2D Perovskite Research Articles

Ionic liquid engineering enables 1D/3D perovskite photovoltaics with > 25 % efficiency: A real-time study exploring formation mechanism of 1D perovskites

The advancements in low-dimensional/three-dimensional (LD/3D) perovskite devices represent a promising approach to enhancing both the efficiency and stability of of perovskite solar cells (PSCs). However, while significant efforts have been dedicated to understanding the role of already formed low-dimensional perovskites in passivating defects, refining the work function, little attention has been given to the crystallization process of LD perovskites, particularly when induced by ionic liquids (ILs) as green and stable additive. In this work, the formation process of IL Tetrabutylammonium Thiocyanate (TBASCN)-induced 1D perovskite onto the 3D perovskite under varying annealing conditions were explored by in-situ Grazing-Incidence Wide-Angle X-ray Scattering (GIWAXS) technology, providing a comprehensive investigation into the distinct impacts of 1D perovskite formed under diverse annealing processes on device performance. Owing to the robust interaction and favorable binding energy between the IL TBASCN and perovskite components, coupled with the low formation energy of 1D perovskites, 1D perovskites exhibit rapid formation on the surface of 3D perovskites and display markedly distinct crystallization processes under distinguished annealing conditions. Achieving full crystallization of 1D perovskites necessitates optimal temperature of 100 °C and adequate duration of 100 s. Once fully crystallized, the highly crystalline 1D perovskites and anions SCN- present in ILs can synergistically passivate defects in 3D perovskites, mitigate ion migration and impeding moisture infiltration. Benefiting from the optimized formation process of 1D perovskites, the champion device achieves a power conversion efficiencie (PCE) of 25.18 % and retains 91.0 % of its initial efficiency after 2000 h under RH=40 %. Our research provides new insights for optimizing the formation process of LD perovskites induced by different materials and their application in high-performance LD/3D PSCs.

Judicious Fluorination of Perovskite Quantum Wells Enables Over 25% Efficiency in Inverted Solar Cells

AbstractThe photovoltaic performance of inverted perovskite solar cells (PSCs) is often hindered by trap‐induced non‐radiative recombination and photochemical degradation occurring at the upper interfaces and the grain boundaries of perovskite films. Herein, ortho‐, meta‐, and para‐isomers of fluorophenylethylammonium iodine (F‐PEAI) organic spacer molecules are evaluated for the construction of perovskite quantum wells (2D or quasi‐2D, PQWs) to encapsulate 3D perovskites. Among the three variants, p‐F‐PEAI leads to the most symmetric charge distribution and the weakest steric hindrance which resulting in reinforced interactions with PbI2 and perovskite, the enhanced out‐of‐plane orientation is confirmed by Grazing incidence wide‐angle X‐ray scattering (GIWAXS) results. Density functional theory and crystal orbital Hamilton population (COHP) calculations further confirm that p‐F‐PEAI engages most strongly with the perovskite structure. Moreover, transmission electron microscopy (TEM) characterization is used to illustrate that p‐F‐PEAI‐assisted 2D PQWs effectively passivate both the grain boundaries and surfaces of perovskites. This configuration facilitates effective surface passivation, improves charge carrier transport, and significantly suppresses non‐radiative recombination. The resultant inverted PSCs achieve an excellent power conversion efficiency (PCE) of 25.03% with a fill factor (FF) of 85.11%. The unencapsulated devices exhibit enhanced long‐term stability under ambient environments and continuous light illumination.

Narrow Bandgap 1D Lead Iodide Perovskite with Aminophenyl Viologen.

One-dimensional (1D) perovskites (perovskitoids) occupy an important place among modern semiconducting materials, offering design flexibility together with a wide range of properties. However, most such materials have a large bandgap, which limits their application in photovoltaics. Here, we present a new 1D hybrid perovskite containing the functional cation aminophenyl viologen (APhV). Similar to other materials from the viologen perovskite family, aminophenyl viologen iodidoplumbate(II) (APhV[Pb2I6]·2NMP) exhibits a broad absorption with a narrow and direct bandgap of 1.66 eV, which was calculated from the experimental data and is supported also by our first-principles simulations. Close contact between electron-rich inorganic chains and electron-accepting viologen molecules suggests charge transfer within the hybrid, which is also visible in the density of states. Considering its reasonable thermal stability, aminophenyl viologen iodidoplumbate can find a wide application in photovoltaics.

