Sn-based Perovskites Research Articles

Comprehensive study on phase stability of lead-free Sn-based perovskite FAxMA1-xSnI3

Perovskite solar cells have become the most important devices for solar power to electricity conversion. However, currently, high-efficiency perovskite solar cells still rely on the use of Pb, which is harmful to the environment. Seeking environmentally friendly perovskite solar cells is imperative, and Sn is the most effective substitute for Pb. However, Sn-based perovskites face challenges due to their brief lifespan and rapid degradation, underscoring the need to improve their phase stability - a problem with still unclear mechanisms. This study addresses this by adjusting the ratio of formamidinium to methylammonium (FA/MA) in FAxMA1-xSnI3, experimentally finding optimal stability in phase composition and photoluminescence intensity at a ratio where x = 0.75. Using Density Functional Theory (DFT) and a pre-trained, fine-tuned machine-learning model, we explore the favorable molecular structures and configurations within FAxMA1-xSnI3. We discover that the FA0.75MA0.25SnI3 composition exhibits the lowest valence band maximum, indicating minimal oxidation tendency. Further DFT calculations of mixing and formation energies confirm that this composition is the most stable, aligning well with experimental observations and elucidating the underlying mechanisms of phase stability in Sn-based perovskite solar cells.

Single Crystal Sn-Based Halide Perovskites.

Sn-based halide perovskites are expected to be the best replacement for toxic lead-based counterparts, owing to their similar ionic radii and the optimal band gap for use in solar cells, as well as their versatile use in light-emitting diodes and photodetection applications. Concerns, however, exist about their stability under ambient conditions, an issue that is exacerbated in polycrystalline films because grain boundaries present large concentrations of defects and act as entrance points for oxygen and water, causing Sn oxidation. A current thriving research area in perovskite materials is the fabrication of perovskite single crystals, promising improved optoelectronic properties due to excellent uniformity, reduced defects, and the absence of grain boundaries. This review summarizes the most recent advances in the fabrication of single crystal Sn-based halide perovskites, with emphasis on synthesis methods, compositional engineering, and formation mechanisms, followed by a discussion of various challenges and appropriate strategies for improving their performance in optoelectronic applications.

Molecularly Engineered Alicyclic Organic Spacers for 2D/3D Hybrid Tin-based Perovskite Solar Cells.

The high defect density and inferior crystallinity remain great hurdles for developing highly efficient and stable Sn-based perovskite solar cells (PSCs). 2D/3D heterostructures show strong potential to overcome these bottlenecks; however, a limited diversity of organic spacers has hindered further improvement. Herein, a novel alicyclic organic spacer, morpholinium iodide (MPI), is reported for developing structurally stabilized 2D/3D perovskite. Introducing a secondary ammonium and ether group to alicyclic spacers in 2D perovskite enhances its rigidity, which leads to increased hydrogen bonding and intermolecular interaction within 2D perovskite. These strengthened interactions facilitate the formation of highly oriented 2D/3D perovskite with low structural disorder, which leads to effective passivation of Sn and I defects. Consequently, the MP-based PSCs achieved a power conversion efficiency (PCE) of 12.04% with superior operational and oxidative stability. This work presents new insight into the design of organic spacers for highly efficient and stable Sn-based PSCs.

Synchronized crystallization in tin-lead perovskite solar cells

Tin-lead halide perovskites with a bandgap near 1.2 electron-volt hold great promise for thin-film photovoltaics. However, the film quality of solution-processed Sn-Pb perovskites is compromised by the asynchronous crystallization behavior between Sn and Pb components, where the crystallization of Sn-based perovskites tends to occur faster than that of Pb. Here we show that the rapid crystallization of Sn is rooted in its stereochemically active lone pair, which impedes coordination between the metal ion and Lewis base ligands in the perovskite precursor. From this perspective, we introduce a noncovalent binding agent targeting the open metal site of coordinatively unsaturated Sn(II) solvates, thereby synchronizing crystallization kinetics and homogenizing Sn-Pb alloying. The resultant single-junction Sn-Pb perovskite solar cells achieve a certified power conversion efficiency of 24.13 per cent. The encapsulated device retains 90 per cent of the initial efficiency after 795 h of maximum power point operation under simulated one-sun illumination.

