quasi-2D Perovskite Research Articles

Performance-optimized and phase purity-improved high-n quasi-two-dimensional perovskite for green light-emitting diodes

Quasi-two-dimensional (quasi-2D) perovskite has the advantage of enlarging exciton binding energy and is more suitable for efficient perovskite light-emitting diodes (PeLEDs). However, the quasi-2D perovskite films deposited with solution methods are usually mixtures of multiple phases with different inorganic layer numbers (n), unfavorable to obtaining high emission efficiency. In this study, we selected formamidinium lead bromide (FAPbBr3) as the light emitter and (2-phenylethyl)ammonium cation (PEA+) as the long-chain organic spacer cation to prepare high-n (n = 9) quasi-2D perovskite films with improved phase purity. Based on the multiple cations mixed engineering, the quality of these films improved obviously by partly replacing FA+ with minute quantities of cesium cation (Cs+). The improvement focused on remarkably enhanced photoluminescence, few low-n phases, and decreased grain sizes. The green PeLED based on the performance-optimized and phase purity-improved high-n quasi-2D perovskite reached a high brightness of 28 960 cd/m2 together with a maximum current efficiency of 44.8 cd/A and a maximum external quantum efficiency of 9.99%.

Boosting Carrier Transport in Quasi-2D/3D Perovskite Heterojunction for High-Performance Perovskite/Organic Tandems.

Wide-bandgap (WBG) perovskites are continuously in the limelight owing to their applicability in tandem solar cells. The main bottlenecks of WBG perovskites are interfacial non-radiative recombination and carrier transport loss caused by interfacial defects and large energy-level offsets, which induce additional energy losses when WBG perovskites are stacked with organic solar cells in series because of unbalanced carrier recombination in interconnecting layer (ICL). To solve these issues, 1,3-propanediammonium iodide (PDADI) is incorporated to form Dion-Jacobson -phase quasi-2D perovskites with mixed high-n-values in WBG perovskites. PDADI simultaneously repairs the shallow/deep defects and establishes a Type-II energy-level alignment between quasi-2D/3D and 3D perovskites for rapid carrier extraction. More importantly, the short-chain diammonium cation in quasi-2D perovskite with high n-values results in a short Pb-I inorganic layer spacing, which enhances the interlayer electronic coupling and weakens the quantum-well confinement effect that restricts carrier transport. The suppressed transport loss increases the electron concentration in the ICL for balanced carrier recombination. The 0.0628 and 1.004 cm2 perovskite/organic tandems achieve remarkable efficiencies of 25.92% and 24.63%, respectively. The quasi-2D capping layer can inhibit ion migration, allowing perovskite/organic tandems to show excellent operational stability (T85 >1000h).

Low-dimensional phase optimization and defect passivation of quasi-2D perovskite to enhance electroluminescence by introducing b-NA

The energy funnel effect holds significant potential for enhancing light-emitting diode (LED) performance in the Quasi-two-dimensional (Quasi-2D) perovskite, which feature a unique multi-quantum well structure. However, random phase distribution and defects within Quasi-2D films pose challenges, leading to inefficient energy transfer and nonradiative recombination, thereby limiting device performance. Here, sodium 2-naphthalene sulfonate (b-NA) is introduced into the Quasi-2D perovskite film to enhance its the optical and electrical properties. The strong interaction between the S = O group and Na+ in b-NA with the perovskite matrix leads to reduced grain size, facilitating agglomeration and densification. This modification decreases the proportion of the low-n phase, enhances thermal stability, and passivates surface defects. Therefore, compared to the control device, the maximum brightness and external quantum efficiency of Quasi-2D perovskite LEDs with the optimal concentration (8b-NA) more than double, and the operational lifetime (T50) of the unpackaged device extends from 70.1 min to 168.5 min.

