Reduced-dimensional Perovskite Research Articles

Reduced-Dimensional Perovskites: Quantum Well Thickness Distribution and Optoelectronic Properties.

Reduced-dimensional perovskites (RDPs), a large category of metal halide perovskites, have attracted considerable attention and shown high potential in the fields of solid-state displays and lighting. RDPs feature a quantum-well-based structure and energy funneling effects. The multiple quantum well (QW) structure endows RDPs with superior energy transfer and high luminescence efficiency. The effect of QW confinement directly depends on the number of inorganic octahedral layers (QW thickness, i.e., n value), so the distribution of n values determines the optoelectronic properties of RDPs. Here, it is focused on the QW thickness distribution of RDPs, detailing its effect on the structural characteristics, carrier recombination dynamics, optoelectronic properties, and applications in light-emitting diodes. The reported distribution control strategies is also summarized and discuss the current challenges and future trends of RDPs. This review aims to provide deep insight into RDPs, with the hope of advancing their further development and applications.

Deciphering the Interplay of Structure and Charge Carrier Dynamics in Reduced-Dimensional Perovskites

Reduced-dimensional perovskites (RDPs) have advanced the development of perovskite solar cells (PSCs) due to their tunable energy landscape, structure, and orientation. Thus, we aim for an increase in the understanding of structure-photophysical properties of Dion-Jacobson (DJ) and Ruddlesden-Popper (RP) RDPs with different dimensionalities. Our findings reveal that RP RDPs with lower dimensionality exhibits a dominant n=2 phase, preferential out-of-plane orientation, and longer charge carrier lifetime compared with DJ RDPs, as evidenced by X-ray scattering technique and transient absorption spectroscopy. In addition, we unveil the film growth of respective RDPs by in-situ X-ray scattering, showing the stoichiometry-determined phase growth. The formation of lower-n phases in RP RDPs with higher dimensionality is thermodynamically favored, while those phases are likely in the form of “intermediate phase”, which bridge the 3d-like and lower-n phases in DJ RDPs. DJ RDPs with higher dimensionality demonstrate comparable phase purity, giving rise to more sufficient energy transfer and longer charge carrier lifetime. As such, DJ-based PSCs (n=4) demonstrate better device stability under ISOS-I-L conditions compared to RP-based PSCs. Leveraging these structural and photophysical insights, our work paves the way for dictating the utilization of RDPs in 3D PSCs and the fabrication of quasi-2D solar cells.

Reduced-dimensional perovskites with dithioketal-containing intercalating cations for near-infrared light-emitting diodes

Reduced-dimensional (RD) metal halide perovskites (MHPs) have received much attention from scientific researchers for their highly tunable optoelectronic properties and solution processability.

Unveiling the degraded electron durability in reduced-dimensional perovskites.

The operational stability of reduced-dimensional metal halide perovskites (RD-MHPs) lags far behind the practical requirements for future high-definition displays. Thereinto, the electron durability of RD-MHPs plays a critical role in stable LEDs during continuous operation, however, it still lacks adequate research and a deep understanding. Herein, the electron durability and deterioration mechanism of phenethylammonium (PEA+)-modified RD-MHPs are systematically conducted through an in situ photoelectron spectroscopy technique by implementing tunable electron-beam radiation to simulate device operation. The formation of detrimental metallic lead (Pb0) caused by the reduction of lead ions (Pb2+) is observed along with the decomposition of PEA+ under electron-beam radiation, thereby changing the photophysical properties of PEA+-doped RD-MHPs. These results provide deep insight into the process of how injected electrons affect the performance of PEA+-doped perovskite LEDs, which may also provide potential guidance for designing robust and effective organic spacers for RD-MHPs.

Tailoring the Quantum Well Structure and Distribution of Reduced-Dimensional Perovskites for Charge Dynamics Optimization

Tailoring the Quantum Well Structure and Distribution of Reduced-Dimensional Perovskites for Charge Dynamics Optimization

Deep-Blue Electroluminescence of Perovskites with Reduced Dimensionality Achieved by Manipulating Adsorption-Energy Differences.

