Layered Hybrid Perovskites Research Articles

Cationic ligation guides quantum-well formation in layered hybrid perovskites

Cationic ligation guides quantum-well formation in layered hybrid perovskites

Eliminating Voids and Residual PbI2 beneath a Perovskite Film via Buried Interface Modification for Efficient Solar Cells.

The commercialization process of perovskite solar cells (PSCs) is markedly restricted by the power conversion efficiency (PCE) and long-term stability. During fabrication and operation, the bottom interface of the organic-inorganic hybrid perovskite layer frequently exhibits voids and residual PbI2, while these defects inevitably act as recombination centers and degradation sites, affecting the efficiency and stability of the devices. Therefore, the degradation and nonradiative recombination originating from the buried interface should be thoroughly resolved. Here, we report a multifunctional passivator by introducing malonic dihydrazide as an interfacial chemical bridge between the electron transport layer and the perovskite (PVK) layer. MADH with hydrazine groups improves the surface affinity of SnO2 and provides nucleation sites for the growth of PVK, leading to the reduced residual PbI2 and the voids resulting from the inhomogeneous solvent volatilization at the bottom interface. Meanwhile, the hydrazine group and carbonyl group synergistically coordinate with Pb2+ to improve the crystal growth environment, reducing the number of Pb-related defects. Eventually, the PCE of the PSCs is significantly enhanced benefiting from the reduced interfacial defects and the increased carrier transport. Moreover, the reductive nature of hydrazide further inhibits I2 generation during long-term operation, and the device retains 90% of the initial PCE under a 1 sun continuous illumination exposure of 700 h.

Elucidating the Non-Covalent Interactions that Trigger Interdigitation in Lead-Halide Layered Hybrid Perovskites.

Two-dimensional (2D) hybrid organic-inorganic perovskites constitute a versatile class of materials applied to a variety of optoelectronic devices. These materials are composed of alternating layers of inorganic lead halide octahedra and organic ammonium cations. Most perovskite research studies so far have focused on organic sublattices based on phenethylammonium and alkylammonium cations, which are packed by van der Waals cohesive forces. Here, we report a more complex organic sublattice containing benzotriazole-based ammonium cations packed through interdigitated π-π stacking and hydrogen bonding. Single crystals and thin films of four perovskite derivatives are studied in depth with optical spectroscopy and X-ray diffraction, supported by density-functional theory calculations. We quantify the lattice stabilization of interdigitation, dipole-dipole interactions, and inter- as well as intramolecular hydrogen bonding. Furthermore, we investigate the driving force behind interdigitation by defining a steric occupancy factor σ and tuning the composition of the organic and inorganic sublattice. We relate the phenomenon of interdigitation to the available lattice space and to weakened hydrogen bonding to the inorganic octahedra. Finally, we find that the stabilizing interactions in the organic sublattice slightly improve the thermal stability of the perovskite. This work sheds light on the design rules and structure-property relationships of 2D layered hybrid perovskites.

Fabrication of Highly Efficient and Ambient Stable Planar MAPbI3 Perovskite Solar Cells via Defect Passivation through Crosslinking Strategy

Iodine‐based hybrid planar perovskite solar cells’ (PSCs) overall performance is still very limited. In this work, a highly functionalized iodine‐based hybrid perovskite layer is fabricated by incorporating trimethylolpropane ethoxylated triacrylate (TET) within the perovskite precursor, which can crosslink with the grain boundaries to improve the crystallinity as well as the grain size and passivate the defect states of the perovskite material. The MAPbI3‐based thin films with TET exhibited large grain sizes from 195.73 to 587.49 nm with 8 mg mL−1 of TET concentration. The X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), energy dispersive X‐ray (EDX) elemental mapping, photoluminescence (PL), and time resolved photoluminescence (TRPL) characterization results suggest the strong crosslinking effect between TET and MAPbI3, which improves the crystallinity and reduces the charge trap density. Planar PSCs is fabricated with the device architecture fluorine‐doped tin oxide (FTO)/c‐TiO2/MAPbI3:TET/Spiro‐MeOTAD/Au and achieved a power conversion efficiency (PCE) of 14.75% under 1.5 AM light illumination. The fabricated PSCs shows excellent ambient stability which retains 80% of their PCE after being exposed to the ambient environment of relative humidity (RH) ≈60%, room temperature (RT) ≈27 °C without any encapsulation.