Ternary Passivation for Enhanced Carrier Transport and Recombination Suppression in Highly Efficient Sn-Based Perovskite Solar Cells.

The exploration of nontoxic Sn-based perovskites as a viable alternative to their toxic Pb-based counterparts has garnered increased attention. However, the power conversion efficiency of Sn-based perovskite solar cells lags significantly behind their Pb-based counterparts. This study presents a ternary passivation strategy aimed at enhancing device performance, employing [6,6]-phenyl-C61-butyric-acid-methyl-ester (PCBM), poly(3-hexylthiophene) (P3HT), and indene C60 bisadduct (ICBA). These components play crucial roles in managing energy levels and enhancing carrier transportation, respectively. The results reveal that the introduction of the ternary system leads to improvements in carrier collection and transportation, accompanied by a suppression of the recombination process. Ultimately, the champion device achieves a remarkable performance with an efficiency of 14.64%. Notably, the device also exhibits robust operational and long-term stored stability.

Comparison of Pb-based and Sn-based perovskite solar cells using SCAPS simulation: optimal efficiency of eco-friendly CsSnI3 devices.

In this study, we employed the one-dimensional solar cell capacitance simulator (SCAPS-1D) software to optimize the performance of Pb-based and Sn-based (Pb-free) all-inorganic perovskites (AIPs) and organic-inorganic perovskites (OIPs) in perovskite solar cell (PSC) structures. Due to the higher stability of AIPs, the performance of PSCs incorporating Cs-based perovskites was compared with that of FA-based perovskites, which are more stable than their MA-based counterparts. The impact of AIPs such as CsPbCl3, CsPbBr3, CsPbI3, CsSnCl3, CsSnBr3, and CsSnI3, as well as including FAPbCl3, FAPbBr3, FAPbI3, FASnCl3, FASnBr3, and FASnI3, was investigated. SnO2 and Cu2O were selected as an inorganic electron transport layer (ETL) and a hole transport layer (HTL), respectively. CsSnBr₃, CsSnI₃, FASnCl₃, and FASnBr₃ exhibited higher efficiency compared to their Pb-based counterparts. Additionally, most Cs-based perovskites, excluding CsPbI₃, demonstrated better performance relative to their FA counterparts. CsSnI3 AIP device also shows the highest short circuit current density (JSC) of 32.85mA/cm2, the best power conversion efficiency (PCE) of 16.00%, and the least recombination at the SnO2/CsSnI3 interface. The thickness, doping, and total defect density of CsSnI3 PSC have been systematically investigated and optimized to obtain the PCE of 17.36%. These findings highlight the potential of CsSnI3 PSCs as efficient and environmentally friendly PSCs.

First-principles study of phase-dependent carrier transport mechanism for MASnI3 Sn-based halide perovskite

Organic-inorganic hybrid perovskites have attracted tremendous attentions owing to their excellent properties as next-generation photovoltaic devices. With soft covalent framework, organic-inorganic hybrid perovskites exhibit different phases at different temperatures. The band-edge features of perovskites are mainly contributed by inorganic framework, which means the structural differences between these phases would lead to complex carrier transport. We investigated the carrier transport of Sn-based organic-inorganic hybrid perovskite CH3NH3SnI3 (MASnI3), considering acoustic deformation potential scattering, ionized impurity scattering, and polar optical phonon scattering. It is found that the electron mobility of each phase of MASnI3 is strongly correlated with the Sn–I–Sn bond angle and there is in-plane/out-of-plane anisotropy. The projected crystal orbital Hamilton population analysis suggested that the tilt and rotation of the [SnI6]4− octahedron influence the Sn(p)–I(p) orbital electron coupling and the electron transport, leading to different band-edge features in multiple phases. The carrier mobility with respect to temperature was further calculated for each phase of MASnI3 in respective temperature intervals, showing lower carrier mobility in high temperature. Comparing the contribution of different scattering mechanisms, it was found that the dominant scattering mechanism is polar optical phonon scattering, while multiple scattering mechanisms compete in individual cases.