The lagging development of deep-blue perovskite light-emitting diodes (PeLEDs) heavily impedes their practical applications in full-color display due to the absence of spectrally stable emitters and the mismatch of carrier injection capacity. Herein, we report highly efficient deep-blue PeLEDs through a new chemical strategy that addresses the dilemma for simultaneously constant electroluminescence (EL) spectra and high-purify phase in reduced-dimensional perovskites. The success lies in the control of adsorption-energy differences between phenylbutylamine (PBA) and ethylamine (EA) interacting with perovskites, which facilitates narrow n-value distribution. This approach leads to an increased exciton binding energy and enhanced surface potential, hence improving radiative recombination. As a result, an external quantum efficiency of 4.62 % is achieved in PeLEDs with a stable EL peak at 457 nm, demonstrating the best reported result for deep-blue PeLEDs so far.

High-Throughput Evaluation of Emission and Structure in Reduced-Dimensional Perovskites.

High-throughput experimentation (HTE) seeks to accelerate the exploration of materials space by uniting robotics, combinatorial methods, and parallel processing. HTE is particularly relevant to metal halide perovskites (MHPs), a diverse class of optoelectronic materials with a large chemical space. Here we develop an HTE workflow to synthesize and characterize light-emitting MHP single crystals, allowing us to generate the first reported data set of experimentally derived photoluminescence spectra for low-dimensional MHPs. We leverage the accelerated workflow to optimize the synthesis and emission of a new MHP, methoxy-phenethylammonium lead iodide ((4-MeO-PEAI)2-PbI2). We then synthesize 16 000 MHP single crystals and measure their photoluminescence to study the effects of synthesis parameters and compositional engineering on the emission intensity of 54 distinct MHPs: we achieve an acceleration factor of more than 100 times over previously reported HTE MHP synthesis and characterization methods. Using insights derived from this analysis, we screen an existing database for new, potentially emissive MHPs. On the basis of the Tanimoto similarity of the bright available emitters, we present our top candidates for future exploration. As a proof of concept, we use one of these (3,4-difluorophenylmethanamine) to synthesize an MHP which we find has a photoluminescence quantum yield of 10%.

Effect of post-annealing on thermally evaporated reduced-dimensional perovskite LEDs

Reduced-dimensional perovskites (RDPs) with self-assembled multi-quantum well structures have emerged as promising candidates for light-emitting diodes (LEDs) due to their high color purity, high photoluminescence quantum yield, and decent stability. Compared to the traditional RDP film preparation methods reported in the previous literature, thermal evaporation is an appealing option for RDP film fabrication with uniform crystallization, high repeatability, and precise control. Here, based on the vacuum deposition method, we adopted a combined strategy, including annealing treatment and device structure optimization. Meanwhile, we investigated the effects of post-annealing on charge carrier recombination kinetics, exciton energy transfer, and phase distribution of vacuum-deposited RDP films. As a result, we achieved an external quantum efficiency of 6.5% for the device, which is one of the best performances among prevailing research on vacuum-processed RDP-based LEDs.

Monodispersed perovskite quantum wells for efficient LEDs

The ability to fabricate monodisperse reduced-dimensional perovskite (RDP) films would enable researchers to further understand and apply RDP films in various optoelectronic applications. <i>Nature</i> recently published a study by Ma et al. where monodisperse RDP was fabricated using a bifunctional molecular additive. The monodisperse-RDP-based LED achieved an external quantum efficiency of 25.6% with an exceptional half-life at an initial luminance of 7,200 cd m⁻².