Multi-layered quasi-2D perovskite based triboelectric nanogenerator

Inorganic-organic perovskites are considered as one of the emerging candidates as a tribopositive material in triboelectric nanogenerators (TENG) owing to their unique functionalities. Among them, quasi-two-dimensional (quasi-2D) perovskites are promising materials for TENG due to layered nature, excellent environmental and chemical stability, tunability, and excellent electrical properties. Herein, we investigate the performance of TENG based on multiple series of perovskite layers using simple solution processing technique. The dimensionality of the perovskite layers is attained by changing the stoichiometric ratios of phenylethylammonium iodide (PEAI), lead iodide (PbI2), methylammonium iodide (MAI). The quasi-2D based TENG generates the maximum output electrical performance with a voltage of 306V, current of 4.71µA, and maximum power density of 3.48µW/cm2 at the optimum value of (<n> = 5) due to the higher concentration of C–N and N–H groups. Moreover, the fabricated device shows stable performance for 12000 cycles. The TENG device is further utilized to charge the various commercially available capacitors, for lightning of light-emitting diodes (LEDs), and to power up low-power electronic devices. These results demonstrate the effect of the dimensionality of perovskites on the output performance of the TENG for use in next-generation energy harnessing.

Grain size control in quasi-two-dimensional perovskite thin film via intermediate phase engineering for efficient bound exciton generation

AbstractQuasi-two dimensional (2D) perovskites have emerged as a promising class of materials due to their remarkable photoluminescence efficiency, which stems from their exceptionally high exciton binding energies. The spatial confinement of excitons within smaller grain sizes could enhance the formation of biexcitons leading to higher radiative recombination efficiency. However, the synthesis of high-quality quasi-2D perovskite thin films with controllable grain sizes remains a challenging task. In this study, we present a facile method for achieving quasi-2D perovskite thin films with controllable grain sizes ranging from 500 to 900 nm. This is accomplished by intermediate phase engineering during the film fabrication process. Our results demonstrate that quasi-2D perovskite films with smaller grain sizes exhibit more efficient bound exciton generation and a reduced stimulated emission threshold down to 15.89 µJ cm−2. Furthermore, femtosecond transient absorption measurements reveal that the decay time of bound excitons is shorter in quasi-2D perovskites with smaller grain sizes compared to that of those with larger grains at the same pump density, which is 230.5 ps. This observation suggests a more efficient exciton recombination process in the smaller grain size regime. Our findings would offer a promising approach for the development of efficient bound exciton lasers.

Tailored Polymer Hole-Transporting Materials with Multisite Passivation Functions for Effective Buried-Interface Engineering of Inverted Quasi-2D Perovskite Solar Cells.

Although quasi-2D Ruddlesden‒Popper (RP) perovskite exhibits advantages in stability, their photovoltaic performance are still inferior to 3D counterparts. Optimizing the buried interface of RP perovskite and suppress energetic losses can be a promising approach for enhancing efficiency and stability of inverted quasi-2D RP perovskite solar cells (PSCs). Among which, constructing polymer hole-transporting materials (HTMs) with defect passivation functions is of great significance for buried-interface engineering of inverted quasi-2D RP PSCs. Herein, by employing side-chain tailoring strategy to extend the π-conjugation and regulate functionality of side-chain groups, target polymer HTMs (PVCz-ThSMeTPA and PVCz-ThOMeTPA) with high mobility and multisite passivation functions are achieved. The presence of more sulfur atom-containing groups in side-chain endows PVCz-ThSMeTPA with increased intra/intermolecular interaction, appropriate energy level, and enhanced buried interfacial interactions with quasi-2D RP perovskite. The hole mobility of PVCz-ThSMeTPA is up to 9.20×10-4 cm2 V-1 S-1. Furthermore, PVCz-ThSMeTPA as multifunctional polymer HTM with multiple chemical anchor sites for buried-interface engineering of quasi-2D PSCs can enable effective charge extraction, defects passivation, and perovskite crystallization modulation. Eventually, the PVCz-ThSMeTPA-based inverted quasi-2D PSC achieves a champion power conversion efficiency of 22.37%, which represents one of the highest power conversion efficiencies reported to date for quasi-2D RP PSCs.

Bilateral Embedded Anchoring via Tailored Polymer Brush for Large-Area Air-Processed Blue Light-Emitting Diodes.