Mn-Doped M2CdCl4 (M = CH3NH3+, C2H8N+, and C3H10N+) Layered Hybrid Perovskite and Its Flexible Film Based on Simple Mechanochemical Synthesis.

Layered hybrid perovskites show significant advantages in the field of optoelectronics. However, the low quantum efficiency and complex preparation methods limit their applications. In this work, we developed a series of perovskite powders with a two-dimensional (2D) layered structure of organic-inorganic hybrid metal halides M2CdCl4:x%Mn (M = CH3NH3+, C2H8N+, C3H10N+) via facile mechanochemical methods. The prepared manganese Mn-doped MA2CdCl4 produces orange emission at 605 nm under both 254 and 420 nm excitation, which originates from a dual excitation channel competition mechanism, and its excitation channel could be changed with the increase of Mn2+ ion concentration. Typically, MA2CdCl4:20%Mn powder exhibits high photoluminescence quantum yield (PLQY) close to 90% at 605 nm due to the organic amine ions enlarging the Mn-Mn interlayer distances. In addition, we prepared MA2CdCl4:x%Mn@PVA flexible films, which also exhibit good luminescence at 254 nm excitation and were unexpectedly found to have a better response to Cs+, which could be a candidate for anticounterfeiting applications.

Mixed ionic-electronic conduction in Ruddlesden–Popper and Dion–Jacobson layered hybrid perovskites with aromatic organic spacers

Mixed ionic-electronic conduction in Ruddlesden–Popper and Dion–Jacobson layered hybrid perovskites with aromatic organic spacers

Unraveling the influence of organic cations on tuning electronic structures and spin-splitting in two-dimensional layered organic-inorganic tin-iodine perovskites.

The solar cell and light-emitting device research community is currently focusing on investigating two-dimensional (2D) hybrid perovskite materials owing to their remarkable stability and intriguing optoelectronic characteristics, which hold significant promise for various applications. In general, the introduction of chirality in hybrid perovskites arises from symmetry breaking within their inorganic frameworks. Nevertheless, despite this understanding, the specific factors driving the observed increase in splitting remain obscure due to a lack of comprehensive investigations. Our research delves into the electronic properties of 2D layered hybrid perovskites, considering their behavior with and without spin-orbit coupling. We specifically focus on effect of Rashba splitting and the impact of electronic structure variation across a range of chiral perovskites by introducing chiral organic cations with differing degrees of π-conjugation, resulting in significant changes in spin-splitting magnitude. Systematic first principles investigations confirm that the distortion of the cage and d-spacing of chiral perovskites are crucial design parameters for achieving strong spin-splitting in 2D layered perovskites. Furthermore, our investigation reveals that these systems exhibit remarkable absorption capabilities in the visible light spectrum, as demonstrated by their computed optoelectronic characteristics. The chiral perovskites described in this study, which exhibit substantial spin-splitting, present a distinctive prototype with potential implications for spintronics and photovoltaics.

Resistive switching in benzylammonium-based Ruddlesden-Popper layered hybrid perovskites for non-volatile memory and neuromorphic computing.

Artificial synapses based on resistive switching have emerged as a promising avenue for brain-inspired computing. Hybrid metal halide perovskites have provided the opportunity to simplify resistive switching device architectures due to their mixed electronic-ionic conduction, yet the instabilities under operating conditions compromise their reliability. We demonstrate reliable resistive switching and synaptic behaviour in layered benzylammonium (BzA) based halide perovskites of (BzA)2PbX4 composition (X = Br, I), showing a transformation of the resistive switching from digital to analog with the change of the halide anion. While (BzA)2PbI4 devices demonstrate gradual set and reset processes with reduced power consumption, the (BzA)2PbBr4 system features a more abrupt switching behaviour. Moreover, the iodide-based system displays excellent retention and endurance, whereas bromide-based devices achieve a superior on/off ratio. The underlying mechanism is attributed to the migration of halide ions and the formation of halide vacancy conductive filaments. As a result, the corresponding devices emulate synaptic characteristics, demonstrating the potential for neuromorphic computing. Such resistive switching and synaptic behaviour highlight (BzA)2PbX4 perovskites as promising candidates for non-volatile memory and neuromorphic computing.