A-Site Cations Impact on Nonradiative Recombination, Mobility, and Defect Dynamics in Sn-Based Perovskites.

Sn-based perovskites with different cations in the A-site exhibit distinct electronic structures and dynamic properties. By utilizing time-dependent density functional theory and nonadiabatic molecular dynamics, we demonstrate that larger FA cations decrease wave function overlap between initial and final states and slow down nuclear motion. In the case of FASnI3, this alteration decreases the nonadiabatic coupling and increases the nonradiative electron-hole recombination time by 130% and 76%, respectively, compared to CsSnI3 and MASnI3 (CH3NH3SnI3). Furthermore, A-site modification significantly improves electron mobility and changes the properties of defects in FASnI3 (HC(NH2)2SnI3), which achieves higher electron mobility through a polar optical phonon-dominated scattering mechanism and exhibits higher defect formation energy and migration barriers of A-site cations due to increased steric hindrance, relative to CsSnI3 and MASnI3. These results emphasize the critical function of A-site cation substitution in controlling nonradiative recombination dynamics, electron mobility, and defect characteristics in Sn-based perovskites and provide theoretical insights for the advancement of novel lead-free perovskite materials.

First principles insight into the study of the structural, stability, and optoelectronic properties of alkali-based single halide perovskite ZSnCl3 (Z = Na/K) materials for photovoltaic applications.

Metal halide perovskites are crystalline materials with a sharp increase in popularity and rapidly becoming a major contender for optoelectronic device applications. In this work, we provide the optoelectronic features of a possible novel candidate, ZSnCl3 (Z = Na/K) Sn-based on a detailed numerical simulation. The output of the current computations is compared to the results that are currently available, and a respectable agreement is noted. The studied compounds were cubic in nature and structurally stabe. The mechanical properties reflectthe mechanical stability and ductility of the proposed materials. The Sn-based single perovskite compounds proposed in this study are mechanically stable and ductile. The narrow direct band gap for NaSnCl3 and KSnCl3 are 1.36 eV and 1.47 eV, respectively, using the HSE06 hybrid function with the Boltztrp2 integrated in Quantum ESPRESSO (QE) software. The effective use of these compounds in perovskite solar cells and other optoelectronic applications was confirmed by optical absorption spectral measurements conducted in the photon energy range of 0-20 eV.

Controlling Tin Halide Perovskite Oxidation Dynamics in Solution for Perovskite Optoelectronic Devices.

As a leading contender to replace lead halide perovskites, tin-based perovskites have demonstrated ever increasing performance in solar cells and light-emitting diodes (LEDs). They tend to be processed with dimethyl sulfoxide (DMSO) solvent, which has been identified as a major contributor to the Sn(II) oxidation during film fabrication, posing a challenge to the further improvement of Sn-based perovskites. Herein, we use NMR spectroscopy to investigate the kinetics of the oxidation of SnI2, revealing that autoamplification takes place, accelerating the oxidation as the reaction progresses. We propose a mechanism consistent with these observations involving water participation and HI generation. Building upon these insights, we have developed low-temperature Sn-based perovskite LEDs (PeLEDs) processed at 60 °C, achieving enhanced external quantum efficiencies (EQEs). Our research underscores the substantial potential of low-temperature DMSO solvent processes and DMSO-free solvent systems for fabricating oxidation-free Sn-based perovskites, shaping the future direction in processing Sn-containing perovskite materials and optoelectronic devices.

Odd-Even Alkyl Chain Effects on the Structure and Charge Carrier Transport of Two-Dimensional Sn-Based Perovskite Semiconductors.