Perovskite light-emitting diodes (PeLEDs) that can be air-processed promises the development of displaying optoelectronic device, while is challenged by technical difficulty on both the active layer and hole transport layer (HTL) caused by the unavoidable humidity interference. Here, we propose and validate that, planting the polymer brush with tailored functional groups in inorganic HTL, provides unique bilateral embedded anchoring that is capable of simultaneously addressing the n phases crystallization rates in the active layer as well as the deteriorated particulate surface defects in HTL. Exemplified by zwitterionic polyethyleneimine-sulfonate (PEIS) in present study, its implanting in NiOx HTL offers abundant nuclei sites of amino and sulfonate groups that balance the growth rate of different n phases in quasi-2D perovskite films. Moreover, the PEIS effectively nailed the interfacial contact between perovskite and NiOx, and reduced the particulate surface defects in HTL, leading to the enhanced PLQY and stability of large-area blue perovskite film in ambient air. By virtue of these merits, present work achieves the first demonstration of the air-processed blue PeLEDs in large emitting area of 1.0 cm2 with peak external quantum efficiency (EQE) of 2.09 %, which is comparable to the similar pure-bromide blue PeLEDs fabricated in glovebox.

Achieving vertical orientation films with superior environmental stability in quasi-2D lead iodide perovskites

The incorporation of a spacer cation to improve the stability of lead halide perovskites entails a trade-off, notably compromising film quality and device performance, particularly in quais-2D variants employing a higher proportion of hydrophobic, larger spacer cations. Addressing this challenge in quasi-2D perovskite-based devices requires enhancement in film morphology, crystallinity, and vertical orientation to optimize charge transport. Herein, we present a simple one step spin coating synthesis approach for producing PEA2MAn-1PbnI3n+1 (n = 5–2) thin films from a single precursor solution. Notably, our method operates at room temperature without the need of usually toxic anti-solvent or specialized additives, resulting in high quality crystalline films that are vertically oriented and smooth. We systematically investigate the impact of annealing processes on crystal structure, including gradient annealing (GA) as well as thermal annealing at 100℃ for durations of 10 and 15 minutes. Our findings indicate that the films with n = 4 exhibits superior crystallinity and vertical crystallographic orientation, alongside reduced roughness, and minimal contamination of the lower n mixtures. Gradient annealing notably enhances the crystallinity of n = 3 films. While the surface of all the films appears smooth with flake-like structure, the n = 2 sample notably exhibits pitting.

Coherence Programming for Efficient Linearly Polarized Perovskite Light-Emitting Diodes.

Although quasi-two-dimensional (quasi-2D) perovskites are ideal material platforms for highly efficient linearly polarized electroluminescence owing to their anisotropic crystal structures, so far, there has been no practical implementation of these materials for the demonstration of linearly polarized perovskite light-emitting diodes (LP-PeLEDs). This scarcity is due to difficulty in orientation and phase distribution control of the quasi-2D perovskites while minimizing the defects, all of which are required to manifest aligned transition dipole moments (TDMs). To achieve this multifaceted goal, herein, we introduce a synergistic strategy to quasi-2D perovskites by incorporating both a trimethylolpropane triacrylate anchoring layer and 18-Crown-6 molecular passivator into the film fabrication process. It is found that the interfacial anchoring layer guides the oriented growth of perovskites along the (110) plane, whereas the molecular passivator reduces the number of defects and homogenizes the crystal phase. As a result, a quasi-2D perovskite film with macroscopically aligned TDM that renders high radiative recombination and the degree of linear polarization (DoLP) is constructed. This "coherence-programmed emission layer" demonstrates highly efficient LP-PeLEDs, not only achieving a maximum external quantum efficiency of ∼23.7%, a brightness of ∼36,142 cd/m2, and a DoLP of ∼38%, but also significantly improving the signal-to-interference-and-noise ratio in a multi-cell visible light communication system.

Phase Distribution Dictates Charge Transfer and Transport Dynamics in Layered Quasi-2D Perovskite.

Strategic manipulation of spatiotemporal evolution of charge carriers is critical for optimizing performance of quasi-two-dimensional (2D) perovskite-based optoelectronic devices. Nonetheless, the inhomogeneous phase distribution and band alignment engender intricate energy landscapes, complicating internal charge and energy funneling processes. Herein, we integrate high spatiotemporal resolution transient absorption microscopy with multiple time-resolved spectroscopy and find that asynchronous electron and hole transfers rather than direct energy transfer govern the funneling mechanisms. Notably, the charge funneling pathways and transport behaviors can be modifiable by phase manipulation. The accumulation of small-n phases suppresses the electron funneling toward large-n phases and doubles the carrier diffusion rate from 0.085 to 0.20 cm2/s, yielding a 1.5-fold enhancement in diffusion length. Phase order engineering is further corroborated for facilitating charge separation. Our investigation underscores the prospects of manipulating the phase distribution to control internal charge funneling and transport, thereby substantiating the theoretical foundations for optimizing optoelectronic devices.