Effects of Ligand Chemistry on Ion Transport in 2D Hybrid Organic–Inorganic Perovskites

Abstract2D hybrid organic–inorganic perovskites are potentially promising materials as passivation layers that can enhance the efficiency and stability of perovskite photovoltaics. The ability to suppress ion transport is proposed as a stabilization mechanism, yet an effective characterization of relevant modes of halide diffusion in 2D perovskites is nascent. In light of this knowledge gap, molecular dynamics simulations with enhanced sampling and experimental validation to systematically characterize how ligand chemistry in seven (R‐NH3)2PbI4 systems impacts halide diffusion, particularly in the out‐of‐plane direction is combined. It is found that increasing stiffness and length of ligands generally inhibits ion transport, while increasing ligand polarization generally enhances it. Structural and energetic analyses of the migration pathways provide quantitative explanations for these trends, which reflect aspects of the disorder of the organic layer. Overall, this mechanistic analysis greatly enhances the current understanding of halide migration in 2D hybrid organic–inorganic perovskites and yields insights that can inform the design of future passivation materials.

Enhanced Stability of Spin-Dependent Chiral 2D Perovskite Embedded PV-Biased Anode via Cross-Linking Strategy

Enhanced Stability of Spin-Dependent Chiral 2D Perovskite Embedded PV-Biased Anode via Cross-Linking Strategy

Robust and Efficient Out-of-Plane Exciton Transport in Two-Dimensional Perovskites via Ultrafast Förster Energy Transfer.

Two-dimensional (2D) perovskites, comprising inorganic semiconductor layers separated by organic spacers, hold promise for light harvesting and optoelectronic applications. Exciton transport in these materials is pivotal for device performance, often necessitating deliberate alignment of the inorganic layers with respect to the contacting layers to facilitate exciton transport. While much attention has focused on in-plane exciton transport, little has been paid to out-of-plane interlayer transport, which presumably is sluggish and unfavorable. Herein, by time-resolved photoluminescence, we unveil surprisingly efficient out-of-plane exciton transport in 2D perovskites, with diffusion coefficients (up to ∼0.1 cm2 s-1) and lengths (∼100 nm) merely a few times smaller or comparable to their in-plane counterparts. We unambiguously confirm that the out-of-plane exciton diffusion coefficient corresponds to a subpicosecond interlayer exciton transfer, governed by the Förster resonance energy transfer (FRET) mechanism. Intriguingly, in contrast to temperature-sensitive intralayer band-like transport, the interlayer exciton transport exhibits negligible temperature dependence, implying a lowest-lying bright exciton state in 2D perovskites, irrespective of spacer molecules. The robust and ultrafast interlayer exciton transport alleviates the constraints on crystal orientation that are crucial for the design of 2D perovskite-based light harvesting and optoelectronic devices.

Bottom-up construction of low-dimensional perovskite thick films for high-performance X-ray detection and imaging

Quasi-two-dimensional (Q-2D) perovskite exhibits exceptional photoelectric properties and demonstrates reduced ion migration compared to 3D perovskite, making it a promising material for the fabrication of highly sensitive and stable X-ray detectors. However, achieving high-quality perovskite films with sufficient thickness for efficient X-ray absorption remains challenging. Herein, we present a novel approach to regulate the growth of Q-2D perovskite crystals in a mixed atmosphere comprising methylamine (CH3NH2, MA) and ammonia (NH3), resulting in the successful fabrication of high-quality films with a thickness of hundreds of micrometers. Subsequently, we build a heterojunction X-ray detector by incorporating the perovskite layer with titanium dioxide (TiO2). The precise regulation of perovskite crystal growth and the meticulous design of the device structure synergistically enhance the resistivity and carrier transport properties of the X-ray detector, resulting in an ultrahigh sensitivity (29721.4 μC Gyair−1 cm−2) for low-dimensional perovskite X-ray detectors and a low detection limit of 20.9 nGyair s−1. We have further demonstrated a flat panel X-ray imager (FPXI) showing a high spatial resolution of 3.6 lp mm−1 and outstanding X-ray imaging capability under low X-ray doses. This work presents an effective methodology for achieving high-performance Q-2D perovskite FPXIs that holds great promise for various applications in imaging technology.