Oscillations in the chemical or physical properties of materials, composed of an odd or even number of connected repeating methylene units, are a well-known phenomenon in organic chemistry and materials science. So far, such behavior has not been reported for the important class of materials, perovskite semiconductors. This work reports a distinct odd-even oscillation of the molecular structure and charge carrier transport properties of phenylalkylammonium two-dimensional (2D) Sn-based perovskites in which the alkyl chains in the phenylalkylammonium cations contain varying odd and even carbon numbers. Density functional theory calculations and grazing-incidence wide-angle X-ray scattering characterization reveal that perovskites with organic ligands containing an alkyl chain with an odd number of carbon atoms display a disordered crystal lattice and tilted inorganic octahedra accompanied by reduced mobilities. In contrast, perovskites with cations of an even number of carbon atoms in the alkyl chain form more ordered crystal structures, resulting in improved charge carrier mobilities. Our findings disclose the importance of minor changes in the molecular conformation of organic cations have an effect on morphology, photophysical properties, and charge carrier transport of 2D layered perovskites, showcasing alkyl chain engineering of organic cations to control key properties, of layered perovskite semiconductors.

The origins of dual-peak emission and anomalous exciton decay in 2D Sn-based perovskites.

Two-dimensional (2D) Sn-based perovskites exhibit significant potential in diverse optoelectronic applications, such as on-chip lasers and photodetectors. Yet, the underlying mechanism behind the frequently observed dual-peak emission in 2D Sn-based perovskites remains a subject of intense debate, and there is a lack of research on the carrier dynamics in these materials. In this study, we investigate these issues in a representative 2D Sn-based perovskite, namely, PEA2SnI4, through temperature-, excitation intensity-, angle-, and time-dependent photoluminescence studies. The results indicate that the high- and low-energy peaks originate from in-face and out-of-face dipole transitions, respectively. In addition, we observe an anomalous increase in the non-radiative recombination rate as temperature decreases. After ruling out enhanced electron-phonon coupling and Auger recombination as potential causes of the anomalous carrier dynamics, we propose that the significantly increased exciton binding energy (Eb) plays a decisive role. The increased Eb arises from enhanced electronic localization, a consequence of weakened lattice distortion at low temperatures, as confirmed by first-principles calculations and temperature-dependent x-ray diffraction measurements. These findings offer valuable insights into the electronic processes in the unique 2D Sn-based perovskites.

Minimization of Energy Level Mismatch of PCBM and Surface Passivation for Highly Stable Sn-Based Perovskite Solar Cells by Doping n-Type Polymer.

Developing high-performance and stable Sn-based perovskite solar cells (PSCs) is difficult due to the inherent tendency of Sn2+ oxidation and, the huge energy mismatch between perovskite and Phenyl-C61-butyric acid methyl ester (PCBM), a frequently employed electron transport layer (ETL). This study demonstrates that perovskite surface defects can be passivated and PCBM's electrical properties improved by doping n-type polymer N2200 into PCBM. The doping of PCBM with N2200 results in enhanced band alignment and improved electrical properties of PCBM. The presence of electron-donating atoms such as S, and O in N2200, effectively coordinates with free Sn2+ to prevent further oxidation. The doping of PCBM with N2200 offers a reduced conduction band offset (from 0.38 to 0.21eV) at the interface between the ETL and perovskite. As a result, the N2200 doped PCBM-based PSCs show an enhanced open circuit voltage of 0.79V with impressive power conversion efficiency (PCE) of 12.98% (certified PCE 11.95%). Significantly, the N2200 doped PCBM-based PSCs exhibited exceptional stability and retained above 90% of their initial PCE when subjected to continuous illumination at maximum power point tracking for 1000h under one sun.

Dion-Jacobson-Phase 2D Sn-Based Perovskite Comprising a High Dipole Moment of π-Conjugated Short-Chain Organic Spacers for High-Performance Solar Cell Applications.