Defect passivation with spectral shift for improved efficiency and stability of quasi-2D blue perovskite light emitting diodes

Metal halide perovskites are emerging as promising materials for next-generation light-emitting diodes (LEDs), owing to their cost-effectiveness, facile manufacturing, and excellent optoelectronic properties including a narrow emission-line full width at half maximum, high photoluminescence quantum yield, and spectral stability. However, blue-emission perovskite LEDs (PeLEDs) exhibit perovskite phase segregation and halogen ion migration during operation, attributed to crystal defects, halogen vacancies, and phase instability of mixed-halide perovskites. These defects compromise the spectral stability of blue-emitting PeLEDs, resulting in an undesirable color shift toward longer wavelengths. In this study, we introduce a dynamic treatment with phenylphosphonic dichloride (PPOCl2) to address these challenges and achieve blue-emitting PeLEDs. The chloride in PPOCl2 penetrates the quasi-2D sky-blue perovskite, reducing halide defects. Meanwhile, the phosphonic group forms covalent bonds with undercoordinated Pb on the perovskites, effectively passivating defects. PPOCl2-treated perovskite exhibits a spectral blue shift toward a deep-blue wavelength (≤467 nm), enhancing electroluminescence performance. The quasi-2D PPOCl2-treated PeLEDs achieve a maximum external quantum efficiency of 2.31 % with an emission peak at 488 nm. Dynamic treatment with PPOCl2 shows the potential to improve the performance and stability of blue emission perovskite-based LEDs, providing a spectral shift mechanism to achieve deep-blue emission in PeLEDs.

The Deepest Blue: Major Advances and Challenges in Deep Blue Emitting Quasi-2D and Nanocrystalline Perovskite LEDs.

In this review, the recent development of blue perovskite light-emitting diodes (PeLED) are summarized. On deep-blue (≤465nm) perovskite nanomaterials of different structural forms are mainly focused, including nanocrystals (NCs), quantum dots (QDs), nanoplatelets (NPLs), quasi-2D thin film, 3D bulk thin film, as well as lead-free perovskite nanomaterials. The current challenges are also examined in producing efficient deep-blue PeLED, such as material and spectral instability, imbalance charge transport, Joule heat impact, and poor optoelectronic performance. Several strategies are further discussed to overcome these challenges and achieve efficient deep-blue PeLED for next-generation display technology.

Efficient perovskite light-emitting diodes on a flexible substrate.

The surface properties of target substrates are crucial for the in situ crystallization and growth of metal halide perovskite films fabricated by the anti-solvent method. In this work, a high-quality quasi-2D perovskite film with various-n phases is fabricated on the commonly used poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) by introducing a branched polyethylenimine (PEI) modifying layer. PEI suppresses the influence of acidic surface of the PEDOT:PSS and regulates the components of the perovskite film, increasing the proportion of large-n phases. Additionally, PEI reduces the formation of defects in perovskite films, leading to higher photoluminescence quantum efficiency and longer photoluminescence lifetime. Based on this high-quality perovskite film, a flexible light-emitting diode with an ultimate current efficiency of 63.2 cd/A is achieved, nearly twofold higher than that of the device (35.1 cd/A) without a PEI modifying layer.

High-Sensitivity and Fast-Response Photomultiplication Type Photodetectors Based on Quasi-2D Perovskite Films for Weak-Light Detection.

