Homogenizing The Low-Dimensional Phases for Stable 2D-3D Tin Perovskite Solar Cells.

2D-3D tin-based perovskites are considered as promising candidates for achieving efficient lead-free perovskite solar cells (PSCs). However, the existence of multiple low-dimensional phases formed during the film preparation hinders the efficient transport of charge carriers. In addition, the non-homogeneous distribution of low-dimensional phases leads to lattice distortion and increases the defect density, which are undesirable for the stability of tin-based PSCs. Here, mixed spacer cations [diethylamine (DEA+) and phenethylamine (PEA+)] are introduced into tin perovskite films to modulate the distribution of the 2D phases. It is found that compared to the film with only PEA+, the combination of DEA+ and PEA+ favors the formation of homogeneous low-dimensional perovskite phases with three octahedral monolayers (n = 3), especially near the bottom interface between perovskite and hole transport layer. The homogenization of 2D phases help improve the film quality with reduced lattice distortion and released strain. With these merits, the tin PSC shows significantly improved stability with 94% of its initial efficiency retained after storing in a nitrogen atmosphere for over 4600 h, and over 80% efficiency maintained after continuous illumination for 400 h.

Dual-Stage Reduction Strategy of Tin Perovskite Enables High Performance Photovoltaics.

The rapid oxidation of Sn2+ in tin-based perovskite solar cells (TPSCs) restricts their efficiency and stability have been main bottleneck towards further development. This study developed a novel strategy which utilizes thiosulfate ions (S2O32-) in the precursor solution to enable a dual-stage reduction process. In the solution stage, thiosulfate acted as an efficacious reducing agent to reduce Sn4+ to Sn2+, meanwhile, its oxidation products were able to reduce I2 to I- during the film stage. This dual reduction ability effectively inhibited the oxidation of Sn2+ and passivated defects, further promising an excellent stability of the perovskite devices. As a result, thiosulfate-incorporated devices achieved a high efficiency of 14.78% with open-circuit voltage reaching 0.96 V. The stability of the optimized devices achieved a remarkable improvement, maintaining 90% of their initial efficiencies after 628 hours at maximum-power-point (MPP). The findings provid research insights and experimental data support for the sustained dynamic reduction in TPSCs.

Coevaporation Stabilizes Tin-Based Perovskites in a Single Sn-Oxidation State.

Chemically processed methylammonium tin-triiodide (CH3NH3SnI3) films include Sn in different oxidation states, leading to poor stability and low power conversion efficiency of the resulting solar cells (PSCs). The development of absorbers with Sn [2+] only has been identified as one of the critical steps to develop all Sn-based devices. Here, we report on coevaporation of CH3NH3I and SnI2 to obtain absorbers with Sn being only in the preferred oxidation state [+2] as confirmed by X-ray photoelectron spectroscopy. The Sn [4+]-free absorbers exhibit smooth highly crystalline surfaces and photoluminescence measurements corroborating their excellent optoelectronic properties. The films show very good stability under heat and light. Photoluminescence quantum yields up to 4 × 10-3 translate in a quasi Fermi-level splittings exceeding 850 meV under one sun equivalent conditions showing high promise in developing lead-free, high efficiency, and stable PSCs.

Antioxidative Stannous Oxalate Derived Lead-Free Stable CsSnX3 (X=Cl, Br, and I) Perovskite Nanocrystals.

Lead-free CsSnX3 perovskite NCs are becoming a promising alternative to CsPbX3 (X=Cl, Br, I), but suffer from extremely poor stability. Herein, we highlight the significant effect of SnII precursors used in the synthesis on the stability of the resultant CsSnX3 NCs. A method is proposed for synthesizing CsSnX3 NCs using Cs2 CO3 , SnC2 O4 , and NH4 X as corresponding constituent precursors, wherein the ratio of reactants can be easily adjusted. Stable CsSnX3 NCs can be obtained with the use of antioxidative SnC2 O4 as the SnII precursor. Experimental results show that the improvement of NCs stability is mainly ascribed to the role of oxalate in the SnC2 O4 precursor. Oxalate ion has a strong antioxidative ability and can effectively inhibit the oxidation of SnII during the synthesis. Besides, oxalate as a bidentate capping ligand is shown to be coordinated on the surface of formed NCs. This can not only passivate the uncoordinated Sn on the surface but also prevent the oxidation of the NCs.

