Tin Halide Perovskites Research Articles

Quasi-Single-Crystal Tin Halide Perovskite Films with High Structural Integrity for Near-Infrared Imaging Array Enabling Hidden Object Recognition.

Near-infrared (NIR) image sensors based on solution-processed thin film are gaining prominence in various applications, including security detection, remote sensing, medical imaging, and environmental monitoring, owing to superior penetration capabilities of NIR light. However, the reported perovskite image sensors suffer from limited resolution and performance due to poor structural integrity, bioincompatibility, and constrained response wavelength range from lead-based perovskite materials employed. In this study, we present non-toxic quasi-single-crystal (QSC) CH(NH2)2SnI3 (FASnI3) perovskite films, prepared via a simple spin-coating technique, that demonstrate high structural integrity and effective NIR response. Through a series of in situ characterizations, we reveal that the orderly growth mode of QSC-FASnI3 perovskite films enables a more oriented crystal growth with reduced trap and grain boundaries. Consequently, self-powered NIR photodetector based on QSC-FASnI3 films exhibited large detectivity over 1013 Jones in the NIR range (780-890 nm). Ultimately, due to the high structural integrity, the high-resolution 64×64 (4096) pixels NIR imaging array, exhibiting reduced photo and dark response non-uniformity value, was fabricated on the thin-film transistors (TFT) backplanes, enabling ultraweak NIR light (63 nW cm-2) real-time imaging, fingerprint imaging, and hidden object recognition. This work pioneers the application of lead-free perovskite for high-resolution NIR imaging arrays.

Directional Regulation of Photogenerated Carriers in Tin Halide Perovskites for Enhanced Thermoelectrics

Directional Regulation of Photogenerated Carriers in Tin Halide Perovskites for Enhanced Thermoelectrics

Effects of A-Site Cation Structure on the Stability of 2D Tin Halide Perovskites

Effects of A-Site Cation Structure on the Stability of 2D Tin Halide Perovskites

Formation and Passivation of Surface Defects in Lead-Free Tin Halide Perovskites

Formation and Passivation of Surface Defects in Lead-Free Tin Halide Perovskites

Double-Shell Encapsulation of Lead-Free Tin Halide Perovskite for Self-Powered Smart Windows.

Luminescent solar concentrators (LSC) have the potential application in building integrated photovoltaic (BIPV). 0D tin-based perovskites are a promising embedding phosphor in LSC due to the large Stokes shift and high photoluminescence quantum yield. But the instability and uncontrollable crystal growth are severe limiting their successful utilization in device fabrication. To tackle these issues, double-shell encapsulated configurations are presented, soft ligands of hypophosphorous acid and hard-shell of hollow mesoporous silica are simultaneously suppressing the oxidation of Sn2+ and restricting crystal growth within nano-matrix. The stable phosphor is subsequently embedded into LSC for harvesting solar energy and the resulting output power efficiently drives the combined electrochromic glass under natural light. These fabricated devices also offer the self-adaptable switch on/off functionality to regulate light absorption with variable solar irradiation intensity in real time. This approach is anticipated to open new avenues for utilizing lead-free perovskite nanomaterials in self-powered smart windows for BIPV.

A-Site Engineering with Thiophene-Based Ammonium for High-Efficiency 2D/3D Tin Halide Perovskite Solar Cells.

TTin halide perovskites are the most promising candidate materials for lead-free perovskite solar cells (PSCs) thanks to their low toxicity and ideal bandgap energies. The introduction of 2D/3D mixed perovskite phases in tin-based PSCs (TPSCs) has proven to be the most effective approach to improving device efficiency and stability. However, a 2D perovskite phase normally shows relatively low carrier mobility, which will be unfavorable for carrier transfer in the devices. In this work, we used a thiophene-based cation 2-(thiophen-3-yl)ethan-1-aminium (3-TEA) as a spacer to form a novel 2D perovskite phase in TPSCs, which shows the most promising effect on the performance enhancement in comparison with other cations like 2-(thiophen-2-yl)ethan-1-aminium (2-TEA) and benzene-based 2-phenylethan-1-aminium (PEA). Theoretical calculations reveal that 3-TEA enables the most compact crystal packing of [SnI6]4- octahedral layers, resulting in the lowest hole effective mass and formation energy in the 2D phase. This effect significantly enhances device efficiency and stability by facilitating more efficient carrier transfer within the 2D phase. These findings indicate that thiophene-based 2D perovskites are well-suited for high-performance TPSCs.