A comparative simulation study of light–matter coupling in 1D photonic crystals with 2D perovskite active layer

Light–matter interaction operating in the strong coupling regime offers wide prospects of applications going from nano-photonics to quantum communications. The most practical implementations are to embed the active matter into Fabry–Perot microcavities or photonic crystals. In this work we focus on the strong coupling of two-dimensional (2D) perovskite in 1D grating waveguide. We use rigorous coupled wave analysis to simulate electromagnetic wave confinement in the 1D waveguide. Various sets of waveguide geometrical parameters are examined to achieve the strong coupling regime for three different configurations of the active layer in the waveguide. To extract quantitatively the relevant physical parameters, such as strength of light–matter interaction, we develop a Hamiltonian formalism to reproduce results obtained by simulation. It is shown that the strongest interaction is to have the active layer inserted in the main slab of the waveguide. It is, however, still weaker by about 20% as compared to the use of Fabry–Perot microcavities.

2D Metal Enabled Weak Fermi Level Pinning Effect and Tunable Charge Injection in Contacts with Inorganic 2D Perovskites.

Tow-dimensional (2D) perovskites have invoked extensive interest because of their good stability and intriguing optoelectronic properties. However, in practical applications, the hampered carrier transportation imposed by the vertical array of large dielectric organic cations and the generally seen Fermi level pinning (FLP) effect in conventional metal-2D semiconductors need to be solved urgently. Sb3+/Bi3+-based inorganic lead-free 2D Cs3(M3+)2X9 perovskites (M = Sb3+, Bi3+; X = Cl-, Br-, I-) are promising candidates to replace the toxic 2D hLHP. The contact properties of Cs3Sb2Cl9 with 2D metals are studied in this work to achieve tunable Schottky barrier heights (SBH). Density functional theory calculations reveal a weak FLP factor of 0.91 in the studied junctions, which is beneficial for improving the carrier injection efficiency through electrode design. Calculations of tunneling properties indicate that a Cd3C2 electrode tends to achieve low SBH and high tunneling probability, while a VS2 (H) electrode tends to realize high SBH and low tunneling probability, suggesting that diverse applications of Cs3Sb2Cl9 can be achieved through electrode engineering.

Mitigating Noise Current in 2D Perovskite Single Crystal Photodetectors for Imaging under Black‐Light Condition

Mitigating Noise Current in 2D Perovskite Single Crystal Photodetectors for Imaging under Black‐Light Condition

Building New Structural Distortion Descriptors through Pressure Engineering toward Enhanced Violet Emission in 2D Hybrid Perovskite

AbstractBuilding an explicit structure‐property relationship for two‐dimensional (2D) hybrid perovskites is critical to guide the synthesis of highly luminescent materials. However, traditional studies are limited to the deviation of individual intra‐octahedron, which fails to well reflect collective lattice distortion. Here, a set of new structural distortion descriptors associated with inter‐octahedra is introduced for 2D perovskite (C7H10N)2PbBr4, that is,(PMA)2PbBr4 through pressure engineering. An experimental conclusion is reached that adjacent Pb displacement, as the inter‐octahedron distortion, is an effective parameter in determining the structural distortion and emission behavior of (PMA)2PbBr4 under high pressure. Under high pressure, 2D perovskite (PMA)2PbBr4 exhibits two emission behaviors, free excitons (FEs) emission and self‐trapped excitons (STEs) emission. Different types of four‐Pb‐shaped quadrilateral correspond to different emissions: square‐type (only FEs emission), parallelogram‐type (coexistence of FEs emission and STEs emission), kite‐type (only STEs emission). Moreover, an enhanced violet emission at ≈431 nm is achieved under a mild pressure of 1.0 GPa, which is a crucial light source of medical sterilization. The underlying structure‐property relationship is clarified fundamentally deepens the photophysical mechanism of (PMA)2PbBr4, thus facilitating the design of high‐efficiency perovskite luminophores.

