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Antiferroelectric (AFE) materials, characterized by double electric hysteresis loops, can be transformed to the ferroelectric (FE) phase under an external electric field, making them promising candidates for electronic energy storage and solid-state refrigeration. Additionally, the field-induced strain in AFE materials is contingent upon the direction of the electric field, rendering it with a switching characteristic. Although AFE materials have made progress in the field of energy storage and negative electrocaloric effect, the coexistence of AFE and ferroelasticity is still rarely reported. Here, two isomorphic organic-inorganic hybrid perovskites, HDAEPbCl4 and HDAEPbBr4 (HDAE is [2-(hydroxydimethylammonio)ethan-1-aminium]), exhibiting FE-AFE-PE (PE is paraelectric) phase transitions, are presented. Remarkably, the temperature range where AFE and ferroelasticity coexist is significantly broadened from 59.9 K to 115.1 K by strengthening short-range forces via halogen substitution. This discovery extends the family of FE, AFE, and ferroelastic materials, contributing to the development of multifunctional materials and advancing multifunctional material development.
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CONTEXT: Novel optoelectronic and thermoelectric properties with broad compositional range, non-toxic nature and structural stability make halide-based double perovskites fascinating for flexible optoelectronic devices. In this work, the structural electronic, optical and transport properties of Rb2TlSbX6 (X = Cl, Br, I) were studied using density functional theory for optoelectronic devices. The elastic analysis demonstrates ductile nature, mechanical stability, anisotropic behaviour and feasibility for flexible optoelectronic devices. The band structure study using Tran-Blaha-modified Becke-Johnson (TB-mBJ) potential shows that all studied materials have direct bandgap. In addition, the bandgap of Rb2TlSbCl6 is more appropriate for optoelectronic devices. The small loss and maximum absorption in visible regions make these materials prime candidates for optoelectronic devices. The transport features indicate that all the studied double perovskites reflect p-type semiconducting behaviour as highlighted by positive Seebeck coefficient values. Furthermore, the high power factor values of Rb2TlSbX6 (X = Cl, Br, I) double perovskites make them suitable for thermoelectric device applications at high temperatures. Based on electronic optical and thermoelectric properties Rb2TlSbCl6 is the best candidate for flexible optoelectronic devices. METHODS: In this paper, structural optimization of Rb2TlSbX6 (X = Cl, Br, I) double perovskites was conducted utilizing the Wien2k software based on first principle calculations with Perdew-Burke-Ernzerhof's generalized-gradient approximation (PBE-sol approximation). The TB-mBJ potential was employed to compute the accurate band gap of studied materials. The thermoelectric properties are evaluated with BoltzTraP code, showing a predominance of P-type charge carriers in all studied perovskites. This methodological strategy verifies the material's remarkable stability and optical properties and offers a solid framework for examining its potential in optoelectronic devices.
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Simultaneous enhancement of free excitons (FEs) emission and self-trapped excitons (STEs) emission remains greatly challenging because of the radiative pathway competition. Here, a significant fluorescence improvement, associated with the radiative recombination of both FEs and STEs is firstly achieved in an unconventional ACI-type hybrid perovskite, (ACA)(MA)PbI4 (ACA=acetamidinium) crystals with {PbI6} octahedron units, through hydrostatic pressure processing. Note that (ACA)(MA)PbI4 exhibits a 91.5-fold emission enhancement and considerable piezochromism from green to red in a mild pressure interval of 1 atm to 2.5 GPa. The substantial distortion of both individual halide octahedron and the Pb-I-Pb angles between two halide octahedra under high pressure indeed determines the pressure-tuning localized excitons behavior. Upon higher pressure, photocurrent enhancement is also observed, which is attributed to the promoted electronic connectivity in (ACA)(MA)PbI4. The anisotropic compaction reduces the distance between neighboring organic molecules and {PbI6} octahedra, leading to the enhancement of hydrogen bonding interactions. This work not only offers a deep understanding of the structure-optical relationships of ACI-type perovskites, but also presents insights into breaking the limits of luminescent efficiency by pressure-suppressed nonradiative recombination.