A‐Site Engineering with Thiophene‐Based Ammonium for High‐Efficiency 2D/3D Tin Halide Perovskite Solar Cells

TTin halide perovskites are the most promising candidate materials for lead‐free perovskite solar cells (PSCs) thanks to their low toxicity and ideal bandgap energies. The introduction of 2D/3D mixed perovskite phases in tin‐based PSCs (TPSCs) has proven to be the most effective approach to improving device efficiency and stability. However, a 2D perovskite phase normally shows relatively low carrier mobility, which will be unfavorable for carrier transfer in the devices. In this work, we used a thiophene‐based cation 2‐(thiophen‐3‐yl)ethan‐1‐aminium (3‐TEA) as a spacer to form a novel 2D perovskite phase in TPSCs, which shows the most promising effect on the performance enhancement in comparison with other cations like 2‐(thiophen‐2‐yl)ethan‐1‐aminium (2‐TEA) and benzene‐based 2‐phenylethan‐1‐aminium (PEA). Theoretical calculations reveal that 3‐TEA enables the most compact crystal packing of [SnI6]4‐ octahedral layers, resulting in the lowest hole effective mass and formation energy in the 2D phase. This effect significantly enhances device efficiency and stability by facilitating more efficient carrier transfer within the 2D phase. These findings indicate that thiophene‐based 2D perovskites are well‐suited for high‐performance TPSCs.

Robust excitonic light emission in 2D tin halide perovskites by weak excited state polaronic effect

2D perovskites hold immense promise in optoelectronics due to their strongly bound electron-hole pairs (i.e., excitons). While exciton polaron from interplay between exciton and lattice has been established in 2D lead-based perovskites, the exciton nature and behavior in the emerging 2D tin-based perovskites remains unclear. By combining spin-resolved ultrafast spectroscopy and sophisticated theoretical calculations, we reveal 2D tin-based perovskites as genuine excitonic semiconductors with weak polaronic screening effect and persistent Coulomb interaction, thanks to weak exciton-phonon coupling. We determine an excited state exciton binding energy of ~0.18 eV in n = 2 tin iodide perovskites, nearly twice of that in lead counterpart, despite of same large value of ~0.2 eV from steady state measurement. This finding emphasizes the pivotal role of excited state polaronic effect in these materials. The robust excitons in 2D tin-based perovskites exhibit excitation power-insensitive, high-efficiency and color-purity emission, rendering them superior for light-emitting applications.

Optimization of laser patterning process for eco-friendly tin-halide perovskite solar module – with a nanosecond green laser

The tin-based perovskite solar cells are promising future eco-friendly photovoltaic technology with increasing efficiency, which relies on fluorine-doped tin oxide (FTO) or indium tin oxide (ITO) as a transparent conducting oxide (TCO) for front contact. In the monolithic module fabrication process interconnections are executed by a series of three scribes with two different lasers 1064 nm and 532 nm. This study aims to simplify the interconnection process in tin-based perovskite solar modules by using a single visible laser source to perform all three scribes. The study uses an inverted device structure of Glass/TCO/ Poly(3,4-ethylenedioxythiophene): Polystyrene sulfonate (PEDOT: PSS)/Formamidinium-tin-iodide (FASnI3)/C60/Bathocuproine (BCP)/Ag and a 532 nm nanosecond pulsed laser source to pattern the ITO and FTO (P1 scribe), the PEDOT: PSS/FASnI3/C60/BCP stack (P2 scribe), and the PEDOT: PSS/FASnI3/C60/BCP/Ag (P3 scribe). The quality of the P1 scribe is assessed by examining the edges, completeness of film removal, cracking, film delamination, and elemental mapping using a stylus profiler, optical microscope, and energy dispersive x-ray spectroscopy. The P1 scribe is completely removed with line widths of 70 µm and 110 µm of ITO and FTO, respectively, without damage to the glass substrate. The profiles are steep, and the electrical isolation is greater than 40 MΩ. The same 532 nm laser is used for P2 and P3 scribes. The ablation of PEDOT: PSS during P2 and P3 scribe is studied by Raman spectroscopy. The results show that the use of a single 532 nm laser source can simplify the patterning process of monolithic tin-based perovskite solar modules, and potentially reduce production costs.