The stability issue of Sn-based perovskite solar cells (PSCs) is expected to be resolved by involving a two-dimensional (2D) layered structure. However, Sn-based 2D PSCs, especially Dion-Jacobson (DJ)-phase ones with potentially good stability, have rarely been reported. Herein, superior DJ-phase Sn 2D perovskites with 3-aminobenzylamine (3ABA2+) or 4-aminobenzylamine (4ABA2+) π-conjugated short-chain ligands are reported to fabricate efficient 2D lead-free PSCs. Notably, the high dipole moment of the 3ABAI2 organic spacer is approved to possess faster charge transfer for forming (3ABA)FA4Sn5I16 2D perovskite with an extremely low exciton binding energy (only 84 meV). In combination with a diacetate partial substitution and methylamine iodide/bromide (MAI/MABr) post-treatment strategy to delay crystallization and improve compactness and coverage of the perovskite film, a record power conversion efficiency (PCE) of 6.81% and stability of 840 h (less than 5% degradation in a N2 atmosphere for unencapsulated devices) are acquired in eventual (3ABA)FA4Sn5I16 2D PSCs, which are among the highest PCE and the longest stability of Sn-based 2D PSCs reported to date. Our work provides a prospective molecule design and film preparation strategy of 2D Sn perovskites toward nontoxic high-performance tin-based PSCs, which pushes the almost stagnant research forward.

Synergistic Modulation of Sn-Based Perovskite Solar Cells with Crystallization and Interface Engineering.

A high-quality Sn-based perovskite absorption layer and effective carrier transport are the basis for high-performance Sn-based perovskite solar cells. The suppression of Sn2+ oxidation and rapid crystallization is the key to obtaining high-quality Sn-based perovskite film. And interface engineering is an effective strategy to enhance carrier extraction and transport. In this work, tin fluoride (SnF2) was introduced to the perovskite precursor solution, which can effectively modulate the crystallization and morphology of Sn-based perovskite layer. Furthermore, the hole-transporting layer of PEDOT:PSS was modified with CsI to enhance the hole extraction and transport. As a result, the fabricated inverted Sn-based perovskite solar cells demonstrated a power conversion efficiency of 7.53% with enhanced stability.

Counter-Doping Effect by Trivalent Cations in Tin-Based Perovskite Solar Cells.

Tin (Sn) -based perovskite solar cells (PSCs) normally show low open circuit voltage due to serious carrier recombination in the devices, which can be attributed to the oxidation and the resultant high p-type doping of the perovskite active layers. Considering the grand challenge to completely prohibit the oxidation of Sn-based perovskites, a feasible way to improve the device performance is to counter-dope the oxidized Sn-based perovskites by replacing Sn2+ with trivalent cations in the crystal lattice, which however is rarely reported. Here, the introduction of Sb3+, which can effectively counter-dope the oxidized perovskite layer and improve the carrier lifetime, is presented. Meanwhile, Sb3+ can passivate deep-level defects and improve carrier mobility of the perovskite layer, which are all favorable for the photovoltaic performance of the devices. Consequently, the target devices yield a relative enhancement of the power conversion efficiency (PCE) of 31.4% as well as excellent shelf-storage stability. This work provides a novel strategy to improve the performance of Sn-based PSCs, which can be developed as a universal way to compensate for the oxidation of Sn-based perovskites in optoelectronic devices.

Piperidine and Pyridine Series Lead-Free Dion-Jacobson Phase Tin Perovskite Single Crystals and Their Applications for Field-Effect Transistors.

Two-dimensional (2D) organic-inorganic metal halide perovskites have gained immense attention as alternatives to three-dimensional (3D) perovskites in recent years. The hydrophobic spacers in the layered structure of 2D perovskites make them more moisture-resistant than 3D perovskites. Moreover, they exhibit unique anisotropic electrical transport properties due to a structural confinement effect. In this study, four lead-free Dion-Jacobson (DJ) Sn-based phase perovskite single crystals, 3AMPSnI4, 4AMPSnI4, 3AMPYSnI4, and 4AMPYSnI4 [AMP = (aminomethyl)-piperidinium, AMPY = (aminomethyl)pyridinium] are reported. Results reveal structural differences between them impacting the resulting optical properties. Namely, higher octahedron distortion results in a higher absorption edge. Density functional theory (DFT) is also performed to determine the trends in energy band diagrams, exciton binding energies, and formation energies due to structural differences among the four single crystals. Finally, a field-effect transistor (FET) based on 4AMPSnI4 is demonstrated with a respectable hole mobility of 0.57 cm2 V-1 s-1 requiring a low threshold voltage of only -2.5 V at a drain voltage of -40 V. To the best of our knowledge, this is the third DJ-phase perovskite FET reported to date.

