Ruddlesden-Popper Perovskites Research Articles

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.

Boosting CO2 electrolysis via synergy between active heterogeneous interface and oxygen defects

The commercial viability of solid oxide electrolysis cells (SOECs) for the electrochemical reduction of CO2 to CO is hampered by the sluggish electrocatalytic activity of the electrode materials. In this study, a series of perovskites, Pr0.5Sr0.5Cr0.1Fe0.9-xNixO3-δ (x = 0.1, 0.2, PSCFNx) with different Ni doping levels were synthesized. The results showed that increasing Ni doping led to the creation of more oxygen vacancies. Furthermore, treatment of PSCFNx in a reducing atmosphere resulted in a structural transformation into a composite with a heterogeneous interface between the Ruddlesden-Popper perovskite (RP-PSCFNx) and an exsolved Ni-Fe metal alloy. The re-PSCFN0.2-based cell showed a current density of 2.40 A cm−2 and a Faraday efficiency (FE%) of almost 100 % at 850 °C and 1.6 V, an improvement of 18 % in comparison to the re-PSCFN0.1-based cell. This study provides a strategy to synergistically improve the electrochemical reduction of CO2 activity of SOECs by constructing an active heterogeneous interface and increasing the oxygen vacancy content.

Prediction of the photovoltaic performance of the lead-free layered Ruddlesden–Popper organic–inorganic perovskite (CH3NH3)2GeI4

Using the density functional theory (DFT) and the spectral limited maximum efficiency (SLME) model, we thoroughly evaluate the material MA2GeI4 as a prospective absorber for photovoltaic applications. This material belongs to the family of layered material organic-inorganic Ruddlesden-Popper perovskites, which have attracted interest due to their stability. Our first-principles calculations show that MA2GeI4 has a direct bandgap that is suitable for light absorption at 1.37 eV. To understand the source of its exceptional optical properties, the electronic structure, density of states, and optical properties were examined. Also, we used the SLME model to estimate the MA2GeI4 solar cell efficiency. The latter was found to be about 32.6% power conversion efficiency. The material’s excellent absorption and promising photovoltaic properties contribute to its high efficiency, even when quantum confinement occurs between layers. We found that MA2GeI4 is a potential absorber material for solar applications, demonstrating both good absorption characteristics and advantageous electrical properties. This discovery lays the path for additional experimental investigation of MA2GeI4 based solar cell.

Optical-Electrical Coordinately Modulated Memristor Based on 2D Ferroelectric RP Perovskite for Artificial Vision Applications.

Traditional artificial vision systems built using separate sensing, computing, and storage units have problems with high power consumption and latency caused by frequent data transmission between functional units. An effective approach is to transfer some memory and computing tasks to the sensor, enabling the simultaneous perception-storage-processing of light signals. Here, an optical-electrical coordinately modulated memristor is proposed, which controls the conductivity by means of polarization of the 2D ferroelectric Ruddlesden-Popper perovskite film at room temperature. The residual polarization shows no significant decay after 109-cycle polarization reversals, indicating that the device has high durability. By adjusting the pulse parameters, the device can simulate the bio-synaptic long/short-term plasticity, which enables the control of conductivity with a high linearity of ≈0.997. Based on the device, a two-layer feedforward neural network is built to recognize handwritten digits, and the recognition accuracy is as high as 97.150%. Meanwhile, building optical-electrical reserve pool system can improve 14.550% for face recognition accuracy, further demonstrating its potential for the field of neural morphological visual systems, with high density and low energy loss.

Tuning Electronic and Structural Properties of Lead-Free Metal Halide Perovskites: A Comparative Study of 2D Ruddlesden-Popper and 3D Compositions.

In recent decades, two-dimensional (2D) perovskites have emerged as promising semiconductors for next-generation photovoltaics, showing notable advancements in solar energy conversion. Herein, we explore the impact of alternative inorganic lattice BX-based compositions (B=Ge or Sn, X=Br or I) on the energy gap and stability. Our investigation encompasses BA2Man-1BnX3n+1 2D Ruddlesden-Popper perovskites (for n=1-5 layers) and 3D bulk (MA)BX3 systems, employing first-principles calculations with spin-orbit coupling (SOC), DFT-1/2 quasiparticle, and D3 dispersion corrections. The study unveils how atoms with smaller ionic radii induce anisotropic internal and external distortions within the inorganic and organic lattices. Introducing the spacers in the low-layer regime reduces local distortions but widens band gaps. Our calculation protocol provides deeper insights into the physics and chemistry underlying 2D perovskite materials, paving the way for optimizing environmentally friendly alternatives that can efficiently replace with sustainable materials.