Photolithography-Free, Solution-Processable Perovskite Electrodes for High-Performance Organic Transistors.

Solution-processable electrodes are promising for next-generation electronics due to their simplicity, cost-effectiveness, and potential for large-area fabrication. However, current solution-processable electrodes based on conductive polymers, carbon-based compounds, and metal nanowires face challenges related to stability, patterning, and production scalability. Here we introduce a novel approach using 3D tin halide perovskites (THPs) combined with a photolithography-free solution patterning technique to fabricate solution-processed electrodes. We demonstrate the preparation of highly conductive CsSnI3 films (234.9 S cm-1) and the fabrication of patterned 35 × 35 perovskite electrode arrays on a 4-in. silicon wafer. These electrodes, used as source/drain electrodes in organic transistors, resulted in devices showing high uniformity and stability. This electrode fabrication strategy is also applicable to other 3D THPs like FASnI3 and MASnI3, showcasing versatility for diverse applications. The results highlight the feasibility and advantages of using 3D THPs as solution-processable electrodes, providing a new material system for the advancement of solution-processed electronics.

Plasma-Based Modification of Tin Halide Perovskite Interfaces for Photovoltaic Applications.

Tin halide perovskites represent the most suitable alternative to their lead-based counterparts for sustainable photovoltaics. One of the most important drawbacks of this class of materials is the intrinsic tendency of tin (II) to oxidize under certain conditions and as a consequence of aging. Here, we explore plasma processing to gently treat the surface of the tin perovskite films. As shown by chemical, optical, and morphological analyses, this treatment by generating transient active species on the surface of the material impacts its aging, inhibiting the tendency of tin (II) to oxidize. Plasma-treated stored devices show a power conversion efficiency slightly higher and narrower in the distribution than that of the reference devices. The positive impact of this noninvasive technique, which can be easily implemented in large-area manufacturing facilities, increases the potential of lead-free alternative perovskite photovoltaics.

Achieving Inkjet‐Printed 2D Tin Iodide Perovskites: Excitonic and Electro‐Optical Properties

AbstractCurrently, there is a great demand for non‐toxic lead‐free halide perovskites as active materials for solar cells, light‐emitting diodes and other optoelectronic devices. Although an essential progress has been made using tin(II) halide perovskites, still greater efforts are needed to improve their stability and manufacture films and devices under a scalable technology. The first goal of the work is to achieve suitable physical properties of 2D Sn(II) polycrystalline perovskite films obtained by the industrially scalable inkjet printing deposition technique. In the present work, inks of 2D tin(II) halide perovskite 2‐thiopheneethylammonium tin(II) iodide, TEA2SnI4, have been successfully formulated in DMF (toxic) and DMSO (non‐toxic) solutions and using appropriate additives (SnF2 and reducing agents) for improving the stability of the inks and the resulting films. Room‐ and low‐temperature excitonic photoluminescence (PL), charge carrier recombination dynamics and µ‐PL is used to explain the observed two excitonic bands, which are associated to the bulk and edges of perovskite grains nanoplatelet‐like composing the polycrystalline films. Promising electro‐optical properties are also obtained in the TEA2SnI4 films inkjet‐printed from DMSO formulations onto ITO‐interdigitated electrodes, such as low dark currents, ≈10 – 20 nA at 10 V of bias voltage, and high responsivities ≈1–20 A/W.

First-Principle Characterization of Structural, Electronic, and Optical Properties of Tin-Halide Monomers.

