Efficient Homojunction Tin Perovskite Solar Cells Enabled by Gradient Germanium Doping.

P-type self-doping is known to hamper tin-based perovskites for developing high-performance solar cells by increasing the background current density and carrier recombination processes. In this work, we propose a gradient homojunction structure with germanium doping that generates an internal electric field across the perovskite film to deplete the charge carriers. This structure reduces the dark current density of perovskite by over 2 orders of magnitude and trap density by an order of magnitude. The resultant tin-based perovskite solar cells exhibit a higher power conversion efficiency of 13.3% and excellent stability, maintaining 95% and 85% of their initial efficiencies after 250 min of continuous illumination and 3800 h of storage, respectively. We reveal the homojunction formation mechanism using density functional theory calculations and molecular level characterizations. Our work provides a reliable strategy for controlling the spatial energy levels in tin perovskite films and offers insights into designing intriguing lead-free perovskite optoelectronics.

Synergistically Coupling Atomic-Level Defect-Manipulation and Nanoscopic-Level Interfacial Engineering Enables Fast and Durable Sodium Storage.

Through inducing interlayer anionic ligands and functionally modifying conductive carbon-skeleton on the transition metal chalcogenides (TMCs) parent to achieve atomic-level defect-manipulation and nanoscopic-level architecture design is of great significance, which can broaden interlayer distance, optimize electronic structure, and mitigate structural deformation to endow high-efficiency battery performance of TMCs. Herein, an intriguing 3D biconcave hollow-tyre-like anode constituted by carbon-packaged defective-rich SnSSe nanosheet grafting onto Aspergillus niger spores-derived hollow-carbon (ANDC@SnSSe@C) is reported. Systematically experimental investigations and theoretical analyses forcefully demonstrate the existence of anion Se ligand and outer-carbon all-around encapsulation on the ANDC@SnSSe@C can effectively yield abundant structural defects and Na+-reactivity sites, accelerate rapid ion migration, widen interlayer spacing, as well as relieve volume expansion, thus further resolving the critical issues throughout the charge-discharge processes. As anticipated, as-fabricated ANDC@SnSSe@C anode contributes extraordinary reversible capacity, wonderful cyclic lifespan with 83.4% capacity retention over 2000 cycles at 20.0 A g-1, and exceptional rate capability. A series of correlated kinetic investigations and ex situ characterizations deeply reveal the underlying springheads for the ion-transport kinetics, as well as synthetically elucidate phase-transformation mechanism of the ANDC@SnSSe@C. Furthermore, the ANDC@SnSSe@C-based sodium ion full cell and hybrid capacitor offer high-capacity contribution and remarkable energy-density output, indicative of its great practicability.

Doping Strategies for Promising Organic-Inorganic Halide Perovskites.

Organic-inorganic halide perovskites (OIHPs) obtained tremendous attention due to their low cost and excellent properties. However, the stability and toxicity of Pb-based OIHPs (POIHPs), as well as the weakness of efficiency and stability in Sn-based OIHPs (SOIHPs), are still serious issues for commercial application. Notably, composition engineering is an effective and direct strategy for improving these issues along with the control and modification of properties. Recently, the doping strategies for POIHPs and SOIHPs are booming. Based on the relationship between properties and composition, the doping strategies for POIHPs and SOIHPs, aiming to provide a comprehensive review and guidance for the research are systematically summarized. Moreover, the doping strategies for Pb-Sn mixed OIHPs are also discussed. Finally, a brief perspective and conclusion toward future possible doping schemes and properties designment of POIHPs and SOIHPs are offered.

Morphology and Performance Enhancement through the Strong Passivation Effect of Amphoteric Ions in Tin-based Perovskite Solar Cells.

Despite the optoelectronic similarities between tin and lead halide perovskites, the performance of tin-based perovskite solar cells remains far behind, with the highest reported efficiency to date being ≈14%. This is highly correlated to the instability of tin halide perovskite, as well as the rapid crystallization behavior in perovskite film formation. In this work, l-Asparagine as a zwitterion plays a dual role in controlling the nucleation/crystallization process and improving the morphology of perovskite film. Furthermore, tin perovskites with l-Asparagine show more favorable energy-level matching, enhancing the charge extraction and minimizing the charge recombination, leading to an enhanced power conversion efficiency of 13.31% (from 10.54% without l-Asparagine) with remarkable stability. These results are also in good agreement with the density functional theory calculations. This work not only provides a facile and efficient approach to controlling the crystallization and morphology of perovskite film but also offers guidelines for further improved performance of tin-based perovskite electronic devices.

The Defect Passivation of Tin Halide Perovskites Using a Cesium Iodide Modification.