Superior Stability and Emission Quantum Yield (23% ± 3%) of Single-Layer 2D Tin Perovskite TEA2 SnI4 via Thiocyanate Passivation.

Tin-based perovskite, which exhibits narrower bandgap and comparable photophysical properties to its lead analogs, is one of the most forward-looking lead-free semiconductor materials. However, the poor oxidative stability of tin perovskite hinders the development toward practical application. In this work, the effect of pseudohalide anions on the stability and emission properties of single-layer 2D tin perovskite nanoplates with chemical formula TEA2 SnI4 (TEA = 2-thiophene-ethylammonium) is reported. The results reveal that ammonium thiocyanate (NH4 SCN) is the most effective additive in enhancing the stability and photoluminescence quantum yield of 2D TEA2 SnI4 (23 ± 3%). X-Ray photoelectron spectroscopic investigations on the thiocyanate passivated TEA2 SnI4 nanoplate show less than a 1% increase of Sn4+ signal upon 30 min exposure to air under ambient conditions (298 K, humidity ≈70%). Furthermore, no noticeable decrease in emission intensity of the nanoplate is observed after 20 h in air. The SCN- passivation during the growth stage of TEA2 SnI4 is proposed to play a crucial role in preventing the oxidation of Sn2+ and hence boosts both stability and photoluminescence yield of tin perovskite nanoplates.

On the Durability of Tin-Containing Perovskite Solar Cells.

Tin (Sn)-containing perovskite solar cells (PSCs) have gained significant attention in the field of perovskite optoelectronics due to lower toxicity than their lead-based counterparts and their potential for tandem applications. However, the lack of stability is a major concern that hampers their development. To achieve the long-term stability of Sn-containing PSCs, it is crucial to have a clear and comprehensive understanding of the degradation mechanisms of Sn-containing perovskites and develop mitigation strategies. This review provides a compendious overview of degradation pathways observed in Sn-containing perovskites, attributing to intrinsic factors related to the materials themselves and environmental factors such as light, heat, moisture, oxygen, and their combined effects. The impact of interface and electrode materials on the stability of Sn-containing PSCs is also discussed. Additionally, various strategies to mitigate the instability issue of Sn-containing PSCs are summarized. Lastly, the challenges and prospects for achieving durable Sn-containing PSCs are presented.

Synthesis of Hybrid Tin-Based Perovskite Microcrystals for LED Applications.

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 the stability and the efficiency. However, thinking on the final commercialization scope, other considerations such as precursor stability and cost are major factors to carry about. In this regard, this work presents a robust and facile synthesis of 2D A2SnX4 (A = 4-fluorophenethylammonium(4-FPEA); X = I, Br, I/Br) and 3D FASnI3 perovskite microcrystals following a developed synthesis strategy with low-cost starting materials. In this developed methodology, acetic acid is used as a solvent, which helps to protect from water by making a hydrophobic network over the perovskite surface, and hence provides sufficient ambient and long-term inert atmosphere stability of the microcrystals. Further, the microcrystals are recrystallized in thin films for LED application, allowing the fabrication of orange, near-infrared and purered emitting LEDs. The two-step recrystallized devices show better performance and stability in comparison to the reference devices made by using commercial precursors. Importantly, the developed synthesis methodology is defined as a generic method for the preparation of varieties of hybrid tin-based perovskites microcrystals and application in optoelectronic devices.

Engineering Stable Lead-Free Tin Halide Perovskite Solar Cells: Lessons from Materials Chemistry.