Self-powered photodetectors based on Ruddlesden–Popper 2D hybrid perovskites with carbazole derivatives

Recently, carbazole-based organic cations have garnered interest for their potential application in two-dimensional (2D) layered hybrid perovskite solar cells because of their strong hole extraction and transport as well as humidity resistance. However, the potential incorporation of carbazole-based Ruddlesden–Popper 2D hybrid perovskites in photodetectors has been largely unexplored. In this study, we synthesized ammonium 1-(9H-carbazol-9-yl) ethanaminium iodide (CzEAI) and fabricated (CzEA)2PbI4 2D perovskite thin films via varying solvent conditions to control film morphology. We constructed photodiode-type photodetectors with the active layer of (CzEA)2PbI4 2D perovskites and demonstrated a specific detectivity of 6.95 × 1010 Jones at 485 nm illumination without external bias. These results demonstrate the potential of carbazole-based 2D perovskites in a wide range of optoelectronic applications.

Stable and rapid thermochromic reversibility in acene alkylamine intercalated layered hybrid perovskites

Since the discovery of thermochromism in halide perovskites, new perovskite materials with excellent thermochromic properties have been developed. Among them, two-dimensional (2D) layered hybrid perovskites have been extensively explored because of their highly tunable structures and unique thermochromic responses. In this study, the thermochromism in acene alkylamine-spaced 2D perovskite single crystals (PEA)2PbI4 and (NEA)2PbI4 (PEA = 2-phenylethylammonium, NEA = 2-(2-naphthyl)-ethanammonium) is studied. These 2D perovskites undergo a distinct color change between orange and red during heating and cooling cycles, with the corresponding optical bandgap modulation monitored by variable-temperature absorption spectroscopy. The thermochromism in (PEA)2PbI4 and (NEA)2PbI4 is caused by lattice expansion, as confirmed by thermogravimetric–differential scanning calorimetry and variable-temperature powder X-ray diffraction. Compared with the thermochromism caused by structural phase transition, lattice-expansion-modulated thermochromism demonstrates rapid color change and luminescence recovery, and enhanced thermal cycling stability. This study presents a new strategy for developing thermochromic halide perovskites for multifunctional applications.

Large Enhancement of Polarization in a Layered Hybrid Perovskite Ferroelectric Semiconductor via Molecular Engineering.

Switchable spontaneous polarization is the vital property of ferroelectrics, which leads to other key physical properties such as piezoelectricity, pyroelectricity, and nonlinear optical effects, etc. Recently, organic-inorganic hybrid perovskites with 2D layered structure have become an emerging branch of ferroelectric materials. However, most of the 2D hybrid ferroelectrics own relatively low polarizations (<15µC cm-2 ). Here, a strategy to enhance the polarization of these hybrid perovskites by using ortho-, meta-, para-halogen substitution is developed. Based on (benzylammonium)2 PbCl4 (BZACL), the para-chlorine substituted (4-chlorobenzylammonium)2 PbCl4 (4-CBZACL) ferroelectric semiconductor shows a large spontaneous polarization (23.3µCcm-2 ), which is 79% larger than the polarization of BZACL. This large enhancement of polarization is successfully explained via ab initio calculations. The study provides a convenient and efficient strategy to promote the ferroelectric property in the hybrid perovskite family.

Probing intrinsic magnon bandgap in a layered hybrid perovskite antiferromagnet by a superconducting resonator

Probing intrinsic magnon bandgap in a layered hybrid perovskite antiferromagnet by a superconducting resonator

Bulk Photovoltaic Effect in Chiral Layered Hybrid Perovskite Enables Highly Sensitive Near-Infrared Circular Polarization Photodetection

Bulk Photovoltaic Effect in Chiral Layered Hybrid Perovskite Enables Highly Sensitive Near-Infrared Circular Polarization Photodetection

Discovery of enhanced lattice dynamics in a single-layered hybrid perovskite.