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2D metal halide perovskites (MHPs), mainly the studied Ruddlesden-Popper (RP) and Dion-Jacobson (DJ) phases, have gained enormous popularity as optoelectronic materials owing to their self-assembled multiple quantum well structures, tunable semiconducting properties, and improved structural stability compared to their bulk 3D counterparts. The performance of polycrystalline thin film devices is limited due to the formation of defects and trap states. However, as studied so far, single crystal-based devices can provide a better platform to improve device performance and investigate their fundamental properties more reliably. This Review provides the first comprehensive report on the emerging field of RP and DJ perovskite single crystals and their use in visible light photodetectors of varied device configurations. This Review structurally summarizes the 2D MHP single crystal growth methods and the parameters that control the crystal growth process. In addition, the characterization techniques used to investigate their crystal properties are discussed. The review further provides detailed insights into the working mechanisms as well as the operational performance of 2D MHP single crystal photodetector devices. In the end, to outline the present status and future directions, this Review provides a forward-looking perspective concerning the technical challenges and bottlenecks associated with the developing field of RP and DJ perovskite single crystals. Therefore, this timely review will provide a detailed overview of the fast-growing field of 2D MHP single crystal-based photodetectors as well as ignite new concepts for a wide range of applications including solar cells, photocatalysts, solar H2 production, neuromorphic bioelectronics, memory devices, etc.
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The correlation between structural transformation and optical characteristics of cesium lead bromide (CsPbBr3) nanocrystals (NCs) suggests insights into their growth mechanism and optical performance. Systematic control of reaction parameters led to the successful fabrication of on-demand shape-morphing CsPbBr3 NCs. Transmission electron microscopy observations showed that the shape transformation from nanocubes to microcrystals could be accelerated by increasing the precursor:ligand molar ratio and reaction time. Further evidence for orthorhombic CsPbBr3 NCs was obtained from their selected-area electron diffraction pattern, which exhibits a twin domain induced by the presence of large NCs. Likewise, we observed a substantial decrease in photoluminescence (PL) intensity of CsPbBr3 due to surface decomposition or surface ligand loss resulting from increased size. In addition, fusion of smaller particles having other dimensionality induced the increase in the PL full-width at half maximum. In particular, existence of larger bulk material caused a reduction in the peak intensity in the absorption spectra and a trend of decreasing tendency in intensity of the absorption bands related to bromoplumbate species provided direct evidence of fully converted Cs-oleate.
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Inorganic colloidal cesium lead halide perovskite nanocrystals (NCs) encapsulated by surface capping ligands exhibit tremendous potential in optoelectronic applications, with their surface structure playing a pivotal role in enhancing their photophysical properties. Soy lecithin, a tightly binding zwitterionic surface-capping ligand, has recently facilitated the high-yield synthesis of stable ultraconcentrated and ultradilute colloids of CsPbX3 NCs, unlocking a myriad of potential device applications. However, the atomic-level understanding of the ligand-terminated surface structure remains uncertain. Herein, we use a versatile solid-state nuclear magnetic resonance (NMR) spectroscopic approach, in combination with dynamic nuclear polarization (DNP) and atomistic molecular dynamics (MD) simulations, to explore the effect of lecithin on the core-to-surface structures of CsPbX3 (X = Cl or Br) perovskites, sized from micron to nanoscale. Surface-selective (cross-polarization, CP) solid-state and DNP NMR (133Cs and 207Pb) methods were used to differentiate the unique surface and core chemical environments, while the head-groups {trimethylammonium [-N(CH3)3+] and phosphate (-PO4-)} of lecithin were assigned via 1H, 13C, and 31P NMR spectroscopy. A direct approach to determining the surface structure by capitalizing on the unique heteronuclear dipolar couplings between the lecithin ligand (1H and 31P) and the surface of the CsPbCl3 NCs (133Cs and 207Pb) is demonstrated. The 1H-133Cs heteronuclear correlation (HETCOR) DNP NMR indicates an abundance of Cs on the NC surface and an intimate proximity of the -N(CH3)3+ groups to the surface and subsurface 133Cs atoms, supported by 1H{133Cs} rotational-echo double-resonance (REDOR) NMR spectroscopy. Moreover, the 1H-31P{207Pb} CP REDOR dephasing curve provides average internuclear distance information that allows assessment of -PO4- groups binding to the subsurface Pb atoms. Atomistic MD simulations of ligand-capped CsPbCl3 surfaces aid in the interpretation of this information and suggest that ligand -N(CH3)3+ and -PO4- head-groups substitute Cs+ and Cl- ions, respectively, at the CsCl-terminated surface of the NCs. These detailed atomistic insights into surface structures can further guide the engineering of various relevant surface-capping zwitterionic ligands for diverse metal halide perovskite NCs.