Substituting toxic lead with tin (Sn) in perovskite solar cells (PSCs) is the most promising route toward the development of high-efficiency lead-free devices. Despite the encouraging efficiencies of Sn-PSCs, they are still yet to surpass 15% and suffer detrimental oxidation of Sn(II) to Sn(IV). Since their first application in 2014, investigations into the properties of Sn-PSCs have contributed to a growing understanding of the mechanisms, both detrimental and complementary to their stability. This review summarizes the evolution of Sn-PSCs, including early developments to the latest state-of-the-art approaches benefitting the stability of devices. The degradation pathways associated with Sn-PSCs are first outlined, followed by describing how composition engineering (A, B site modifications), additive engineering (oxidation prevention), and interface engineering (passivation strategies) can be employed as different avenues to improve the stability of devices. The knowledge about these properties is also not limited to PSCs and also applicable to other types of devices now employing Sn-based perovskite absorber layers. A detailed analysis of the properties and materials chemistry reveals a clear set of design rules for the development of stable Sn-PSCs. Applying the design strategies highlighted in this review will be essential to further improve both the efficiency and stability of Sn-PSCs.

Reduced VOC Deficit of Mixed Lead-Tin Perovskite Solar Cells via Strain-Releasing and Synergistic Passivation Additives.

The power conversion efficiency (PCE) of tin-lead perovskite solar cells (PSCs) is normally lower than that of Pb cells, mainly due to greater open circuit voltage (VOC ) losses. Herein, the additive 2,6-diaminopyridine (TNPD) is designed to anchor on the surface of the perovskite precursor colloid as nucleating agent to modulate the growth of Pb-Sn perovskites. It is observed that the TNPD not only effectively induces crystal growth during the nucleation stage, remaining on the crystal surface and ultimately passivating the resulting perovskite films, but also releases the micro-strain generated during the film growth. Furthermore, TNPD could lower the defect density (Sn4+ amount) by screening the perovskite against oxygen and by synergistically bonding with undercoordinated Sn/Pb on the surface. Finally, a high VOC of 0.85 V is obtained, corresponding to a voltage deficit of 0.41 V using a perovskite absorber with a bandgap of 1.26 eV, and a high PCE (20.35%) reported so far for Pb-Sn PSCs. Moreover, the stability of the TNPD-incorporated device is significantly improved, and the PCE maintains 50% of the initial value after about 1000 h storage in glovebox without encapsulated, in comparison to that of the control device (about 700 h, maintaining 30% of the initial value).

Sn-Based Perovskite Solar Cells towards High Stability and Performance.

Recent years have witnessed rapid development in the field of tin-based perovskite solar cells (TPSCs) due to their environmental friendliness and tremendous potential in the photovoltaic field. Most of the high-performance PSCs are based on lead as the light-absorber material. However, the toxicity of lead and the commercialization raise concerns about potential health and environmental hazards. TPSCs can maintain all the optoelectronic properties of lead PSCs, as well as feature a favorable smaller bandgap. However, TPSCs tend to undergo rapid oxidation, crystallization, and charge recombination, which make it difficult to unlock the full potential of such perovskites. Here, we shed light on the most critical features and mechanisms affecting the growth, oxidation, crystallization, morphology, energy levels, stability, and performance of TPSCs. We also investigate the recent strategies, such as interfaces and bulk additives, built-in electric field, and alternative charge transport materials that are used to enhance the performance of the TPSCs. More importantly, we have summarized most of the recent best-performing lead-free and lead-mixed TPSCs. This review aims to help future research in TPSCs to produce highly stable and efficient solar cells.

Reductant Engineering in Stable and High-Quality Tin Perovskite Single Crystal Growth for Heterojunction X-Ray Detectors.

Tin perovskites have emerged as a promising alternative material to address the toxicity of lead perovskites and the low bandgap of around 1.1 eV is also compatible with tandem solar cell applications. Nevertheless, the optoelectronic performance of solution-processed tin perovskite single-crystal counterparts still lags behind because of the tin instability under ambient conditions during crystal growth and limited reductants to protect the Sn2+ ions from oxidation. Here, the reductant engineering to grow high-quality tin perovskite single crystals under ambient conditions is studied. Oxalic acid (H2 C2 O4 ) serves as an excellent reductant and sacrificial agent to protect Sn2+ ions in methanol due to its suitable redox potential of -0.49 V, and the CO2 as the oxidation product in the gas state can be easily separated from the solution. The FPEA2 SnI4 single crystal grown by this strategy exhibits low trap density perovskite surface by constructing an FPEA2 PbI4 -FPEA2 SnI4 (FPI-FSI) single crystal heterojunction for X-ray detection. An improved X-ray sensitivity of 1.7 × 105 µC Gy-1 cm-2 is realized in the heterojunction device, outperforming the control FPEA2 PbI4 counterpart.