A Lead-Free Ferroelectric 2D Dion-Jacobson Tin Iodide Perovskite.

2D hybrid organic-inorganic halide perovskites emerge as a new class of 2D semiconductors with the potential to combine excellent optoelectronic properties with symmetry-enabled properties such as ferroelectricity. Although many lead-based ferroelectric 2D halide perovskites are reported, there is yet to be a conclusive report of ferroelectricity in tin-based 2D perovskites. Here, the structures and properties of a new series of 2D Dion-Jacobson (DJ) Sn perovskites: (4AMP)SnI4, (4AMP)(MA)Sn2I7, and (4AMP)(FA)Sn2I7 (4AMP = 4-(aminomethyl)piperidinium, MA = methylammonium, and FA = formamidinium), are reported. Structural characterization reveals that (4AMP)SnI4 is polar with in-plane spontaneous polarization whereas (4AMP)(MA)Sn2I7 and (4AMP)(FA)Sn2I7 are centrosymmetric. Further, (4AMP)SnI4 displays second harmonic generation (SHG) and polarization-electric field hysteresis measurements confirm it is ferroelectric with a spontaneous polarization of 10.0 µC cm-2 at room temperature. (4AMP)SnI4 transitions into a centrosymmetric structure above 367 K. As the first direct experimental observation of the spontaneous ferroelectric polarization of a Sn-based 2D hybrid perovskite, this work opens up environmentally friendly 2D tin halide perovskites for ferroelectricity and other physical property studies.

Structure and Optical Properties of Sn-Based Halide Perovskites (C10H18N2)SnX4 (X = Cl, Br, I).

Low-dimensional tin-based halide perovskites are considered as eco-friendly substitutions of the iconic lead-based perovskites to host the potential as optoelectronic materials. However, a fundamental understanding of the structure-property relationship of these Sn(II)-based hybrids is still inadequate due to the limited members of this material family. To our knowledge, there is still lack of reports on a series of Sn(II)-based halide perovskites with the same organic cation but covering chloride, bromide, and iodide. In this work, three new halide perovskites TMPDASnX4 (X = Cl, Br, I) (TMPDA = N,N,N',N'-tetramethyl-1,4-phenylenediamine) are successfully synthesized, which provide the ideal paradigm to study the halogen-dependent evolution of the structure and properties of Sn(II)-based hybrid perovskites. Despite sharing the same monoclinic lattice (P21/m space group), it is demonstrated that TMPDASnCl4 adopts a one-dimensional structure composed of a five-coordinated pyramid configuration due to an extremely long Sn···Cl distance, while the typical two-dimensional motif is still maintained in TMPDASnBr4 and TMPDASnI4. The ambient stability is declined in the order from chloride to bromide and then to iodide. TMPDASnCl4 exhibits a broad-band bluish-white-light emission (centered at 515 nm, full width at half-maximum (fwhm) = 193 nm) with the Commission Internationale de l' Elairage (CIE) coordinates as (0.29, 0.34). Further, the correlated color temperature and color-rendering index were determined as 7617 K and 80.5, respectively. Based on the synthesis of new crystals, our work sheds light on the composition-structure-property relationship of hybrid Sn(II)-based halide perovskites.

Trap-Induced Long-Lived Internal Charge Separation in Sn-Doped MAPbBr3 Perovskite Films.

Sn-doped lead halide perovskites (LHPs) have attracted considerable attention for their lower bandgap and lower toxicity. While it is well-established that Sn doping easily introduces a lot of structural defects into LHP films, the extent to which these defects impact carrier dynamics has yet to be fully elucidated. Herein, we take Sn-doped MAPbBr3 films as an example to explore the influence of Sn doping on their carrier dynamics. The results show that Sn doping can simultaneously introduce many fillable electron traps and unfillable hole traps, consequently instigating an ultrafast carrier capture process. This further elicits long-lived internal charge separation between band edge and trap states or between two kinds of trap states, thereby enabling these carriers to persist for up to ∼2.6 μs. Our findings suggest that Sn doping potentially serves as an effective strategy to prolong the carrier lifetime in LHPs, which could pave the way for potential applications within Sn-based perovskites.