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Narrow-bandgap Sn-Pb alloying perovskites showcased great potential in constructing multiple-junction perovskite solar cells (PSCs) with efficiencies approaching or exceeding the Shockley-Queisser limit. However, the uncontrollable surface metal abundance (Sn2+ and Pb2+ ions) hinders their efficiency and versatility in different device structures. Additionally, the undesired Pb distribution mainly at the buried interface accelerates the Pb leakage when devices are damaged. In this work, a novel strategy is presented to modulate crystallization kinetics and surface metal abundance of Sn-Pb perovskites using a cobweb-like quadrangular macrocyclic porphyrin material, which features a molecular size compatible with the perovskite lattice and robustly coordinates with Pb2+ ions, thus immobilizing them and increasing surface Pb abundance by 61%. This modulation reduces toxic Pb leakage rates by 24-fold, with only â¼23 ppb Pb in water after severely damaged PSCs are immersed in water for 150 h.This strategy can also enhance chemical homogeneity, reduce trap density, release tensile strain and optimize carrier dynamics of Sn-Pb perovskites and relevant devices. Encouragingly, the power conversion efficiency (PCEs) of 23.28% for single-junction, full-stack devices and 21.34% for hole transport layer-free Sn-Pb PSCs are achieved.Notably, the related monolithic all-perovskite tandem solar cell also achieves a PCE of 27.03% with outstanding photostability.
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Cesium lead halide perovskite (CsPbX3; X = Cl, Br, I) nanocrystals showing intense band-edge emission and high photoluminescence quantum yield are known to be a potential candidate for application in optoelectronic devices. However, controlling toxicity due to the presence of Pb2+ in lead-based halide perovskites is a major challenge for the environment that needs to be tackled cautiously. In this work, we have partially replaced Pb2+ with Mn2+ ions in the CsPb(Cl/Br)3 nanocrystals and investigated their impact on the structural and optical properties. The Rietveld refinement shows that CsPbCl2Br nanocrystals possess a cubic crystal structure with Pm3 Ì m space group, the Mn2+ doping results in the contraction of the unit cell. The CsPb(Cl/Br)3: Mn nanocrystals show a substantial change in the optical properties with an additional emission band at ~588 nm through a d-d transition, changing the emission color from blue to pink. Here, a didodecyldimethylammonium bromide (DDAB) ligand that triggers both anion and ligand exchange in the CsPb(Cl/Br)3: Mn nanocrystals have been used to regulate the exchange reaction and tune the emission color of halide perovskites by changing the peak position and the PL intensities of band-edge and Mn2+ defect states. We have also shown that oleic acid helps in the desorption of oleylamine capping from the CsPb(Cl/Br)3: Mn nanocrystal surfaces and DDAB, resulting in the substitution of Cl¯ with Br¯ as well as provides capping with shorter branched length ligand which led to increase in the overall PL intensity by many folds.
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Ferroelectricity has recently been demonstrated in germanium-based halide perovskites. We use first-principles-based simulations to study 4-18 nm CsGeBr3 films and develop a theory for ferroelectric ultrathin films. The theory introduces (i) a local order parameter, which identifies phase transitions into both monodomain and polydomain phases, and (ii) a dipole pattern classifier, which allows efficient and reliable identification of dipole patterns. Application of the theory to both halides CsGeBr3 and CsGeI3 and oxide BiFeO3 ultrathin ferroelectrics reveals two distinct scenarios. First, the films transition into a monodomain phase below the critical value of the residual depolarizing field. Above this critical value, the second scenario occurs, and the film undergoes a transition into a nanodomain phase. The two scenarios exhibit opposite responses of Curie temperature to thickness reduction. Application of a dipole pattern classifier reveals rich nanodomain phases in halide films: nanostripes, labyrinths, zig-zags, pillars, and lego domains.