Surface Defect Formation and Passivation in Formamidinium Lead Triiodide (FAPbI3) Perovskite Solar Cell Absorbers

Formamidinium lead iodide based hybrid perovskite materials with improved efficiency and stability still lack well-understood surface defect formation mechanisms. Controlling the surface termination and defects has the potential to improve the performance of both conventional 3D and latterly reduced-dimensional perovskites photovoltaics. Here, we characterized the termination and all possible defect formations in FAPbI3 surface by the first-principles calculations. We found that, among the surfaces we considered, FAI-termination exhibits the most stable surface with a high defect tolerance. The PbI2-terminated surface is also found to be relatively stable; however, certain defects, such as electron-donating FA-interstitial and Pb-interstitial defects, can create deep-level stable charge-traps, potentially limiting the optoelectronic performance. We further investigate the surface treatment on these deep defects by model small molecule additives. We found that benzene additive with delocalized electron distribution can effectively passivate the deep FA-interstitial and Pb-interstitial defects by electron donating to the surface defect through charge-transfer.

Distribution control enables efficient reduced-dimensional perovskite LEDs.

Light-emitting diodes (LEDs) based on perovskite quantum dots have shown external quantum efficiencies (EQEs) of over 23% and narrowband emission, but suffer from limited operating stability1. Reduced-dimensional perovskites (RDPs) consisting of quantum wells (QWs) separated by organic intercalating cations show high exciton binding energies and have the potential to increase the stability and the photoluminescence quantum yield2,3. However, until now, RDP-based LEDs have exhibited lower EQEs and inferior colour purities4-6. We posit that the presence of variably confined QWs may contribute to non-radiative recombination losses and broadened emission. Here we report bright RDPs with a more monodispersed QW thickness distribution, achieved through the use of a bifunctional molecular additive that simultaneously controls the RDP polydispersity while passivating the perovskite QW surfaces. We synthesize a fluorinated triphenylphosphine oxide additive that hydrogen bonds with the organic cations, controlling their diffusion during RDP film deposition and suppressing the formation of low-thickness QWs. The phosphine oxide moiety passivates the perovskite grain boundaries via coordination bonding with unsaturated sites, which suppresses defect formation. This results in compact, smooth and uniform RDP thin films with narrowband emission and high photoluminescence quantum yield. This enables LEDs with an EQE of 25.6% with an average of 22.1 ±1.2% over 40 devices, and an operating half-life of two hours at an initial luminance of 7,200 candela per metre squared, indicating tenfold-enhanced operating stability relative to the best-known perovskite LEDs with an EQE exceeding 20%1,4-6.

Abnormal Phase Transition and Band Renormalization of Guanidinium-Based Organic-Inorganic Hybrid Perovskite.

Low-dimensional organic-inorganic hybrid perovskites have attracted much interest owing to their superior solar conversion performance, environmental stability, and excitonic properties compared to their three-dimensional (3D) counterparts. Among reduced-dimensional perovskites, guanidinium-based perovskites crystallize in layered one-dimensional (1D) and two-dimensional (2D). Here, our studies demonstrate how the dimensionality of the hybrid perovskite influences the chemical and physical properties under different pressures (i.e., bond distance, angle, vdW distance). Comprehensive studies show that 1D GuaPbI3 does not undergo a phase transition even up to high pressures (∼13 GPa) and its band gap monotonically reduces with pressure. In contrast, 2D Gua2PbI4 exhibits an early phase transition at 5.5 GPa and its band gap follow nonmonotonic pressure response associated with phase transition as well as other bond angle changes. Computational simulations reveal that the phase transition is related to the structural deformation and rotation of PbI6 octahedra in 2D Gua2PbI4 owing to a larger degree of freedom of deformation. The soft lattice allows them to uptake large pressures, which renders structural phase transitions possible. Overall the results offer the first insights into how layered perovskites with different dimensionality respond to structural changes driven by pressure.

Thiophene Cation Intercalation to Improve Band-Edge Integrity in Reduced-Dimensional Perovskites.