Crystal field anisotropy correlated charge disproportionation in Ruddlesden-Popper Sr3-xCaxFe2O7-δ perovskites

A series of Ca2+-doped Ruddlesden-Popper phase perovskites Sr3-xCaxFe2O7-δ (x = 0∼0.4) were synthesized. Strong asymmetric FeO6 octahedral distortion was confirmed at x = 0.2 owing to the anisotropic chemical pressure applied from preferable occupation of Ca2+ ion at Sr2 site. Unusual high-charged oxidation state of iron ion with enhanced p→d charge transfer was collectively evidenced by X-ray photoelectron spectroscopy and Mössbauer spectroscopy. Combined electron emission spectroscopy further revealed a narrowing of the surface band gap accompanied by an apparent lowering of the conduction band edge at x = 0.2. These observations can be explained by a nontrivial partial charge disproportionated (CD) regime: d5L + d5L → d5L1−n + d5L1+n, which reflects a significant correlation between anisotropic chemical pressure and CD ground state. The d5L1−n ground state, which dominates the conduction band, is largely stabilized by enhancing the d(Fe)-p(O) hybridization along the c-axis. In addition, abrupt changes in both magnetism and dc electrical properties were also observed at x = 0.2. It is believed that the anisotropic crystal field correlated electronic state fluctuation of iron may facilitate magnetic phase competition and carrier transport. This work provides a comprehensive understanding of the crystallographic anisotropy and correlated valence electron behavior in Fe-base Ruddlesden-Popper perovskites, as well as quasi two-dimensional perovskite materials.

Design and simulation of 2D Ruddlesden–Popper perovskite solar cells under LED illumination: Role of ETL and front contact band alignment

This paper focuses on the design and simulation of 2D Ruddlesden-Popper halide perovskite (RPHP) solar cells, emphasizing their optimization for indoor LED illumination conditions. The design process begins with the validation of physical models within the SCAPS device simulator, accomplished through careful calibration against experimental (MAMP)MAn−1PbnI3n+1 RPHP cell data. Subsequently, different values of <n> (with n = 1, 2, 3, and 4) are explored to study the impact of different band gap energies, aiming to identify the most suitable option for optimal efficiency across diverse LED color temperatures. By addressing both material-specific considerations and device architecture optimization, this study aims to establish a comprehensive framework for designing RPHP solar cells tailored for white LED illumination. Additionally, the simulation reveals that optimizing the electron affinity of the Electron Transport Layer (ETL) significantly impacts device performance, with efficiencies exceeding 25 %. Furthermore, the study discusses emerging trends such as ETL-free structures, which aim to address interface defects and enhance device performance. In addition, we analyze the impact of bulk trap density and thickness of the 2-D perovskite absorber on efficiency limitations. With an absorber thickness set at 800 nm, a marginal decrease in PCE is observed, for the ETL-free solar cell, from around 34 % to 32 % as the trap density ranges from 1011 to 1014 cm−3. In contrast, for the ETL-based structure with the same variations, PCE experiences a substantial decline, dropping from approximately 47 % to 37 %. While the ETL-free structure may exhibit a lower PCE compared to the ETL-based cell, its capacity to endure fluctuations in trap density offers a notable advantage.These efforts underscore the potential of 2D RPHP photovoltaic cells for indoor applications, presenting a pathway towards efficient, stable, and cost-effective photovoltaic technology suited for diverse lighting environments.

Recent advances and future perspectives of Ruddlesden–Popper perovskite oxides electrolytes for all‐solid‐state batteries

AbstractAll‐solid‐state batteries equipped with solid‐state electrolytes (SSEs) have gained significant interest due to their enhanced safety, energy density, and longevity in comparison to traditional liquid organic electrolyte‐based batteries. However, many SSEs, such as sulfides and hydrides, are highly sensitive to water, limiting their practical use. As one class of important perovskites, the Ruddlesden–Popper perovskite oxides (RPPOs), show great promise as SSEs due to their exceptional stability, particularly in terms of water resistance. In this review, the crystal structure and synthesis methods of RPPOs SSEs are first introduced in brief. Subsequently, the mechanisms of ion transportation, including oxygen anions and lithium‐ions, and the relevant strategies for enhancing their ionic conductivity are described in detail. Additionally, the progress made in developing flexible RPPOs SSEs, which are critical for flexible and wearable electronic devices, has also been summarized. Furthermore, the key challenges and prospects for exploring and developing RPPOs SSEs in all‐solid‐state batteries are suggested. This review presents in detail the synthesis methods, the ion transportation mechanism, and strategies to enhance the room temperature ionic conductivity of RPPOs SSEs, providing valuable insights on enhancing their ionic conductivity and thus for their practical application in solid‐state batteries.image

Metastructure Engineering with Ruddlesden-Popper 2D Perovskites: Stability, Flexibility, and Quality Factor Trade-Offs.