Tin-based perovskites are promising for realizing lead-free perovskite solar cells; however, there remains a significant challenge to achieving high-performance tin-based perovskite solar cells. In particular, the device fill factor was much lower than that of other photovoltaic cells. Therefore, understanding how the fill factor was influenced by device physical mechanisms is meaningful. In this study, we reported a method to improve the device fill factor using a thin cesium iodide layer modification in tin-based perovskite cells. With the thin passivation layer, a high-quality perovskite film with larger crystals and lower charge carrier densities was obtained. As a result, the series resistance of devices was decreased; the shunt resistance of devices was increased; and the non-radiative recombination of devices was suppressed. Consequently, the fill factor, and the device efficiency and stability were greatly enhanced. The champion tin-based perovskite cells showed a fill factor of 63%, an efficiency of 6.1% and excellent stability. Our study reveals that, with a moderate thin layer modification strategy, the long-term stability of tin-based PSCs can be developed.

Hole Transport Materials for Tin-Based Perovskite Solar Cells: Properties, Progress, Prospects.

The power conversion efficiency of modern perovskite solar cells has surpassed that of commercial photovoltaic technology, showing great potential for commercial applications. However, the current high-performance perovskite solar cells all contain toxic lead elements, blocking their progress toward industrialization. Lead-free tin-based perovskite solar cells have attracted tremendous research interest, and more than 14% power conversion efficiency has been achieved. In tin-based perovskite, Sn2+ is easily oxidized to Sn4+ in air. During this process, two additional electrons are introduced to form a heavy p-type doping perovskite layer, necessitating the production of hole transport materials different from that of lead-based perovskite devices or organic solar cells. In this review, for the first time, we summarize the hole transport materials used in the development of tin-based perovskite solar cells, describe the impact of different hole transport materials on the performance of tin-based perovskite solar cell devices, and summarize the recent progress of hole transport materials. Lastly, the development direction of lead-free tin-based perovskite devices in terms of hole transport materials is discussed based on their current development status. This comprehensive review contributes to the development of efficient, stable, and environmentally friendly tin-based perovskite devices and provides guidance for the hole transport layer material design.

Monodisperse Adducts-Induced Homogeneous Nucleation Towards High-Quality Tin-Based Perovskite Film.

The classic solvent system can't sufficiently separate one-dimensional edge-sharing SnI2 crystals in solution, which severely restricts the fabrication of high-quality tin-based perovskite film. Herein, a strong Lewis base (hexamethylphosphoramide, HMPA) has been introduced to coordinate Sn2+ to modulate solvation behaviours on perovskite precursor and regulate crystallization kinetics. The large molecular volume of HMPA and stronger bind energy of SnI2 ⋅ 2HMPA (-0.595 eV vs -0.118 eV for SnI2 ⋅ 2DMSO) change the solvation structure of SnI2 from edge-sharing cluster to monodisperse adduct, which contributes to uniform nucleation sites and prolongs crystal growth process. Delightfully, a fully-covered perovskite film is formed on the large-area substrate and tin-based perovskite solar cells processed with HMPA exhibit an excellent efficiency of 13.46 %. This research provides novel insights and directions for the solution preparation of smooth and uniform large-area tin-based perovskite film.

Mechanistic Understanding of Oxidation of Tin-based Perovskite Solar Cells and Mitigation Strategies.

Tin (Sn)-based perovskites as the most promising absorber materials for lead-free perovskite solar cells (PSCs) have achieved the record efficiency of over 14 %. Although suppressing the oxidation of Sn-based perovskites is a frequently concerned topic for Sn-based PSCs, many studies have given vague explanations and the mechanisms are still under debate. This is in principal due to the lack of an in-depth understanding of various and complex intrinsic and extrinsic factors causing the oxidation process. In this context, we critically review the chemical mechanism of facile oxidation of Sn-based perovskites and differentiate its detrimental effects at material- and device-level. More importantly, we classify and introduce the intrinsic factors (raw materials and solvent of perovskite precursors) and extrinsic factors (exposure to neutral oxygen and superoxide) causing the oxidation with their corresponding anti-oxidation improvement methods. The presented comprehensive understanding and prospect of the oxidation provide insightful guidance for suppressing the oxidation in Sn-based PSCs "from the beginning to the end".

Birefringence Regulation by Clarifying the Relationship Between Stereochemically Active Lone Pairs and Optical Anisotropy in Tin-based Ternary Halides.