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This article presents the research results of lead-free Ba1-3/2xLax(Fe0.5Nb0.5)O3 (BFNxLa) ceramic materials doped with La (x = 0.00-0.06) obtained via the solid-state reaction method. The tests of the BFNxLa ceramic samples included structural (X-ray), morphological (SEM, EDS, EPMA), DC electrical conductivity, and dielectric measurements. For all BFNxLa ceramic samples, the X-ray tests revealed a perovskite-type cubic structure with the space group Pm3¯m. In the case of the samples with the highest amount of lanthanum, i.e., for x = 0.04 (BFN4La) and x = 0.06 (BFN6La), the X-ray analysis also showed a small amount of pyrochlore LaNbO4 secondary phase. In the microstructure of BFNxLa ceramic samples, the average grain size decreases with increasing La content, affecting their dielectric properties. The BFN ceramics show relaxation properties, diffusion phase transition, and very high permittivity at room temperature (56,750 for 1 kHz). The admixture of lanthanum diminishes the permittivity values but effectively reduces the dielectric loss and electrical conductivity of the BFNxLa ceramic samples. All BFNxLa samples show a Debye-like relaxation behavior at lower frequencies; the frequency dispersion of the dielectric constant becomes weaker with increasing admixtures of lanthanum. Research has shown that using an appropriate amount of lanthanum introduced to BFN can obtain high permittivity values while decreasing dielectric loss and electrical conductivity, which predisposes them to energy storage applications.
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2D organic-inorganic hybrid perovskites (OIHPs) have shown great promise in direct X-ray detection. The development of high-performance passive X-ray detectors in 2D OIHPs calls for an increase in material density while maintaining structural polarity, which is becoming quite challenging. Here, a high-density, polar 2D alternating-cation-intercalated (ACI) perovskite, (4-AP)Cs2Pb2I8 (B, 4-AP = 4-amidinopyridinium), capable of addressing this problem is successfully constructed by introducing heavy Cs+ into the interlayer space of an aromatic Dion-Jacobson (DJ) perovskite (4-AP)PbI4 (A). Through such a DJ-to-ACI design, the newly developed 2D OIHP B not only significantly increases its density to 4.23 g cm-3 (even higher than that of 3D MAPbI3) but also crystallizes in a polar space group (Ama2), which further leads to enhanced X-ray attenuation and an obvious polar photovoltage (1.1 V) under X-ray irradiation. As a result, X-ray detectors fabricated by high-quality single crystals of B exhibit excellent and stable detection performance under self-powered mode with a high sensitivity of 107 µC Gy-1 cm-2 and a low detection limit of 289 nGy s-1. This work provides implications for the future exploration and regulation of novel ACI OIHPs for high-performance photoelectronic devices.
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Halide perovskites (HPs) have gained significant interest in the scientific and technological sectors due to their unique optical, catalytic, and electrical characteristics. However, the HPs are prone to decomposition when exposed to air, oxygen, or heat. The instability of HP materials limits their commercialization, prompting significant efforts to address and overcome these limitations. Transition metal dichalcogenides, such as MoS2, are chemically stable and are suitable for electronic, optical, and catalytic applications. Moreover, it can be used as a protective media or shell for other nanoparticles. In this study, a novel CsPbBr3@MoS2 core-shell nanostructure (CS-NS) is successfully synthesized by enveloping CsPbBr3 within a MoS2 shell for the first time. Significant stability of CS-NSs dispersed in polar solvents for extended periods is also demonstrated. Remarkably, the hybrid CS-NS exhibits an absorption of MoS2 and quenching of the HP's photoluminescence, implying potential charge or energy transfer from HPs to MoS2. Using finite difference time domain simulations, it is found that the CS-NSs can be utilized to produce efficient solar cells. The addition of a MoS2 shell enhances the performance of CS-NS-based solar cells by 220% compared to their CsPbBr3 counterparts. The innovative CS-NS represents important progress in harnessing HPs for photovoltaic and optoelectronic applications.