In this study, we investigate the opto-electro-mechanical properties, thermodynamic stability, and moisture stability of the Ruddlesden-Popper (RP) two-dimensional perovskites of L2PbI4 (L = PEA, FPEA, BA, and BZA) using density functional theory. The goal is to explore their potential application in metastructures. The results show that the stability of FPEA2PbI4 is better than that of PEA2PbI4, BA2PbI4, and BZA2PbI4 due to the replacement of a hydrogen atom with a fluorine atom. On the other hand, BA2PbI4 is more flexible than other materials because it lacks an aromatic ring in its spacer cation, but it is less stable. We introduce a new kind of metastructure composed of an RP perovskite film and conduct an extensive investigation of the quasi-bound states in the continuum (q-BIC) characteristics by near-field analysis and multipole decomposition calculations. The q-BIC resonances in BZA2PBI4 have a greater quality factor due to its larger refractive index in comparison to other materials. Therefore, based on these results, the perovskite materials can be selected for the metastructures from different aspects of stability, flexibility, and refractive index.

Self‐Assembled Molecules Fostering Ordered Spatial Heterogeneity for Efficient Ruddlesden‐Popper Perovskite Solar Cells

Abstract2D Ruddlesden‐Popper perovskites (RPP) with formamidinium‐cesium (FAC) alloyed cations possess powerful thermal‐moisture stability. However, their photovoltaic performance is hindered by the elusive spatial heterogeneity at multiscale lengths, highly associated with their coupled charge selective contacts. Herein, it reports on how the rational formation of self‐assembly molecules (SAMs) govern the orderliness of the spatial heterogeneity and crystal growth model in FACs‐RPP films, which is proposed to dictate the charge‐carrier dynamics. Unlike the disordered RPP film driven by the amorphous polymeric contacts, the laterally ordered crystallized SAM contacts facilitate a spatially ordered 2D/3D heterogeneity of FACs‐RPP film in long range, where distinct minor 2D phases are tightly coupled in short range. Such ordered heterogeneity can improve the energy transfer efficiency, facilitating the charge‐carrier dynamics in a well‐aligned 2D/3D landscape is discovered. Finally, the champion solar cells using selective SAM‐based FACs‐RPP films (n = 5) yield an efficiency of 18.85% (certified 18.19%) and excellent damp‐heat/operational stability, ranking in the top league of reported 2D RPP solar cells. More importantly, this SAM‐based principle can be adapted to diverse 2D structures, active areas, and substrate types. This work provides design directions for leveraging bottom‐selective contacts to tune spatial heterogeneity in state‐of‐the‐art 2D RPP optoelectronics.

Purely ionically bonded cation paving the way to ultralow thermal conductivity and large thermoelectric figure of merit in Ruddlesden–Popper perovskite Cs2SnI2Br2

Lower dimensional materials have gained quite a bit of popularity in the last few decades. Perovskite materials have been studied extensively for their photovoltaic properties. But for large scale application of photovoltaic materials, the thermal properties need to be studied. In this work, using first principles calculations, we have studied the thermal conductivity and thermoelectric performance of quasi two-dimensional (2D) Ruddlesden–Popper phase of perovskite, Cs2SnI2Br2. The Cs atoms are found to be ionically bonded to the halogens leading to low elastic constants and hence give rise to weak bonding. The large anharmonicity in this material causes the lattice thermal conductivity to be ultralow having a value of 0.30 W·m−1·K−1 at 300 K and therefore the thermoelectric figure of merit has been found to be high with a maximum value of 2.08 at 600 K. This lead-free 2D perovskite can be the precursor to a wide variety of similar materials with ultralow thermal conductivity.

Deterministic Fabrication and Quantum-Well Modulation of Phase-Pure 2D Perovskite Heterostructures for Encrypted Light Communication.