Lead-Free Bismuth-Based Perovskite X-ray Detector with High Sensitivity and Low Detection Limit.

Bismuth-based halide perovskites have shown great potential for direct X-ray detection, attributable to their nontoxicity and advantages in detection sensitivity and spatial resolution. However, the practical application of such materials still faces the critical challenge of combining both high sensitivity and low detection limits. Here, we report a new type of zero-dimensional (0D) perovskite (HIS)BiI5 (1, where HIS2+ = histamine) with high sensitivity and a low detection limit. Structurally, the strong N-H···I hydrogen bonds between HIS2+ cations and inorganic frameworks enhance the rigidity of the structure and diminish the intermolecular distance between adjacent inorganic [Bi2I10]4- dimers. By virtue of such structural merits, single crystal 1 exhibits excellent physical properties perpendicular to both the (001) and (010) faces. Perpendicular to the (010) face, 1 exhibited a high electrical resistivity (2.31 × 1011 Ω cm) and a large carrier mobility-lifetime product (μτ) (2.81 × 10-4 cm2 V-1) under X-ray illumination. Benefiting from these superior physical properties, it demonstrates an excellent X-ray detection capability with a sensitivity of approximately 103 μC Gyair-1 cm-2 and a detection limit of 36 nGyair s-1 in both directions perpendicular to the (001) and (010) crystal faces. These results provide a promising candidate material for the development of new, lead-free, high-performance X-ray detectors.

Lattice Dynamics of Quasi-2D Perovskites from First Principles.

We present the vibrational properties and phonon dispersion for quasi-2D hybrid organic-inorganic perovskites (BA)2CsPb2I7, (HA)2CsPb2I7, (BA)2(MA)Pb2I7, and (HA)2(MA)Pb2I7 calculated from first principles. Given the highly complex nature of these compounds, we first perform careful benchmarking and convergence testing to identify suitable parameters to describe their structural features and vibrational properties. We find that the inclusion of van der Waals corrections on top of generalized gradient approximation (GGA) exchange-correlation functionals provides the best agreement for the equilibrium structure relative to experimental data. We also investigate the impact of the molecular orientation on the equilibrium structure of these layered perovskite systems. Our results suggest ground state ferroelectric alignment of molecular dipoles in the out-of-plane direction is unlikely and support the assignment of the centrosymmetric space group for the low-temperature phase of (HA)2(MA)Pb2I7. Finally, we compute vibrational properties under the harmonic approximation. We find that stringent energy cut-offs are required to obtain well-converged phonon properties, and once converged, the harmonic approximation can capture key physics for such a large, hybrid inorganic-organic system with vastly different atom types, masses, and interatomic interactions. We discuss the obtained phonon modes and dispersion behavior in the context of known properties for bulk 3D perovskites and ligand molecular crystals. While many vibrational properties are inherited from the parent systems, we also observe unique coupled vibrations that cannot be associated with vibrations of the pure constituent perovskite and ligand subphases. Energy dispersion of the low energy phonon branches primarily occurs in the in-plane direction and within the perovskite subphase and arises from bending and breathing modes of the equatorial Pb-I network within the perovskite octahedral plane. The analysis herein provides the foundation for future investigations on this class of materials, such as exciton-phonon coupling, phase transitions, and general temperature-dependent properties.