Photovoltaic photodiodes often face challenges in effectively harvesting electrical signals, especially when detecting faint light. In contrast, photomultiplication type photodetectors (PM-PDs) are renowned for their exceptional sensitivity to weak signals. Here, an advanced PM-PD is introduced based on quasi 2D Ruddlesden-Popper (Q-2D RP) perovskites, optimized for weak light detection at minimal operating voltages. The abundant traps at the Q-2D RP surface capture charge carriers, inducing a trap-assisted tunneling mechanism that leads to the photomultiplication (PM) effect. Deep-lying trap states within the Q-2D RP bulk accelerate charge carrier recombination, resulting in an outstanding rise/fall time of 1.14/1.72 µs for the PM-PDs. The PM-PD achieves a remarkable response level of up to 45.89 AW-1 and an extraordinary external quantum efficiency of 14400% at -1V under an illumination of 1 µWcm- 2. The intrinsic high resistance of the Q-2D perovskite results in a low dark current, enabling an impressive detectivity of 4.23 × 1012 Jones based on noise current at -1V. Furthermore, the practical application of PM-PDs has been demonstrated in weak-light, high-rate communication systems. These findings confirm the significant potential of PM-PDs based on Q-2D perovskites for weak light detection and suggest new directions for developing low-power, high-performance PM-PDs for future applications.

Excitonic properties and solar harvesting performance of Cs2ZnY2X2 as quasi-2D mixed-halide perovskites

Due to their low toxicity and high-temperature stability, lead-free quasi-2D metal halide perovskites (MHPs) are promising materials for optoelectronic applications. However, understanding their structural and optoelectronic properties, especially excitonic effects (electron-hole pair, e-h), is challenging due to their quantum well topology. We propose an efficient protocol for band gap correction of Cs2ZnX (X = Cl4, Br2Cl2, and I2Cl2) and Cs2PbI2Cl2 (used as a benchmark) quasi-2D MHPs. This protocol is based on a relativistic quasiparticle approach (DFT-1/2) using density functional theory (DFT). We first examined the hybrid contributions of the halide alloys, leading to excitonic characterization using the Bethe–Salpeter equation within the maximally localized Wannier functions tight-binding method. This method provides a cost-effective approach for describing e-h quasiparticle effects. Additionally, we analyzed the crystal structure, thermodynamic stability, and optoelectronic properties of the newly synthesized Zn-based systems, focusing on their structural stability mechanisms. We found a correlation between the allocation of Cs+ cations in the crystal structure and the formation of two distinct stabilization patterns, influenced by the radii of the metal (Zn or Pb) and halide components. The relativistic correction of the band gap energies yielded results within 10 % of the experimental values. Furthermore, incorporating e-h quasiparticle effects for Cs2PbI2Cl2 resulted in an exciton binding energy of 0.160 eV, in excellent agreement with experimental data. This work represents a significant advance in the optoelectronic characterization of Cs2ZnX systems, previously unexplored for their excitonic properties.

Opto-electrical study of 4T perovskite-chalcogenide tandem solar cell with the addition of quasi-2D perovskite as capping layer of 3D perovskite layer

This study presents a four-terminal (4T) perovskite-chalcogenide tandem solar cell (TSC) that includes quasi-2D perovskite material in the top sub-cell in order to provide a stable structure, and the bottom sub-cell contains Zn(O,S,OH) material to provide a nontoxic buffer layer. First, a reference TSC with a total power conversion efficiency (PCE) of 26.48% is modeled, using MAPbI3 and CIGSSe as 3D perovskite and chalcogenide absorber layers (ALs), respectively. Next, two structures are designed to produce a stable SC using the Ruddlesden Popper (RP) quasi-2D perovskite materials, which have the chemical formula BA2MAm−1PbmI3m+1, m = 2–5. The initial structure uses quasi-2D perovskites in place of the 3D perovskite AL. According to the results, BA2MAPb2I7 represents the maximum PCE of 16.00%, 10.48% less than previously. This is caused by quasi-2D materials’ high Eg and low carrier mobility. In the second structure, 3D perovskite AL is capped with the quasi-2D perovskites. In terms of attaining maximum PCE, the optimal TSC is found for BA2MA3Pb4I13 with a PCE of 25.80%. Compared to the initial structure, this one’s PCE increased by 61.25%. In order to boost PCE, a 80 nm-thick anti-reflection (AR) layer is added to the second structure, and the PCE increased to 27.48%. Therefore, the final TSC is proposed as a 4T quasi-2D/3D perovskite-chalcogenide TSC that is stable, and has nontoxic buffer layer, with 3.78% more PCE than the reference structure.

Halogen-Functionalized Hole Transport Materials with Strong Passivation Effects for Stable and Highly Efficient Quasi-2D Perovskite Solar Cells.