Highly Efficient HTM-Free Tin Perovskite Solar Cells with Outstanding Stability Exceeding 10000 h.

The bottleneck in the rapid development of tin-based perovskite solar cells (TPSCs) is the inherent chemical instability. Although this is being addressed continuously, the device performance has not improved further due to the use of PEDOT:PSS as the hole-transport material (HTM), which has poor long-term stability. Herein we have applied commercial ITO nanoparticles over ITO glass substrates and altered the surface chemistry of the ITO electrode via a simple two-step thermal annealing, followed by a UV-ozone treatment. These surface-modified ITO electrodes display promising interfacial characteristics, such as a suitable band alignment owing to significantly reduced surface carbon contamination, increased In-O bonding, and reduced oxygen vacancies, that enabled fabrication of an HTM-free TPSC device according to a two-step method. The fabricated device possessed an outstanding power conversion efficiency (PCE) of 9.7%, along with a superior long-term stability by retaining over 90% of the initial PCE upon shelf storage in a glovebox for a period of over 10000 h. The application of ITO nanoparticles led to effective interfacial passivation, whose impacts on the long-term durability were assessed using electrochemical impedance spectroscopy, time-resolved photoluminescence decay profiles, and femtosecond transient absorption spectroscopy techniques.

Cs2 SnCl6 : To Emit or to Catalyze? Te4+ Ion Calls the Shots.

A low concentration of Te4+ doping is found to be capable of endowing the lead-free Cs2 SnCl6 perovskites with excellent photoluminescence quantum yield (PLQY), while further increasing Te4+ concentration leads to PLQY deterioration. The mechanism behind the improved PLQY is intensively studied and reported elsewhere. However, little work is conducted to understand the decreased PLQY at high doping levels and to explore its implications for non-PL-related applications. Here, it is demonstrated that the Te4+ -incorporated Cs2 SnCl6 can be promising candidate for efficient CO2 photocatalysis. An optimum photocatalytic performance is achieved when Te4+ concentration reaches as high as 50%, at which point significant PL quenching has occurred. Through a detailed spectral characterization, such concentration-dependent functionality is attributed to systematic changes in both electronic and local crystal structure, which allow a robust regulation of excitation energy relaxation channels. These findings expand the scope of available photocatalysts for CO2 reduction and also inform synthetic planning for the preparation of multifunctional Pb-free metal halide perovskites.

Lasing in Two-Dimensional Tin Perovskites.

Two-dimensional (2D) perovskites have been proposed as materials capable of improving the stability and surpassing the radiative recombination efficiency of three-dimensional perovskites. However, their luminescent properties have often fallen short of what has been expected. In fact, despite attracting considerable attention for photonic applications during the last two decades, lasing in 2D perovskites remains unclear and under debate. Here, we were able to improve the optical gain properties of 2D perovskite and achieve optically pumped lasing. We show that the choice of the spacer cation affects the defectivity and photostability of the perovskite, which in turn influences its optical gain. Based on our synthetic strategy, we obtain PEA2SnI4 films with high crystallinity and favorable optical properties, resulting in amplified spontaneous emission (ASE) with a low threshold (30 µJ/cm2), a high optical gain above 4000 cm-1 at 77 K, and ASE operation up to room temperature.

Fast-Response Oxygen Optical Fiber Sensor based on PEA2 SnI4 Perovskite with Extremely Low Limit of Detection.