Layered hybrid perovskites exhibit emergent physical properties and exceptional functional performances, but the coexistence of lattice order and structural disorder severely hinders our understanding of these materials. One unsolved problem regards how the lattice dynamics are affected by the dimensional engineering of the inorganic frameworks and their interaction with the molecular moieties. Here, we address this question by using a combination of spontaneous Raman scattering, terahertz spectroscopy, and molecular dynamics simulations. This approach reveals the structural dynamics in and out of equilibrium and provides unexpected observables that differentiate single- and double-layered perovskites. While no distinct vibrational coherence is observed in double-layered perovskites, an off-resonant terahertz pulse can drive a long-lived coherent phonon mode in the single-layered system. This difference highlights the dramatic change in the lattice environment as the dimension is reduced, and the findings pave the way for ultrafast structural engineering and high-speed optical modulators based on layered perovskites.

Emissive Dark Excitons in Monoclinic Two-Dimensional Hybrid Lead Iodide Perovskites.

Typically, bright excitons (XB) emit light in two-dimensional (2D) layered hybrid perovskites. There are also dark excitons (XD), for which radiative recombination is spin-forbidden. Application of a magnetic field can somewhat relax the spin-rule, yielding XD emission. Can we obtain XD light emission in the absence of a magnetic field? Indeed, we observe unusually intense XD emission at ∼7 K for (Rac-MBA)2PbI4, (Rac-4-Br-MBA)2PbI4, and (R-4-Br-MBA)2PbI4 (Rac-MBA: racemic methylbenzylammonium), which crystallize in a lower symmetry monoclinic phase. For comparison, orthorhombic (R-MBA)2PbI4 does not exhibit XD emission. XD has a lower energy than XB, with energy difference ΔE. In monoclinic samples, ΔE ∼ 20 meV is large enough to suppress the thermal excitation of XD to XB, at temperatures <30 K. Consequently, XD recombines by emitting light with a long lifetime (∼205 ns). At higher temperatures, the emission switches to the spin-allowed XB (lifetime < 1 ns).

The Impact of Spacer Size on Charge Transfer Excitons in Dion-Jacobson and Ruddlesden-Popper Layered Hybrid Perovskites.

Organic materials can tune the optical properties in layered (2D) hybrid perovskites, although their impact on photophysics is often overlooked. Here, we use transient absorption spectroscopy to probe the Dion-Jacobson (DJ) and Ruddlesden-Popper (RP) 2D perovskite phases. We show the formation of charge transfer excitons in DJ phases, resulting in a photoinduced Stark effect which is shown to be dependent on the spacer size. By using electroabsorption spectroscopy, we quantify the strength of the photoinduced electric field, while temperature-dependent measurements demonstrate new features in the transient spectra of RP phases at low temperatures resulting from the quantum-confined Stark effect. This study reveals the impact of spacer size and perovskite phase configuration on charge transfer excitons in 2D perovskites of interest to their advanced material design.

Lead-Free Double Perovskite Semiconductor with Rigid Spacer-Induced High-Tc Dielectric Switch Features.

Layered hybrid perovskites possess exceptional semiconductor features and structural versality, making them viable candidates for developing multifunctional dielectric phase-transition materials (PTMS). However, most PTMs based on layered hybrid perovskites still suffer from Pb toxicity and low operating temperature. The recently developed hybrid double perovskites provide a new routine to designed PTMs with desired working performance and environment-friendly chemical compositions. Herein, using rigid aromatic cations as templates, we have successfully synthesized a novel double perovskite (benzylammonium)4 AgBiBr8 (1), which consists of corner-sharing AgBr6 and BiBr6 layers and benzylammonium cations. Notably, 1 exhibits a high-temperature first-order reversible solid-state phase transition at 383/387 K (cooling/heating) and switchable dielectric performance around the temperature. Compared with the soft organic chain version of the compound, the phase transition temperature of 1 shows a large enhancement of 99 K, validating the correctness of the designing strategy. In addition, 1 also exhibits semiconductor characteristics with a calculated bandgap of 2.34 eV and an optical bandgap of 2.29 eV. Remarkably, the single crystal photodetector of 1 shows a low dark current (2.12×10-13 A), a high on/off ratio (1.77×103 ), and a fast response (τrise =125 μs and τdecay =419 μs). Such a lead-free phase transition material combined with semiconductor properties provides a new strategy to develop environmentally friendly multifunctional materials.