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The stability of hybrid organic-inorganic halide perovskite semiconductors remains a significant obstacle to their application in photovoltaics. To this end, the use of low-dimensional (LD) perovskites, which incorporate hydrophobic organic moieties, provides an effective strategy to improve their stability, yet often at the expense of their performance. To address this limitation, supramolecular engineering of noncovalent interactions between organic and inorganic components has shown potential by relying on hydrogen bonding and conventional van der Waals interactions. Here, the capacity to access novel LD perovskite structures that uniquely assemble through unorthodox S-mediated interactions is explored by incorporating benzothiadiazole-based moieties. The formation of S-mediated LD structures is demonstrated, including one-dimensional (1D) and layered two-dimensional (2D) perovskite phases assembled via chalcogen bonding and S-π interactions, through a combination of techniques, such as single crystal and thin film X-ray diffraction, as well as solid-state NMR spectroscopy, complemented by molecular dynamics simulations, density functional theory calculations, and optoelectronic characterization, revealing superior conductivities of S-mediated LD perovskites. The resulting materials are applied in n-i-p and p-i-n perovskite solar cells, demonstrating enhancements in performance and operational stability that reveal a versatile supramolecular strategy in photovoltaics.
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Considerable focus on tin-based perovskites lies on substitution to leadhalide perovskites for the fabrication of eco-friendly optoelectronic devices.The major concern related to tin-based perovskite devices are mainly thestability and the efficiency. However, thinking on the final commercializationscope, other considerations such as precursor stability and cost are majorfactors to carry about. In this regard, this work presents a robust and facilesynthesis of 2D A2SnX4 (A = 4-fluorophenethylammonium(4-FPEA); X = I, Br, I/Br) and 3D FASnI3 perovskite microcrystals followinga developed synthesis strategy with low-cost starting materials. In thisdeveloped methodology, acetic acid is used as a solvent, which helps to protectfrom water by making a hydrophobic network over the perovskite surface, andhence provides sufficient ambient and long-term inert atmosphere stability ofthe microcrystals. Further, the microcrystals are recrystallized in thin filmsfor LED application, allowing the fabrication of orange, near-infrared and purered emitting LEDs. The two-step recrystallized devices show better performanceand stability in comparison to the reference devices made by using commercialprecursors. Importantly, the developed synthesis methodology is defined as ageneric method for the preparation of varieties of hybrid tin-based perovskitesmicrocrystals and application in optoelectronic devices.
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Exsolution of metal nanoparticles (NPs) on perovskite oxides has been demonstrated as a reliable strategy for producing catalyst-support systems. Conventional exsolution requires high temperatures for long periods of time, limiting the selection of support materials. Plasma direct exsolution is reported at room temperature and atmospheric pressure of Ni NPs from a model A-site deficient perovskite oxide (La0.43Ca0.37Ni0.06Ti0.94O2.955). Plasma exsolution is carried out within minutes (up to 15 min) using a dielectric barrier discharge configuration both with He-only gas as well as with He/H2 gas mixtures, yielding small NPs (<30 nm diameter). To prove the practical utility of exsolved NPs, various experiments aimed at assessing their catalytic performance for methanation from synthesis gas, CO, and CH4 oxidation are carried out. Low-temperature and atmospheric pressure plasma exsolution are successfully demonstrated and suggest that this approach could contribute to the practical deployment of exsolution-based stable catalyst systems.
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Halide perovskite (HPs) nanostructures have recently gained extensive worldwide attentions because of their remarkable optoelectronic properties and fast developments. However, intrinsic instability against environmental factors-i.e., temperature, humidity, illumination, and oxygen-restricted their real-life applications. HPs are typically synthesized as colloids by employing organic solvents and ligands. Consequently, the precise control and tuning of complex 3D perovskite morphologies are challenging and have hardly been achieved by conventional fabrication methods. Here, we combine the benefits of self-assembly of biomolecules and an ion exchange reaction (IER) approach to customize HPs spatial shapes and composition. Initially, we apply a biomineralization approach, using biological templates (such as biopolymers, proteins, or protein assemblies), modulating the morphology of MCO3 (M = Ca2+, Ba2+) nano/microstructures. We then show that the morphology of the materials can be maintained throughout an IER process to form surface HPs with a wide variety of morphologies. The fabricated core-shell structures of metal carbonates and HPs introduce nano/microcomposites that can be sculpted into a wide diversity of 3D architectures suitable for various potential applications such as sensors, detectors, catalysis, etc. As a prototype, we fabricate disposable humidity sensors with an 11-95% detection range by casting the formed bio-templated nano/micro-composites on paper substrate.