Nanoscale phase management of the 2D/3D heterostructure toward efficient perovskite solar cells

The stabilization of the formamidinium lead iodide (FAPbI3) structure is pivotal for the development of efficient photovoltaic devices. Employing two-dimensional (2D) layers to passivate the three-dimensional (3D) perovskite is essential for maintaining the α-phase of FAPbI3 and enhancing the power conversion efficiency (PCE) of perovskite solar cells (PSCs). However, the role of bulky ligands in the phase management of 2D perovskites, crucial for the stabilization of FAPbI3, has not yet been elucidated. In this study, we synthesized nanoscale 2D perovskite capping crusts with <n> = 1 and 2 Ruddlesden-Popper (RP) perovskite layers, respectively, which form a type-II 2D/3D heterostructure. This heterostructure stabilizes the α-phase of FAPbI3, and facilitates ultrafast carrier extraction from the 3D perovskite network to transport contact layer. We introduced tri-fluorinated ligands to mitigate defects caused by the halide vacancies and uncoordinated Pb2+ ions, thereby reducing nonradiative carrier recombination and extending carrier lifetime. The films produced were incorporated into PSCs that not only achieved a PCE of 25.39% but also maintained 95% of their initial efficiency after 2000 h of continuous light exposure without encapsulation. These findings underscore the effectiveness of a phase-pure 2D/3D heterostructure-terminated film in inhibiting phase transitions passivating the iodide anion vacancy defects, facilitating the charge carrier extraction, and boosting the performance of optoelectronic devices.

High polarization sensitivity passive spin Photogalvanic devices based on 2D perovskite CsMnBr4/CsSbCl3Br/CsMnBr4 heterojunction

In recent years, Dion-Jacobson (D-J) perovskite has been extensively studied. In order to further study the application of D-J perovskite materials in spin-optoelectronic multifunctional devices, this paper is based on CsSbCl3Br and CsMnBr4, a zero-band gap semi-metallic material with the same ferromagnetic ground state and the same crystal structure. In this paper, put forward with transverse CsMnBr4/CsSbCl3Br/CsMnBr4 heterojunction optoelectronic devices. The characteristics of photocurrent are discussed using parallel configuration (PC) and anti-parallel configuration (APC) magnetoelectric poles under two conditions: vertical incidence of linearly polarized light and elliptically polarized light utilizing density functional theory and the non-equilibrium Green’s function method. The results reveal that the device can achieve complete spin polarization photocurrent, pure spin current, perfect spin filtering effect, and excellent spin valve effect, with high extinction ratios. Under linearly polarized light, the maximum extinction ratio reaches 2747 for the PC configuration and 5200 for the APC configuration. For elliptically polarized light, the extinction ratio is 739 for the PC configuration and reaches a maximum of 240 for the APC configuration. These results indicate that the lateral CsMnBr4/CsSbCl3Br/CsMnBr4 heterojunction has broad multi-functional application prospects in the field of optoelectronics and spintronics.

Filterless Bandpass Photodetectors Enabled by 2D/3D Perovskite Heterojunctions

AbstractBandpass photodetectors have tremendous applications in colorimetric analysis, light communication, imaging and machine vision systems. Compared to broadband photodetectors combined with external optical filters, solution‐processed filterless bandpass photodetectors enjoy high integration density and low cost, but suffer from broadened response edges and insufficient spectral rejection ratios (SRRs). Here, prototype filterless bandpass photodetectors with near square‐shape photoresponse are developed based on (CmH2m+1NH3)2PbI4/MAPbI3 (m = 4–8) and (CmH2m+1NH3)2PbBr4/MAPbBr3 (m = 2–8) perovskite heterojunctions. The strong and sharp excitonic absorption of 2D perovskites defines the ultranarrow response onset widths of 10 ± 1 nm. Besides, the strong photoluminescence (PL) self‐absorption of 2D perovskites suppresses the PL leakage from the front absorber to the back photoactive region, which is crucial to the achieved record high SRR of &gt;2000. By integrating Br‐based 2D/3D perovskite photodetectors with onset edge wavelength discrimination of ≈20 nm, a multiple‐channel optical communication system with low spectral crosstalk is demonstrated.

2D Ruddlesden-Popper Perovskites with Polymer Additive as Stable and Transparent Optoelectronic Materials for Building-Integrated Applications.