The growing interest in tin-halide semiconductors for photovoltaic applications demands in-depth knowledge of the fundamental properties of their constituents, starting from the smallest monomers entering the initial stages of formation. In this first-principles work based on time-dependent density-functional theory, we investigate the structural, electronic, and optical properties of tin-halide molecules SnXn 2-n, with and X=Cl, Br, I, simulating these compounds in vacuo as well as in an implicit solvent. We find that structural properties are very sensitive to the halogen species while the charge distribution is also affected by stoichiometry. The ionicity of the Sn-X bond is confirmed by the Bader charge analysis albeit charge displacement plots point to more complex metal-halide coordination. Particular focus is posed on the neutral molecules SnX2, for which electronic and optical properties are discussed in detail. Band gaps and absorption onset decrease with increasing size of the halogen species, and despite general common features, each molecule displays peculiar optical signatures. Our results are elaborated in the context of experimental and theoretical literature, including the more widely studied lead-halide analogs, aiming to contribute with microscopic insight to a better understanding of tin-halide perovskites.

Stabilization of Sn2+ in FA0.75MA0.25SnI3 perovskite thin films using an electron donor polymer, PCDTBT, and an improvement in the charge transport properties of perovskite solar cells

Lead-free tin halide perovskites for the fabrication of perovskite solar cells have attracted considerable attention due to their outstanding optoelectronic and ecofriendly properties. These materials face severe issues, such as poor environmental stability, low formation energy and faster oxidation of tin from the Sn2+ to Sn4+ state, leading to poor film quality and self-doping. In this work, we have fabricated FA0.75MA0.25SnI3 perovskite thin films via a solution processing method and studied the conjugated polymer poly [N-9′-hepta-decanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadia-zole)] (PCDTBT)-induced effects in perovskite thin films. The micro-strain of PCDTBT-doped FA0.75MA0.25SnI3 perovskite reduced without any change in the crystal structure. Reductions in electron trap density have been observed due to improved film quality and enlarged perovskite grains. We have observed that the Sn4+ content in 0.050 wt% PCDTBT-doped FA0.75MA0.25SnI3 perovskite film gets reduced, as shown in the x-ray photoelectron spectroscopy (XPS) results. The reduction in Sn4+ (cause of self-doping) content shows that PCDTBT doping maintains the stability of Sn2+ in FA0.75MA0.25SnI3 perovskite thin film. A decrement in hole density from 3.2 × 1018 cm−3 for pristine films to 1.3 × 1017cm−3 for 0.050 wt% PCDTBT-doped FA0.75MA0.25SnI3 perovskite has been observed from C–V measurement, which is consistent with the XPS results. Thus, PCDTBT doping in perovskite films can effectively tackle the severe issues of tin oxidation and defects in the lead-free tin halide perovskite photoactive layer for solar cell application.

Saturable absorption properties of mixed lead-tin halide perovskites and their application in near-infrared ultrafast lasers

Mixed lead–tin halide perovskites, as highly sensitive materials in the near-infrared region, hold significant potential for optoelectronic device applications. Here, mixed lead–tin halide perovskite saturable absorbers (SAs) have been developed by coupling with the side-polished surfaces of the single-mode fibers and excellent saturable absorption effects of the mixed lead–tin halide perovskite SAs have been demonstrated in the near-infrared region. By constructing the in-gap site assisted carrier transfer mode, the saturation absorption process of the mixed lead–tin halide perovskite SAs can be well explained, in which defects as in-gap sites can help the photon-generated carriers transfer into the conduction band and promote the Pauli-blocking-induced absorption bleaching in the SA. Moreover, ytterbium-doped fiber lasers based on perovskite SAs have been fabricated, and mode-locked operations at 1040 nm are achieved using the mixed lead–tin halide perovskite SA, generating ultra-short pulses with a pulse width of 683 fs, 3 dB bandwidth of 4.88 nm, signal-to-noise ratio exceeding 49.74 dB, and a repetition rate of 3.74 MHz. Our findings demonstrate that the mixed lead–tin halide perovskite SAs have excellent optical modulation capability and promising applications in the field of ultrafast photonics.