The performance of quasi-two-dimensional (Q-2D) perovskite solar cells (PSCs) strongly depends on the interface characteristics between the hole transport material (HTM) and the perovskite layer. In this work, we designed and synthesized a series of HTMs with triphenylamine-carbazole as the core structure and modified end groups with chlorine and bromine atoms. These HTMs show deeper highest occupied molecular orbital energy levels than commercial HTMs. This reduced energy band mismatch between the HTM and perovskite layer facilitates efficient charge extraction at the interface. Moreover, these HTMs containing halogen atoms on the end groups could form halogen bonding with the Pb2+ ions at the buried interface of the perovskite layer, effectively passivating defects to suppress nonradiative recombination. Additionally, halogen bonding also contributes to the formation of vertically oriented perovskite crystals with a high quality. By incorporation of chlorohexane-substituted HTMs, the resultant Q-2D PSCs exhibited the highest power conversion efficiency of 21.07%. Furthermore, the devices show improved stability, retaining 97.2% of their initial efficiency after 1100 h of continuous illumination.

Pressure-Induced Changes in the Phase Distribution and Carrier Dynamics of Quasi-Two-Dimensional Ruddlesden-Popper Perovskites.

Quasi-two-dimensional (quasi-2D) perovskites hold significant potential for diverse design strategies due to their tunable structures, exceptional optical properties, and environmental stability. Due to the complexity of the structure and carrier dynamics, characterization methods such as photoluminescence and absorption spectroscopy can observe but cannot precisely distinguish or identify the phase distribution within quasi-2D perovskite films or correlate phases with carrier dynamics. In this study, we used pressure to modulate the intralayer and interlayer structures of (PEA)2Csn-1PbnBr3n+1 quasi-2D perovskite films, investigating charge carrier dynamics. Steady-state spectroscopy revealed phase transitions at 1.62, 3, and 8 GPa, with free excitons transforming into self-trapped excitons after 8 GPa. Transient absorption spectroscopy elucidated the structural evolution, energy transfer, and pressure-induced transition mechanisms. The results demonstrate that combining pressure and spectroscopy enables the precise identification of phase distribution and pressure response ranges and reveals photophysical mechanisms, providing new insights for optimizing optoelectronic materials.

Assembling the 2D-3D-2D Heterostructure of Quasi-2D Perovskites for High-Performance Solar Cells.

Quasi-two-dimensional (quasi-2D) layered perovskites with mixed dimensions offer a promising avenue for stable and efficient solar cells. However, randomly distributed three-dimensional (3D) perovskites near the film surface limit the device performance of quasi-2D perovskites due to increased nonradiative recombination and ion migration. Herein, we construct a 2D (n = 4 top)-3D-2D (n = 2 bottom) heterostructure of quasi-2D perovskites by using 3-chlorobenzylamine iodine, which can effectively reduce defect density and restrain ion migration. A champion efficiency of 22.22% for quasi-2D perovskite solar cells is achieved due to remarkably reduced nonradiative voltage loss and increased electron extraction. Additionally, the 2D-3D-2D perovskite solar cells also exhibit excellent thermal and humidity stabilities, retaining over 90 and 85% of the initial efficiencies after 2000 h under a heat stress of 65 °C and at air ambient of ∼50% humidity, respectively. Our results provide a general approach to tune perovskite films for suppressing ion migration and achieving high-performance perovskite solar cells.

Resistive random-access memories using quasi-2D halide perovskites for wafer-scale reliable switching behaviors

In this study, we propose the (PEA)2MA3Pb4I13, a quasi-two-dimensional (2D) halide perovskite, in the realm of resistive switching memory devices. A quasi-2D perovskite film (PEA)2MA3Pb4I13, with a thickness measuring 450 nm, has been effectively fabricated on a silicon substrate coated with platinum through an all-solution process conducted at low temperatures. The constructed resistive switching memory devices, incorporating an Ag/(PEA)2MA3Pb4I13/Pt/Ti/SiO2/Si configuration, display dependable and consistent bipolar switching attributes. The device shows an ultra-low operating voltage of less than +0.1 V, an impressive high ON/OFF ratio exceeding 108, reversible resistive switching via pulse voltage operation, and the capability for multilevel data storage. In addition, there is little variation in device characteristics depending on the location on a wafer or device size.