Oxygen sensor is an important technique in various applications including industrial process control, medical equipment, biological fabrication, etc. The reported optical fiber-based configurations so far, using gas-sensitive coating do not meet the stringent performance targets, such as fast response time and low limit of detection (LOD). Tin-based halide perovskites are sensitive to oxygen with potential use for sensor applications. Here, the halide perovskite-based oxygen optical fiber sensor by combining phenylethylammonium tin iodide (PEA2 SnI4 ) and tilted fiber Bragg grating (TFBG) is demonstrated. The PEA2 SnI4 -based oxygen optical fiber sensor is reversible at room temperature with a response time of about 10 s, and the experimental LOD approaches to an extremely low oxygen concentration of about 50 ppm. The as-fabricated oxygen sensor shows a relative response change of 0.6 dB for an oxygen concentration increase from 50 ppm to 5% with good gas selection against NO2 , CO, CO2 , H2 . This work extends the sensor applications of halide perovskites, providing a novel technique for rapid and repeatable oxygen gas detection at a low level.

Vapor-Assisted In Situ Recrystallization for Efficient Tin-Based Perovskite Light-Emitting Diodes.

Tin-based perovskites are a promising candidates to replace their toxic lead-based counterparts in optoelectronic applications, such as light-emitting diodes (LEDs). However, the development of tin perovskite LEDs is slow due to the challenge of obtaining high-quality tin perovskite films. Here, a vapor-assisted spin-coating method is developed to achieve high-quality tin perovskites and high-efficiency LEDs. It is revealed that solvent vapor can lead to in situ recrystallization of tin perovskites during the film-formation process, thus significantly improving the crystalline quality with reduced defects. An antioxidant additive is further introduced to suppress the oxidation of Sn2+ and increase the photoluminescence quantum efficiency up to ≈30%, which is an approximately fourfold enhancement in comparison with that of the control method. As a result, efficient tin perovskite LEDs are achieved with a peak external quantum efficiency of 5.3%, which is among the highest efficiency of lead-free perovskite LEDs.

A Selective Targeting Anchor Strategy Affords Efficient and Stable Ideal-Bandgap Perovskite Solar Cells.

Mixed lead-tin perovskite solar cells (LTPSCs) with an ideal bandgap are demonstrated as a promising candidate to reach higher power conversion efficiency (PCE) than their Pb-counterparts. Herein, a Br-free mixed lead-tin perovskite material, FA0.8 MA0.2 Pb0.8 Sn0.2 I3 , with a bandgap of 1.33 eV, as a perovskite absorber, is selected. Through density functional theory calculations and optoelectronic techniques, it is demonstrated that both Pb- and Sn-related A-site vacancies are pushed into deeper energetic depth, causing severe nonradiative recombination. Hence, a selective targeting anchor strategy that employs phenethylammonium iodide and ethylenediamine diiodide as co-modifiers to selectively anchor with Pb- and Sn-related active sites and passivate bimetallic traps, respectively, is established. Furthermore, the selectivity of the molecular oriented anchor passivation is demonstrated through energetic depth specificity of Pb- and Sn-related traps. As a result, a substantially enhanced open-circuit voltage (VOC ) from 0.79 to 0.90 V for the LTPSCs is achieved, yielding a champion PCE of 22.51%, which is the highest PCE among the reported ideal-bandgap PSCs. The VOC loss is reduced to 0.43 V.

Mixed Lead-Tin Halide Perovskites for Efficient and Wavelength-Tunable Near-Infrared Light-Emitting Diodes.

Near-infrared (NIR) light-emitting diodes (LEDs), with emission wavelengths between 800 and 950 nm, are useful for various applications, e.g., night-vision devices, optical communication, and medical treatments. Yet, devices using thin film materials like organic semiconductors and lead based colloidal quantum dots face certain fundamental challenges that limit the improvement of external quantum efficiency (EQE), making the search of alternative NIR emitters important for the community. In this work, efficient NIR LEDs with tunable emission from 850 to 950 nm, using lead-tin (Pb-Sn) halide perovskite as emitters are demonstrated. The best performing device exhibits an EQE of 5.0% with a peak emission wavelength of 917 nm, a turn-on voltage of 1.65 V, and a radiance of 2.7 W Sr-1 m-2 when driven at 4.5 V. The emission spectra of mixed Pb-Sn perovskites are tuned either by changing the Pb:Sn ratio or by incorporating bromide, and notably exhibit no phase separation during device operation. The work demonstrates that mixed Pb-Sn perovskites are promising next generation NIR emitters.