We report on the use of 2D Ruddlesden-Popper (RP) perovskites as optoelectronic materials in building-integrated applications, addressing the challenge of balancing transparency, photoluminescence, and stability. With the addition of polyvinylpyrrolidone (PVP), the 2D RP films exhibit superior transparency compared to their 3D counterparts with an average visible transmittance (AVT) greater than 50% and photoluminescence stability under continuous illumination and 85 °C heat for up to 100 h as bare, unencapsulated films. Structural investigations show a stress relaxation in the 3D perovskite films after degradation from thermal aging that is not observed in the 2D RP films, which retain their phase after thermal and light aging. We also demonstrate ultrasmooth, wide-bandgap 2D Dion-Jacobson (DJ) films with PVP incorporation up to 2.95 eV, an AVT above 70%, and roughnesses of ~2 nm. These findings contribute to the development of next-generation solar materials, paving the way for their integration into built structures.

Hole Localization in Bulk and 2D Lead-Halide Perovskites Studied by Time-Resolved Infrared Spectroscopy.

Scattering and localization dynamics of charge carriers in the soft lattice of lead-halide perovskites impact polaron formation and recombination, which are key mechanisms of material function in optoelectronic devices. In this study, we probe the photoinduced lattice and carrier dynamics in perovskite thin films (CsFAPbX3, X = I, Br) using time-resolved infrared spectroscopy. We examine the CN stretching mode of formamidinium (FA) cations located within the lead-halide octahedra of the perovskite structure. Our investigation reveals the formation of an infrared mode due to spatial symmetry breaking within a hundred picoseconds in 3D perovskites. Experiments at cryogenic temperatures show much-reduced carrier localization, in agreement with a localization mechanism that is driven by the dynamic disorder. We extend our analysis to 2D perovskites, where the precise nature of charge carriers is uncertain. Remarkably, the signatures of charge localization we found in bulk perovskites are not observed for 2D Ruddlesden-Popper perovskites ((HexA)2FAPb2I7). This observation implies that the previously reported stabilization of free charge carriers in these materials follows different mechanisms than polaron formation in bulk perovskites. Through the exploration of heterostructures with electron/hole excess, we provide evidence that holes drive the formation of the emerging infrared mode.

Band alignment engineering of 2D/3D halide perovskite lateral heterostructures.

Two-dimensional (2D)/three-dimensional (3D) halide perovskite heterostructures have been extensively studied for their ability to combine the outstanding long-term stability of 2D perovskites with the superb optoelectronic properties of 3D perovskites. While current studies mostly focus on vertically stacked 2D/3D perovskite heterostructures, a theoretical understanding regarding the optoelectronic properties of 2D/3D perovskite lateral heterostructures is still lacking. Herein, we construct a series of 2D/3D perovskite lateral heterostructures to study their optoelectronic properties and interfacial charge transfer using density functional theory (DFT) calculations. We find that the band alignments of 2D/3D heterostructures can be regulated by varying the quantum-well thickness of 2D perovskites. Moreover, decreasing the 2D component ratio in 2D/3D heterostructures can be favorable to form type-I band alignment, whereas a large component ratio of 2D perovskites tends to form type-II band alignment. We can improve the amount of charge transfer at the 2D/3D perovskite interfaces and the light absorption of 2D perovskites by increasing quantum-well thickness. These present findings can provide a clear designing principle for achieving 3D/2D perovskite lateral heterostructures with tunable optoelectronic properties.

Nanometer Control of Ruddlesden-Popper Interlayers by Thermal Evaporation for Efficient Perovskite Photovoltaics.

Solution-processed Ruddlesden-Popper (RP) interlayers in lead halide perovskite solar cells (PSCs) present processing challenges due to fast film formation and uncontrolled growth of phases and layer thickness at interfaces. In this work, an alternative, solvent-free, thermal co-evaporation process is developed to deposit RP interlayers. The method provides precise control on interlayer thickness and enables understanding its role on charge-carrier extraction. Studying RP film growth reveals the development of heterointerfaces when deposited on three-dimensional (3D) perovskite layers. This allows a large thickness window with an optimum between 20 nm and 40 nm to improve the optoelectronic properties of the underlying 3D perovskite. Solar cells using evaporated interlayers achieve power conversion efficiency of 21.6%, compared to 19.6% for untreated devices, driven by improvements in the open-circuit voltage and fill factor. This work sheds light on the importance of phase and thickness control of passivation layers, which ultimately determine the solar cell performance in state-of-the-art PSCs.