It is important to establish and clarify the relationship between stereochemically active lone pairs and birefringence, since it is one of the significantly effective routes to explore birefringent crystals by introducing Sn-centered polyhedra with stereochemically active lone pairs. Herein, four tin(II)-based ternary halides A3 SnCl5 and ASn2 Cl5 (A=NH4 and Rb) have been synthesized successfully. The experimental birefringence of Rb3 SnCl5 and RbSn2 Cl5 is larger than or equal to 0.046 and 0.123@546 nm, respectively. Through investigating the alkali or alkaline-earth metal tin(II)-based ternary halides, the structure-performance relationship has been concluded between stereochemically active lone pairs and optical anisotropy. It is beneficial to the analysis and prediction of birefringence in tin-based halides and provides a guide for exploring tin(II)-based optoelectronic functional materials.

Mesoporous Tin-Based Oxide Nanospheres/Reduced Graphene Composites as Advanced Anodes for Lithium-Ion Half/Full Cells and Sodium-Ion Batteries.

The large volume variations of tin-based oxides hinder their extensive application in the field of lithium-ion batteries (LIBs). In this study, structure design, hybrid fabrication, and carbon-coating approaches have been simultaneously adopted to address these shortcomings. To this end, uniform mesoporous NiO/SnO2 @rGO, Ni-Sn oxide@rGO, and SnO2 @rGO nanosphere composites have been selectively fabricated. Among them, the obtained NiO/SnO2 @rGO composite exhibited a high capacity of 800 mAh g-1 at 1000 mA g-1 after 400 cycles. The electrochemical mechanism of NiO/SnO2 as an anode for LIBs has been preliminarily investigated by ex situ XRD pattern analysis. Furthermore, an NiO/SnO2 @rGO-LiCoO2 lithium-ion full cell showed a high capacity of 467.8 mAh g-1 at 500 mA g-1 after 100 cycles. Notably, the NiO/SnO2 @rGO composite also showed good performance when investigated as an anode for sodium-ion batteries (SIBs). It is believed that the unique mesoporous nanospherical framework, synergistic effects between the various components, and uniform rGO wrapping of NiO/SnO2 shorten the Li+ ion diffusion pathways, maintain sufficient contact between the active material and the electrolyte, mitigate volume changes, and finally improve the electrical conductivity of the electrode.

State-of-the-Art: DTM Generation Using Airborne LIDAR Data.

Digital terrain model (DTM) generation is the fundamental application of airborne Lidar data. In past decades, a large body of studies has been conducted to present and experiment a variety of DTM generation methods. Although great progress has been made, DTM generation, especially DTM generation in specific terrain situations, remains challenging. This research introduces the general principles of DTM generation and reviews diverse mainstream DTM generation methods. In accordance with the filtering strategy, these methods are classified into six categories: surface-based adjustment; morphology-based filtering, triangulated irregular network (TIN)-based refinement, segmentation and classification, statistical analysis and multi-scale comparison. Typical methods for each category are briefly introduced and the merits and limitations of each category are discussed accordingly. Despite different categories of filtering strategies, these DTM generation methods present similar difficulties when implemented in sharply changing terrain, areas with dense non-ground features and complicated landscapes. This paper suggests that the fusion of multi-sources and integration of different methods can be effective ways for improving the performance of DTM generation.

Investigation of the Properties of Anti-Friction Coatings Deposited with Different Casting Methods.

This article presents the research results of depositing anti-friction coatings (Babbitt) using three different casting methods: static casting, flame soldering, and clad welding. Babbitt alloy coatings deposited with different casting methods are discussed and explained in terms of changes in the coating properties, such as the microstructure, hardness, strength, and chemical composition. The results showed significant differences in the aforementioned properties, depending on the chosen coating deposition method. The results of the tests confirmed the importance of using shielding gas during deposition to ensure the chemical composition of the coating. The analysis revealed that decreases in the amounts of antimony and copper in the Babbitt coating compared with the initial concentrations were influenced by selective evaporation, oxidation, and the coating process parameters associated with different coating methods. To maintain the desired balance of mechanical properties in Babbitt coatings, it is important to control the antimony and copper contents. Clad welding deposition using a non-consumable tungsten electrode and argon shielding gas achieved a chemically stable coating quite close to the initial chemical composition of the Babbitt alloy.

Enhancing Stability and Performance in Tin-Based Perovskite Field-Effect Transistors Through Hydrogen Bond Suppression of Organic Cation Migration.