Deterministic integration of phase-pure Ruddlesden-Popper (RP) perovskites has great significance for realizing functional optoelectronic devices. However, precise fabrications of artificial perovskite heterostructures with pristine interfaces and rational design over electronic structure configurations remain a challenge. Here, the controllable synthesis of large-area ultrathin single-crystalline RP perovskite nanosheets and the deterministic fabrication of arbitrary 2D vertical perovskite heterostructures are reported. The 2D heterostructures exhibit intriguing dual-peak emission phenomenon and dual-band photoresponse characteristic. Importantly, the interlayer energy transfer behaviors from wide-bandgap component to narrow-bandgap component modulated by comprising quantum wells are thoroughly revealed. Functional nanoscale photodetectors are further constructed based on the 2D heterostructures. Moreover, by combining the modulated dual-band photoresponse characteristic with double-beam irradiation modes, and introducing an encryption algorithm mechanism, a light communication system with high security and reliability is achieved. This work can greatly promote the development of heterogeneous integration technologies of 2D perovskites, and could provide a competitive candidate for advanced integrated optoelectronics.

Controlled Fracture‐Based Micropatterning of Ruddlesden–Popper Halide Perovskite for Ultra High‐Density Arrays of Micro Light Emitting Diodes

AbstractQuasi‐2D Ruddlesden–Popper perovskite (RPP) have surfaced as a promising candidate for light emitting diodes (LEDs) due to its outstanding optoelectronic properties. However, a reliable approach for patterning RPPs remains elusive due to the use of polar solvents in lithographic processes, which can damage the RPP. Here, a reliable and damage‐free dry micropatterning method of RPPs is reported, which also offers a cost/time advantage compared to conventional patterning methods. The sharp edges of high aspect ratio silicon micropillars are used to cut RPPs to a pre‐defined shape and then the cut RPPs are delaminated to obtain a patterned array of RPPs. The resultant patterned array exhibits no sign of degradation or discernable difference between adjacent pixels, achieving a ≈100% yield. The obtained array is utilized to fabricate a pixelated LED where a sharp electroluminescence (EL) spectrum peaking at 410 nm with full‐width‐at‐half‐maximum (FWHM) of 10 nm is observed. The pixelated devices demonstrate the potential to suppress EQE drops as the pixel size decreases, attributed to both the damage‐free micropatterning process and the defect tolerance of RPPs. Moreover, further improvements of the patterning method are demonstrated to avoid parasitic emission and suggest a promising strategy to fabricate pixel‐accessible micro‐LEDs.

Ferroelasticity in Two-Dimensional Hybrid Ruddlesden-Popper Perovskites Mediated by Cross-Plane Intermolecular Coupling and Metastable Funnel-like Phases.

Ferroelasticity is a phenomenon in which a material exhibits two or more equally stable orientation variants and can be switched from one form to another under an applied stress. Recent works have demonstrated that two-dimensional layered organic-inorganic hybrid Ruddlesden-Popper perovskites can serve as ideal platforms for realizing ferroelasticity, however, the ferroelastic (FE) behavior of structures with a single octahedra layer such as (BA)2PbI4 [BA = CH3(CH2)3NH3+] has remained elusive. Herein, by using a combined first-principles and metadynamics approach, the FE behavior of (BA)2PbI4 under mechanical and thermal stresses is uncovered. FE switching is mediated by cross-plane intermolecular coupling, which could occur through multiple rotational modes, rendering the formation of FE domains and several metastable paraelastic (PE) phases. Such metastable phases are akin to wrinkled structures in other layered materials and can act as a "funnel" of hole carriers. Thermal excitation tends to flatten the kinetic barriers of the transition pathways between orientation variants, suggesting an enhanced concentration of metastable PE states at high temperatures, while halogen mixing with Br raises these barriers and conversely lowers the concentration of PE states. These findings reveal the rich structural diversity of (BA)2PbI4 domains, which can play a vital role in enhancing the optoelectronic properties of the perovskite and raise exciting prospects for mechanical switching, shape memory, and information processing.

Orbital-overlap-driven hybridization in 3d-transition metal perovskite oxides LaMO3 (M = Ti-Ni) and La2CuO4

The wide tunability of strongly correlated transition metal (TM) oxides stems from their complex electronic properties and the coupled degrees of freedom. Among the perovskite oxides family, LaMO3 (M = Ti-Ni) allows an M-dependent systematic study of the electronic structure within the same-structure-family motif. While most of the studies have been focusing on the 3d TMs and oxygen sites, the role of the rare-earth site has been far less explored. In this work, we use resonant inelastic X-ray scattering (RIXS) at the lanthanum N4,5 edges and density functional theory (DFT) to investigate the hybridization mechanisms in LaMO3. We link the spatial-overlap-driven hybridization to energetic-overlap-driven hybridization by comparing the RIXS chemical shifts and the DFT band widths. The scope is extended to highly covalent Ruddlesden-Popper perovskite La2CuO4 by intercalating lanthanum atoms to rock-salt layers. Our work evidences an observable contribution of localized lanthanum 5p and 4f orbitals in the band structure.

