a power conversion efficiency of 25%, solar cells based on metal halide perovskite were a game-changer in the quest for photovoltaic performance. A flurry of activity in the fields of structure design, materials chemistry, process engineering, and device physics has helped the solid-state perovskite solar cell to become a leading contender for the next generation of solar energy harvesters in the world today. This follows up on the ground-breaking development of the solid-state perovskite solar cell in 2012. This cell has a higher efficiency compared to commercial silicon or other organic and inorganic solar cells, as well as a lower cost of materials and processes. However, it has the disadvantage that these high efficiencies can only be obtained with lead-based perovskites, which increases the cost of the cell. As a result of this fact, a new study area on lead-free metal halide perovskites was established, and it is now exhibiting a remarkable degree of vibrancy. This provided us with the impetus to review this burgeoning area of research and discuss possible alternative elements according to current theoretical and practical investigations that might be utilized to replace lead in metal halide perovskites as well as the features of the perovskite materials that correspond to these elements.

Design and efficiency enhancement of FTO/PC60BM/CsSn0.5Ge0.5I3/Spiro-OMeTAD/Au perovskite solar cell utilizing SCAPS-1D Simulator

The poisoning potential of lead, which is the main component of the absorber layer of lead halide (Pb) perovskites, as well as the stability problems of the manufactured devices, constitute a major obstacle to the industrialization of this technology. As a result, recent research is concentrating on lead-free metal halide perovskites. Unfortunately, current lead-free perovskites suffer from poor performance, hence the interest of our study. The research presented here shows that optimizing several variables related to the performance of each layer of a perovskite solar cell (PSC) constructed from lead-free inorganic materials provides an efficiency of 18.13%. We designed a structure with outstanding performance using the FTO/PC60BM/CsSn0.5Ge0.5I3/Spiro-OMeTAD/Au configuration. The impact of various relevant factors, such as the thickness and defect density of the absorber layer their doping densities, the back contact work, and the operating temperature, have been thoroughly investigated to boost the performance of the proposed device. The performance of cesium-tin-germanium triiodide (CsSn0.5Ge0.5I3) solar cells with different electron transport materials, including ZnO, TiO2, CdS, C60; Cd0.5Zn0.5S, IGZO, has also been examined. It has been demonstrated that using ZnO as an electron transport layer improves electron extraction and, therefore, performance. The best outcomes are obtained after optimizing all the factors mentioned above, namely: Jsc of 28.70 mA/cm2, Voc of 1.115 V, FF of 87.86%, and PCE of 18.13%. Additionally, the explored structure may be an excellent candidate for the future development of lead-free perovskite solar cells.

Perovskite superlattices with efficient carrier dynamics.

Compared with their three-dimensional (3D) counterparts, low-dimensional metal halide perovskites (2D and quasi-2D; B2An-1MnX3n+1, such as B = R-NH3+, A = HC(NH2)2+, Cs+; M = Pb2+, Sn2+; X = Cl-, Br-, I-) with periodic inorganic-organic structures have shown promising stability and hysteresis-free electrical performance1-6. However, their unique multiple-quantum-well structure limits the device efficiencies because of the grain boundaries and randomlyoriented quantum wells in polycrystals7. In single crystals, the carrier transport through the thickness direction is hindered by the layered insulating organic spacers8. Furthermore, the strong quantum confinement from the organic spacers limits the generation and transport of free carriers9,10. Also, lead-free metal halide perovskites have been developed but their device performance is limited by their low crystallinity and structural instability11. Here we report a low-dimensional metal halide perovskite BA2MAn-1SnnI3n+1 (BA, butylammonium; MA, methylammonium; n = 1, 3, 5) superlattice by chemical epitaxy. The inorganic slabs are aligned vertical to the substrate and interconnected in a criss-cross 2D network parallel to the substrate, leading to efficient carrier transport in three dimensions. A lattice-mismatched substrate compresses the organic spacers, which weakens the quantum confinement. The performance of a superlattice solar cell has been certified under the quasi-steady state, showing a stable 12.36% photoelectric conversion efficiency. Moreover, an intraband exciton relaxation process may have yielded an unusually high open-circuit voltage (VOC).

Temperature-activated dielectric relaxation in lead-free halide perovskite single crystals

Lead-free metal-halide perovskites have recently appeared as a promising candidate in optoelectronics and photovoltaics because of their non-toxicity, stability, and unique photophysical properties. Much scientific research has been done on optoelectronic characteristics and photovoltaic applications of lead-free perovskites, but the dielectric characteristics and insight into the relaxation phenomenon remain elusive. Here, we study the dielectric relaxation and conduction mechanism in the single crystalline (SC) A3Bi2X9 (A = MA+/FA+) perovskite using temperature-dependent electrochemical impedance spectroscopy in correlation with the modulus spectroscopy. With increasing temperature, the peak of −Z″(ω) shifts toward a high-frequency regime which specifies the thermally dependent relaxation mechanism in both crystals. The activation energy was estimated as 381 meV for MA3Bi2I9 (MBI) crystal and 410 meV for the FA3Bi2I9 (FBI) crystal suggesting hopping of mobile ions between lattice sites. The connected orientational polarization with the thermal motion of molecules leads to the enhancement in the dielectric constant (ϵ′) with temperature. The ϵ″(ω) in these crystals shows the significant ionic conductivity with a typical 1/fγ type characteristics (in the low-frequency regime) where γ is found to be in the range of 0.93–1.0 for MBI crystal and 0.88–0.98 for FBI crystal. The correlated imaginary part of impedance (−Z″) and modulus (M″) demonstrate the temperature-activated delocalized relaxation (non-Debye toward the Debye type) in these crystals. Stevels model suggests that the contribution of traps reduces with temperature rise and therefore conductivity enhances. Our study provides a comprehensive analysis and in-depth knowledge about the dielectric and conductivity relaxation mechanism in these lead-free perovskite SCs, which will help to implement efficient energy storage devices using these materials.