Ion migration poses a substantial challenge in perovskite transistors, exerting detrimental effects on hysteresis and operational stability. This study focuses on elucidating the influence of ion migration on the performance of tin-based perovskite field-effect transistors (FETs). It is revealed that the high background carrier density in FASnI3 FETs arises not only from the oxidation of Sn2+ but also from the migration of FA+ ions. The formation of hydrogen bonding between FA+ and F- ions efficiently inhibits ion migration, leading to a reduction in background carrier density and an improvement in the operational stability of the transistors. The strategy of hydrogen bond is extended to fluorine-substituted additives to improve device performance. The incorporation of 4-fluorophenethylammonium iodide additives into FETs significantly minimizes the shift of turn-on voltage during cyclic measurements. Notably, an effective mobility of up to 30 cm2 V-1 s-1 with an Ion/off ratio of 107 is achieved. These findings hold promising potential for advancing tin-based perovskite technology in the field of electronics.

Significantly Improved Efficiency and Stability of Pure Tin-Based Perovskite Solar Cells with Bifunctional Molecules.

Tin-based perovskite solar cells (TPSCs) have become one of the most prospective photovoltaic materials due to their remarkable optoelectronic properties and relatively low toxicity. Nevertheless, the rapid crystallization of perovskites and the easy oxidization of Sn2+ to Sn4+ make it challenging to fabricate efficient TPSCs. In this work, a piperazine iodide (PI) material with -NH- and -NH2+- bifunctional groups is synthesized and introduced into the PEA0.1FA0.9SnI3-based precursor solution to tune the microstructure, charge transport, and stability of TPSCs. Compared with piperazine (PZ) containing only the -NH- group, the PI additive displays better effects on regulating the microstructure and crystallization, inhibiting Sn2+ oxidation and reducing trap states, resulting in an optimal efficiency of 10.33%. This is substantially better than that of the reference device (6.42%). Benefiting from the fact that PI containing -NH- and -NH2+- groups can passivate both positively charged defects and negatively charged halogen defects, unencapsulated TPSCs modified with the PI material can maintain about 90% of their original efficiency after being kept in a N2 atmosphere for 1000 h, much higher than the value of 47% in reference TPSCs without additives. This work provides a practical method to prepare efficient and stable pure TPSCs.

Well-Defined Fullerene Bisadducts Enable High-Performance Tin-Based Perovskite Solar Cells.

Tin-based perovskite solar cells (TPSCs) are attracting intense research interest due to their excellent optoelectric properties and eco-friendly features. To further improve the device performance, developing new fullerene derivatives as electron transporter layers (ETLs) is highly demanded. Four well-defined regioisomers (trans-2, trans-3, trans-4, and e) of diethylmalonate-C60 bisadduct (DCBA) are isolated and well characterized. The well-defined molecular structure enables us to investigate the real structure-dependent effects on photovoltaic performance. It is found that the chemical structures of the regioisomers not only affect their energy levels, but also lead to significant differences in their molecular packings and interfacial contacts. As a result, the devices with trans-2, trans-3, trans-4, and e as ETLs yield efficiencies of 11.69%, 14.58%, 12.59%, and 10.55%, respectively, which are higher than that of the as-prepared DCBA-based (10.28%) device. Notably, the trans-3-based device also demonstrates a certified efficiency of 14.30%, representing one of the best-performing TPSCs.

Mutually Tuned Dual Additive Engineering Synergistically Enhances the Photovoltaic Performance of Tin-Based Perovskite Solar Cells.

Tin-based perovskite solar cells (T-PSCs) have become the star photovoltaic products in recent years due to their low environmental toxicity and superior photovoltaic performance. However, the easy oxidation of Sn2+ and the energy level mismatch between the perovskite film and charge transport layer limit its efficiency. In order to regulate the microstructure and photoelectric properties of tin-based perovskite films to enhance the efficiency and stability of T-PSCs, guanidinium bromide (GABr) and organic Lewis-based additive methylamine cyanate (MAOCN) are introduced into the FA0.9PEA0.1SnI3-based perovskite precursor. A series of characterizations show that the interactions between additive molecules and perovskite mutually reconcile to improve the photovoltaic performance of T-PSCs. The introduction of GABr can adjust the band gap of the perovskite film and energy level alignment of T-PSCs. They significantly increase the open-circuit voltage (Voc). The MAOCN material can form hydrogen bonds with SnI2 in the precursor, which can inhibit the oxidation of Sn2+ and significantly improve the short-circuit current density (Jsc). The synergistic modulation of the dual additives reduces the trap-state density and improves photovoltaic performance, resulting in an increased champion efficiency of 9.34 for 5.22% of the control PSCs. The unencapsulated T-PSCs with GABr and MAOCN dual additives prepared in the optimized process can retain more than 110% of their initial efficiency after aging for 1750 h in a nitrogen glovebox, but the control PSCs maintain only 50% of their initial efficiency kept in the same conditions. This work provides a new perspective to further improve the efficiency and stability of T-PSCs.