High-performance photodetectors based on two-dimensional perovskite crystals with alternating interlayer cations

Organic-inorganic halide perovskite, as a low-cost, solution-processable material with remarkable optoelectronic properties, is ideal candidate to fabricate high-performance photodetectors and is expected to significantly reduce device costs. Compared to the common Dion-Jacobson and Ruddlesden-Popper two-dimensional (2D) layered hybrid perovskite compounds, the perovskites with alternating cations in the interlayer (ACI) phase show higher crystal symmetry and narrower optical bandgaps, which exhibit great potential for excellent photodetection performance. Herein, we report a high-performance photodetector based on the 2D bilayered hybrid lead halide perovskite single crystal with the ACI phase (GAMA2Pb2I7; GA = C(NH2)3 and MA = CH3NH3). The single-crystal photodetector exhibits high photoresponsivity of 1.56, 2.54, and 2.60 A/W for incident light wavelengths of 405, 532, and 635 nm under 9.82 nW, respectively, together with the correspondingly high detectivity values of 1.86 × 1012, 3.04 × 1012, and 3.11 × 1012 Jones under the same operating conditions. Meanwhile, a high-resolution imaging sensor is built based on the GAMA2Pb2I7 single-crystal photodetector, confirming the high stability and photosensitivity of the imaging system. These results show that the 2D hybrid lead halide perovskites with alternating interlayer cations are promising for high-performance visible light photodetectors and imaging systems.

Moisture-Induced Ionovoltaic Electricity Generation by Manipulating Organic–Inorganic Hybrid Halide Perovskites

Attempts to satisfy the vast demands for electric power in our daily lives and to address the depletion of existing fossil fuels have led to the development of new energy conversion technologies. Herein, we present a different type of electric generation, called ionovoltaic electricity generation (IEG), that results from manipulating organic–inorganic hybrid halide perovskite structures with moisture. This IEG can generate an open-circuit voltage of up to ∼0.5 V and a short-circuit current density of ∼0.1 mA cm–2, which is sufficient to power small electronic devices. In this work we have utilized the transformation of structurally zero-dimensional perovskite, specifically MA4PbBr6·2H2O, to three-dimensional MAPbBr3 in the presence of humidity. Flexible power supply devices made of organic–inorganic hybrid perovskite layers are designed and fabricated for harvesting the energy from human breath and some other real-life conditions. This work opens a new direction in the field of organic–inorganic hybrid halide perovskites and offers an extremely simple method for energy conversion of practical importance.

Hybrid magnonics in hybrid perovskite antiferromagnets

Hybrid magnonic systems are a newcomer for pursuing coherent information processing owing to their rich quantum engineering functionalities. One prototypical example is hybrid magnonics in antiferromagnets with an easy-plane anisotropy that resembles a quantum-mechanically mixed two-level spin system through the coupling of acoustic and optical magnons. Generally, the coupling between these orthogonal modes is forbidden due to their opposite parity. Here we show that the Dzyaloshinskii–Moriya-Interaction (DMI), a chiral antisymmetric interaction that occurs in magnetic systems with low symmetry, can lift this restriction. We report that layered hybrid perovskite antiferromagnets with an interlayer DMI can lead to a strong intrinsic magnon-magnon coupling strength up to 0.24 GHz, which is four times greater than the dissipation rates of the acoustic/optical modes. Our work shows that the DMI in these hybrid antiferromagnets holds promise for leveraging magnon-magnon coupling by harnessing symmetry breaking in a highly tunable, solution-processable layered magnetic platform.