The insertion of large organic cations in metal halide perovskites with reduced-dimensional (RD) crystal structures increases crystal formation energy and regulates the growth orientation of the inorganic domains. However, the power conversion performance is curtailed by the insulating nature of the bulky cations. Now a series of RD perovskites with 2-thiophenmethylammonium (TMA) as the intercalating cation are investigated. Compared with traditional ligands, TMA demonstrates improved electron transfer in the inorganic framework. TMA modifies the near-band-edge integrity of the RD perovskite, improving hole transport. A power conversion efficiency of 19 % is achieved, the highest to date for TMA-based RD perovskite photovoltaics; these TMA devices provide a 12 % relative increase in PCE compared to control RD perovskite devices that use PEA as the intercalating ligand, a result of the improved charge transfer from the inorganic layer to the organic ligands.

Thiophene Cation Intercalation to Improve Band‐Edge Integrity in Reduced‐Dimensional Perovskites

AbstractThe insertion of large organic cations in metal halide perovskites with reduced‐dimensional (RD) crystal structures increases crystal formation energy and regulates the growth orientation of the inorganic domains. However, the power conversion performance is curtailed by the insulating nature of the bulky cations. Now a series of RD perovskites with 2‐thiophenmethylammonium (TMA) as the intercalating cation are investigated. Compared with traditional ligands, TMA demonstrates improved electron transfer in the inorganic framework. TMA modifies the near‐band‐edge integrity of the RD perovskite, improving hole transport. A power conversion efficiency of 19 % is achieved, the highest to date for TMA‐based RD perovskite photovoltaics; these TMA devices provide a 12 % relative increase in PCE compared to control RD perovskite devices that use PEA as the intercalating ligand, a result of the improved charge transfer from the inorganic layer to the organic ligands.

Reduced-dimensional perovskite photovoltaics with homogeneous energy landscape

Reduced-dimensional (quasi-2D) perovskite materials are widely applied for perovskite photovoltaics due to their remarkable environmental stability. However, their device performance still lags far behind traditional three dimensional perovskites, particularly high open circuit voltage (Voc) loss. Here, inhomogeneous energy landscape is pointed out to be the sole reason, which introduces extra energy loss, creates band tail states and inhibits minority carrier transport. We thus propose to form homogeneous energy landscape to overcome the problem. A synergistic approach is conceived, by taking advantage of material structure and crystallization kinetic engineering. Accordingly, with the help of density functional theory guided material design, (aminomethyl) piperidinium quasi-2D perovskites are selected. The lowest energy distribution and homogeneous energy landscape are achieved through carefully regulating their crystallization kinetics. We conclude that homogeneous energy landscape significantly reduces the Shockley-Read-Hall recombination and suppresses the quasi-Fermi level splitting, which is crucial to achieve high Voc.

Chloride Insertion-Immobilization Enables Bright, Narrowband, and Stable Blue-Emitting Perovskite Diodes.

Metal halide perovskites show promise for light-emitting diodes (LEDs) owing to their facile manufacture and excellent optoelectronic performance, including high color purity and spectral stability, especially in the green region. However, for blue perovskite LEDs, the emission spectrum line width is broadened to over 25 nm by the coexistence of multiple reduced-dimensional perovskite domains, and the spectral stability is poor, with an undesirable shift (over 7 nm) toward longer wavelengths under operating conditions, degradation that occurs due to phase separation when mixed halides are employed. Here we demonstrate chloride insertion-immobilization, a strategy that enables blue perovskite LEDs, the first to exhibit narrowband (line width of 18 nm) and spectrally stable (no wavelength shift) performance. We prepare bromide-based perovskites and then employ organic chlorides for dynamic treatment, inserting and in situ immobilizing chlorides to blue-shift and stabilize the emission. We achieve sky-blue LEDs with a record luminance over 5100 cd/m2 at 489 nm, and an operating half-life of 51 min at 1500 cd/m2. By device structure optimization, we further realize an improved EQE of 5.2% at 479 nm and an operating half-life of 90 min at 100 cd/m2.