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Developing environmentally friendly and highly efficient inverted perovskite solar cells (PSCs) encounters significant challenges, specifically the potential toxicity and degradation of thin films in hybrid organic-inorganic photovoltaics (PV). We employed theoretical design strategies that produce hysteresis-reduced, efficient, and stable PSCs based on composition and interface engineering. The devices include a mixed-organic-cation perovskite formamidinium methylammonium tin iodide ( FAMASnI 3 ) as an absorber layer and zinc oxide (ZnO) together with a passivation film phenyl-C61-butyric acid methyl ester ( PC 61 BM ) as a double-electron transport layer (DETL). Furthermore, a nickel oxide (NiO) layer and a trap-free junction copper iodide (CuI) are used as a double-hole transport layer (DHTL). The optoelectronic characterization measurements were carried out to understand the physical mechanisms that govern the operation of the devices. The high power conversion efficiencies (PCEs) of 24.27% and 23.50% were achieved in 1D and 2D simulations, respectively. This study illustrates that composition and interface engineering enable eco-friendly perovskite solar cells, improving performance and advancing clean energy.
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Quasi-2D perovskites light-emitting diodes (PeLEDs) have achieved significant progress due to their superior optical and electronic properties. However, the blue PeLEDs still exist inefficient energy transfer and electroluminescence performance caused by mixed multidimensional phase distribution. In this work, transition metal salt (zinc bromide, ZnBr2) is introduced to modulate phase distributions by suppressing the nucleation of high n phase perovskites, which effectively shortens the energy transfer path for blue emission. Moreover, ZnBr2 also facilitates energy level matching and reduces non-radiative recombination, thus improving electroluminescence (EL) efficiency. Benefiting from these combined improvements, an efficient blue PeLEDs is obtained with a maximum external quantum efficiency (EQE) of 16.2% peaking located at 486 nm. This work provides a promising approach to tune phase distribution of quasi-2D perovskites and achieving highly efficient blue PeLEDs.
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Halide perovskites are an emerging family of piezoelectric and ferroelectric materials. These materials can exist in bulk, single-crystal, and thin-film forms. In this article, we review the piezoelectric charge coefficient (dij) of single crystals, thin films, and dimension-tuned halide perovskites based on different measurement methods. Our study finds that the (dij) coefficient of the bulk and single-crystal samples is mainly measured using the quasi-static (Berlincourt) method, though the piezoforce microscopy (PFM) method is also heavily used. In the case of thin-film samples, the (dij) coefficient is dominantly measured by the PFM technique. The reported values of dij coefficients of halide perovskites are comparable and even better in some cases compared to existing materials such as PZT and PVDF. Finally, we discuss the promising emergence of quasi-static methods for thin-film samples as well.
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As one of the most promising photovoltaic technologies, perovskite solar cells (PSCs) exhibit high absorption coefficients, tunable bandgaps, large carrier mobilities, and versatile fabrication techniques. Nevertheless, the commercialization of the technology is hindered by poor material stability, short device lifetimes and the scalability of fabrication techniques. To address these technological drawbacks, various strategies have been explored, with one particularly promising approach involving the formation of a low-dimensional layer on the surface of the three-dimensional perovskite film. In this work, we demonstrate the use of guanidinium tetrafluoroborate, CH6BF4N3, (GATFB) as a post-treatment step to enhance the performance of PSCs. Compared with the control sample, the application of GATFB improves the film surface topology, reduces surface defects, suppresses non-radiative recombination, and optimizes band alignment within the device. These positive effects reduce recombination losses and enhance charge transport in the device, resulting in PSCs with an open-circuit voltage (VOC) of 1.18 V and a power conversion efficiency (PCE) of 19.7%. The results obtained in this work exhibit the potential of integrating low-dimensional structures in PSCs as an effective approach to enhance the overall device performance, providing useful information for further advancement in this rapidly evolving field of photovoltaic technology.