Adhesion-Controlled Heterogeneous Nucleation of Tin Halide Perovskites for Eco-Friendly Indoor Photovoltaics.

The rapid development of the Internet of Things (IoT) has accelerated the advancement of indoor photovoltaics (IPVs) that directly power wireless IoT devices. The interest in lead-free perovskites for IPVs stems from their similar optoelectronic properties to high-performance lead halide perovskites, but without concerns about toxic lead leakage in indoor environments. However, currently prevalent lead-free perovskite IPVs, especially tin halide perovskites (THPs), still exhibit inferior performance, arising from their uncontrollable crystallization. Here, a novel adhesive bonding strategy is proposed for precisely regulating heterogeneous nucleation kinetics of THPs by introducing alkali metal fluorides. These ionic adhesives boost the work of adhesion at the buried interface between substrates and perovskite film, subsequently reducing the contact angle and energy barrier for heterogeneous nucleation, resulting in high-quality THP films. The resulting THP solar cells achieve an efficiency of 20.12% under indoor illumination at 1000 lux, exceeding all types of lead-free perovskite IPVs and successfully powering radio frequency identification-based sensors.

Combining Trivalent Ion-Doping with Halide Alloying to Increase the Efficiency of Tin Perovskites.

Tin-halide perovskites (THP) are emerging materials for photovoltaics with optoelectronic properties potentially rivaling lead-based analoges. Their efficiencies in solar cells are, however, severely limited by the high sensitivity of tin to oxygen and the heavy p-doping natively present in the material. While the effects of oxygen can be mitigated by using reducing agents upon the synthesis and by encapsulating the device, the native p-doping caused by the high density of acceptor defects remains a challenge to be further addressed for prolonging carrier lifetimes and, consequently, device efficiency. In this work, potential compositional engineering strategies aimed at reducing the p-doping of this class of materials and increasing their efficiency in solar cells are investigated. Based on density functional theory simulations it is demonstrated that THP doping with d1s2 trivalent ions effectively decreases the hole background density and the density of the deep defects responsible for the non-radiative recombination in these materials. This effect is enhanced by alloying iodide with small fractions of bromide, up to 33%. Higher bromide fractions, instead, are detrimental due to the increased non-radiative recombination. These results may provide useful guidelines to experimentalists for improving the optoelectronic quality of THPs and consequently of the ensuing devices.

A Revisit of Crystallization in Tin Halide Perovskite Thin Films: From Nucleation, Intermediate to Crystal Growth

AbstractPerovskite solar cells (PSCs) are exuding unique charm in the third generation of thin film solar cell technology with high power conversion efficiency (PCE) and low production cost. Recently, the lead‐free tin halide perovskite solar cells (TPSCs) have drawn significant research interests due to the advantages of low toxicity, near‐ideal bandgap and high carrier mobility. However, the rapid crystallization and easy oxidation limits the film quality and final performance of the solar cells. Therefore, the deposition of high‐quality tin halide perovskite films is key to the advance of TPSCs. In this review, the classical theory of solution nucleation and crystal growth is reviewed and correlated to the practical deposition of tin perovskite film. The physicochemical properties of tin perovskite with those of lead counterpart and the differences in the crystallization process is carefully compared. On this basis, recent regulation strategies are systematically summarized in terms of the nucleation management, intermediate phase engineering and crystal growth regulation. In addition, the preparation of mixed tin‐lead (Sn‐Pb) PSCs toward high performance is also discussed, as well as the limiting factors for device performance and stability. Finally, the future challenges and prospects of the crystallization regulation are discussed toward more efficient and stable TPSCs.

Optimization of Temperature, Defects, and Thickness for High Efficiency of Tin Halide Perovskites

Optimization of Temperature, Defects, and Thickness for High Efficiency of Tin Halide Perovskites

Photo-excited carrier behaviors of two-dimensional tin halide perovskite single crystals

Photo-excited carrier behaviors of two-dimensional tin halide perovskite single crystals