Edge stabilization in reduced-dimensional perovskites

Reduced-dimensional perovskites are attractive light-emitting materials due to their efficient luminescence, color purity, tunable bandgap, and structural diversity. A major limitation in perovskite light-emitting diodes is their limited operational stability. Here we demonstrate that rapid photodegradation arises from edge-initiated photooxidation, wherein oxidative attack is powered by photogenerated and electrically-injected carriers that diffuse to the nanoplatelet edges and produce superoxide. We report an edge-stabilization strategy wherein phosphine oxides passivate unsaturated lead sites during perovskite crystallization. With this approach, we synthesize reduced-dimensional perovskites that exhibit 97 ± 3% photoluminescence quantum yields and stabilities that exceed 300 h upon continuous illumination in an air ambient. We achieve green-emitting devices with a peak external quantum efficiency (EQE) of 14% at 1000 cd m−2; their maximum luminance is 4.5 × 104 cd m−2 (corresponding to an EQE of 5%); and, at 4000 cd m−2, they achieve an operational half-lifetime of 3.5 h.

Ligand-Induced Surface Charge Density Modulation Generates Local Type-II Band Alignment in Reduced-Dimensional Perovskites.

Two-dimensional (2D) and quasi-2D perovskite materials have enabled advances in device performance and stability relevant to a number of optoelectronic applications. However, the alignment among the bands of these variably quantum confined materials remains a controversial topic: there exist multiple experimental reports supporting type-I, and also others supporting type-II, band alignment among the reduced-dimensional grains. Here we report a combined computational and experimental study showing that variable ligand concentration on grain surfaces modulates the surface charge density among neighboring quantum wells. Density functional theory calculations and ultraviolet photoelectron spectroscopy reveal that the effective work function of a given quantum well can be varied by modulating the density of ligands at the interface. These induce type-II interfaces in otherwise type-I aligned materials. By treating 2D perovskite films, we find that the effective work function can indeed be shifted down by up to 1 eV. We corroborate the model via a suite of pump-probe transient absorption experiments: these manifest charge transfer consistent with a modulation in band alignment of at least 200 meV among neighboring grains. The findings shed light on perovskite 2D band alignment and explain contrasting behavior of quasi-2D materials in light-emitting diodes (LEDs) and photovoltaics (PV) in the literature, where materials can exhibit either type-I or type-II interfaces depending on the ligand concentration at neighboring surfaces.

Suppressed Ion Migration in Reduced-Dimensional Perovskites Improves Operating Stability

Impressive progress in halide perovskite solar cells motivates further work to improve operating stability. It is known that ion-migration-driven decomposition represents a degradation pathway in p...

Anchored Ligands Facilitate Efficient B-Site Doping in Metal Halide Perovskites.

Metal halide perovskites exhibit outstanding optoelectronic properties: superior charge carrier mobilities, low densities of deep trap states, high photoluminescence quantum yield, and wide color tunability. The introduction of dopant ions provides pathways to manipulate the electronic and chemical features of perovskites. In metal halide perovskites ABX3, where A is a monovalent cation (e.g., methylammonium (MA+), Cs+), B is the divalent metal ion(s) (e.g., Pb2+, Sn2+), and X is the halide group (e.g., Cl-, Br-, or I-), the isovalent exchange of A- and X-site ions has been widely accomplished; in contrast, strategies to exchange B-site cations are underexamined. The activation energies for vacancy-mediated diffusion of B-site cations are much higher than those for A- and X-sites, leading to slow doping processes and low doping ratios. Herein we demonstrate a new method that exchanges B-site cations in perovskites. We design a series of metal carboxylate solutions that anchor on the perovskite surface, allowing fast and efficient doping of B-sites with both homovalent and heterovalent cations (e.g., Sn2+, Zn2+, Bi3+) at room temperature. The doping process in the reduced-dimensional perovskites is complete within 1 min, whereas a similar reaction only leads to the surface attachment of dopant ions in three-dimensional structures. We offer a model based on ammonium extraction and surface ion-pair substitution.