Enhancing Efficiency and Stability of Tin Halide Perovskite Light-Emitting Diodes via Engineered Alkali/Multivalent Metal Salts.

Sn-based perovskite light-emitting diodes (PeLEDs) have emerged as promising alternatives to Pb-based PeLEDs with their rapid increase in performance owing to the various research studies on inhibiting Sn oxidation. However, the absence of defect passivation strategies for Sn-based perovskite LEDs necessitates further research in this field. We performed systematic studies to investigate the design rules for defect passivation agents for Sn-based perovskites by incorporating alkali/multivalent metal salts with various cations and anions. From the computational and experimental analyses, sodium trifluoromethanesulfonate (NaTFMS) was found to be the most effective passivation agent for PEA2SnI4 films among the explored candidate agents owing to favorable reaction energetics to passivate iodide Frenkel defects. Consequently, the incorporation of NaTFMS facilitates the formation of uniform films with relatively large crystals and reduced Sn4+. The NaTFMS-containing PEA2SnI4 PeLEDs demonstrate an improved luminance of 138.9 cd/m2 and external quantum efficiency (EQE) of 0.39% with an improved half-lifetime of more than threefold. This work provides important insight into the design of defect passivation agents for Sn-based perovskites.

Photoluminescence Intensity Enhancement in Tin Halide Perovskites.

The prevalence of background hole doping in tin halide perovskites usually dominates their recombination dynamics. The addition of excess Sn halide source to the precursor solution is the most frequently used approach to reduce the hole doping and reveals photo-carrier dynamics related to defects activity. This study presents an experimental and theoretical investigation on defects under light irradiation in tin halide perovskites by combining measurements of photoluminescence with first principles computational modeling. It finds that tin perovskite thin films prepared with an excess of Sn halide sources exhibit an enhancement of the photoluminescence intensity over time under continuous excitation in inert atmosphere. The authors propose a model in which light irradiation promotes the annihilation of VSn 2- /Sni 2+ Frenkel pairs, reducing the deep carrier trapping centers associated with such defect and increasing the radiative recombination. Importantly, these observations can be traced in the open-circuit voltage dynamics of tin-based halide perovskite solar cells, implying the relevance of controlling the Sn photochemistry to stabilize tin perovskite devices.

Fullerene Derivative with Flexible Alkyl Chain for Efficient Tin-Based Perovskite Solar Cells.

Fullerene derivatives are considered excellent materials for the extraction and transportation of electrons in the production of efficient tin-based perovskite solar cells (TPSCs). However, it is not clear how the molecular structure of fullerene derivatives affects the efficiency and stability of TPSCs. In this study, the effects of fullerene derivatives, (6,6)-phenyl-C61-butyric acid hexyl ester (PCBH) and (6,6)-phenyl-C61-butyric acid methyl ester (PCBM), with different functional groups, on photovoltaic performance were investigated. The flexible alkyl chain of PCBH effectively improved the film morphology and stability, the electron extraction and transport capabilities, and the interface contact of fullerene and perovskite. As a result, the PCBH-based TPSC yielded a higher efficiency, of 9.21%, than the PCBM-based devices (7.54%). More importantly, the PCBH-based films exhibited higher stability and effectively suppressed the oxidation of Sn2+ by inhibiting oxygen permeation. Therefore, the PCBH-based devices exhibited significantly enhanced stability. This result indicates that optimizing the functional group of fullerene derivatives is crucial for improving the efficiency and stability of TPSCs.

Tin Halide Perovskites: From Fundamental Properties to Solar Cells.

Metal halide perovskites have unique optical and electrical properties, which make them an excellent class of materials for a broad spectrum of optoelectronic applications. However, it is with photovoltaic devices that this class of materials has reached the apotheosis of popularity. High power conversion efficiencies are achieved with lead-based compounds, which are toxic to the environment. Tin-based perovskites are the most promising alternative because of their bandgap close to the optimal value for photovoltaic applications, the strong optical absorption, and good charge carrier mobilities. Nevertheless, the low defect tolerance, the fast crystallization, and the oxidative instability of tin halide perovskites currently limit their efficiency. The aim of this review is to give a detailed overview of the crystallographic, photophysical, and optoelectronic properties of tin-based perovskite compounds in their multiple forms from 3D to low-dimensional structures. At the end, recent progress in tin-based perovskite solar cells are reviewed, mainly focusing on the detail of the strategies adopted to improve the device performances. For each subtopic, the current challenges and the outlook are discussed, with the aim to stimulate the community to address the most important issues in a concerted manner.