Vertically Oriented Quasi-2D Perovskite Grown In-Situ by Carbonyl Array-Synergized Crystallization for Direct X-Ray Detectors.

Quasi-2D perovskite quantum wells are increasingly recognized as promising candidates for direct-conversion X-ray detection. However, the fabrication of oriented and uniformly thick quasi-2D perovskite films, crucial for effective high-energy X-ray detection, is hindered by the inherent challenges of preferential crystallization at the gas-liquid interface, resulting in poor film quality. In addressing this limitation, a carbonyl array-synergized crystallization (CSC) strategy is employed for the fabrication of thick films of a quasi-2D Ruddlesden-Popper (RP) phase perovskite, specifically PEA2MA4Pb5I16. The CSC strategy involves incorporating two forms of carbonyls in the perovskite precursor, generating large and dense intermediates. This design reduces the nucleation rate at the gas-liquid interface, enhances the binding energies of Pb2+ at (202) and (111) planes, and passivates ion vacancy defects. Consequently, the construction of high-quality thick films of PEA2MA4Pb5I16 RP perovskite quantum wells is achieved and characterized by vertical orientation and a pure well-width distribution. The corresponding PEA2MA4Pb5I16 RP perovskite X-ray detectors exhibit multi-dimensional advantages in performance compared to previous approaches and commercially available a-Se detectors. This CSC strategy promotes 2D perovskites as a candidate for next-generation large-area flat-panel X-ray detection systems.

A numerical approach to optimize the efficiency of a novel HTL-free Sr3Ti2S7 Ruddlesden-Popper perovskite solar cell

The exceptional environmental and structural stability of two-dimensional Ruddlesden-Popper perovskites has made them appealing candidates for high-performance perovskite solar cells. Besides, Ruddlesden-Popper perovskites can be synthesized using low-cost solution processing and have tunable bandgaps as compared to their conventional three-dimensional counterparts. Therefore, a Ruddlesden–Popper perovskite solar cell has been reported in this investigation and the SCAPS program has been used to theoretically study the device performance of the proposed lead-free, environmentally friendly perovskite solar cell. A novel Sr3Ti2S7 material has been utilized as the light absorber for the first time in such a theoretical study. Two different configurations, employing WS2 and C60 electron transport layers have been presented and device simulations have been performed to optimize the solar cell. The utilization of C60 as an electron transport material did not prove to be beneficial for the solar cell as it suffered from major recombination losses. It was also found that higher doping concentration of the electron transport materials could help these cells achieve improved fill factor. The diffusion length of the electrons and holes with respect to absorber defect density was also determined. Mott-Schottky analysis proved that the ITO/C60/Sr3Ti2S7/Au structure had a lower flatband potential compared to ITO/WS2/Sr3Ti2S7/Au. Additionally, from the impedance spectroscopy results, the recombination lifetime of the ITO/WS2/Sr3Ti2S7/Au configuration was found to be 46.7 μs compared to only 12.9 μs for the ITO/C60/Sr3Ti2S7/Au architecture. It was also established that if the thickness of the absorber and the bulk defect concentration were optimized the ITO/WS2/Sr3Ti2S7/Au and ITO/C60/Sr3Ti2S7/Au solar cells could achieve conversion efficiencies close to 11.0 % and 10.0 % respectively.

Rational Design of Ruddlesden–Popper Perovskite Ferrites as Air Electrode for Highly Active and Durable Reversible Protonic Ceramic Cells

HighlightsA novel A/B-sites co-substitution strategy was introduced to enhance the performance and durability of Ruddlesden–Popper perovskite Sr3Fe2O7−δ (SF)-based air electrodes for reversible protonic ceramic cells (RePCCs).Simultaneous Sr-deficiency and Nb-substitution in SF result in Sr2.8Fe1.8Nb0.2O7−δ (D-SFN), offering improved structural stability under RePCC conditions by suppressing the formation of Sr3Fe2(OH)12 phase.The introduction of Sr-deficiency enhances oxygen vacancy concentration in D-SFN, promoting efficient oxygen transport within the material and contributing to excellent activity in RePCCs.

Enhanced Photostability of the Colloidal Ruddlesden–Popper Perovskite Nanoplate through 4-Fluorobenzylammonium Iodide-Mediated Surface Engineering for Photoluminescent Application

Enhanced Photostability of the Colloidal Ruddlesden–Popper Perovskite Nanoplate through 4-Fluorobenzylammonium Iodide-Mediated Surface Engineering for Photoluminescent Application