Tailoring the Functionality of Organic Spacer Cations for Efficient and Stable Quasi‐2D Perovskite Solar Cells

The recent development of quasi‐2D perovskite solar cells have drawn significant attention due to the improved stability of these materials and devices against moisture compared to their 3D counterparts. However, the optoelectronic properties of 2D perovskites need to be optimized in order to achieve high efficiency. In this work, the effect of spacer cations, i.e., phenethylammonium (PEA), 4‐fluorophenethylammonium (F‐PEA), and 4‐methoxyphenethylammonium (MeO‐PEA) on the optoelectronic properties and device performance of quasi‐2D perovskites is systematically studied. It is observed that both larger and more hydrophobic cations can improve perovskite stability against moisture, while larger size can adversely influence the device performance. Interestingly, with F‐PEA or MeO‐PEA, distribution of n value can be shifted toward high 3D content in quasi‐2D perovskite layers, which enables lower bandgaps and possibly lower exciton binding energy. Due to the best charge transport and lowest bandgap, the F‐PEAI‐based quasi‐2D perovskite (n = 5) solar cell shows a highest power conversion efficiency (PCE) of 14.5% with excellent stability in air with a humidity of 40–50%, keeping 90% of the original PCE after 40 d. It is believed that the approach may open a way for the design of new organic spacer cations for stable low‐dimensional hybrid perovskites with high performance.     

A Spacer Cation Assisted Nucleation and Growth Strategy Enables Efficient and High-Luminance Quasi-2D Perovskite LEDs

Quasi-2D Ruddlesden-Popper perovskites receive tremendous attention for application in light-emitting diodes (LEDs). However, the role of organic ammonium spacers on perovskite film has not been fully-understood. Herein, a spacer cation assisted perovskite nucleation and growth strategy, where guanidinium (GA⁺) spacer is introduced into the perovskite precursor and at the interface between the hole transport layer (HTL) and the perovskite, to achieve dense and uniform perovskite films with enhanced optical and electrical performance is developed. A thin GABr interface pre-formed on HTL provides more nucleation sites for perovskite crystal; while the added GA⁺ in perovskite reduces the crystallization rate due to strong hydrogen bonding interacts with intermediates, which promotes the growth of enhanced-quality quasi-2D perovskite films. The ionized ammonium group ( NH₃⁺) of GA⁺ also favors formation of polydisperse domain distribution, and amine or imine ( NH₂ or NH) group interact with perovskite defects through coordination bonding. The spacer cation assisted nucleation and growth strategy is advantageous for producing efficient and high-luminance perovskite LEDs, with a peak external quantum efficiency of over 20% and a luminance up to 100 000 cd m⁻². This work can inform and underpin future development of high-performance perovskite LEDs with concurrent high efficiency and brightness.     

Efficient and Stable Quasi-2D Perovskite Solar Cells Enabled by Thermal-Aged Precursor Solution

Quasi-2D perovskites have received wide attention in photovoltaics owing to their excellent materials robustness and merits in the device stability. However, the highest power conversion efficiency (PCE) reported on quasi-2D perovskite solar cells (PSCs) still lags those of the 3D counterparts, mainly caused by the relatively high voltage loss. Here, a study is presented on the mitigation of voltage loss in quasi-2D PSCs via usage of thermal-aged precursor solutions (TAPSs). Based on the (AA)₂MA₄Pb₅I₁₆ (n = 5) quasi-2D perovskite absorber with a bandgap of ≈1.60 eV, a record-high open-circuit voltage of 1.24 V is obtained, resulting in boosting the PCE to 18.68%. The enhanced photovoltaic performance afforded by TAPS is attributed to the thermal-aged solution processing that triggers colloidal aggregations to reduce the nucleation sites inside the solution. As a result, formation of high-quality perovskite films featuring compact morphology, preferential crystal orientation, and lowered trap density is allowed. Of importance, with the improved film quality, the corrosion of Ag electrode induced by ion migrations is effectively restrained, which leads to a satisfactory storage stability with <2% degradation after 1200 h under nitrogen environment without encapsulation.     

High Q-Factor and Low Threshold Continuous-Wave Near-Infrared Lasing with Quasi-2D Perovskites

Quasi-2D perovskites have shown great potential in achieving solution-processed electrically pumped laser diodes due to their multiple-quantum-well structure, which induces a carrier cascade process that can significantly enhance population inversion. However, continuous-wave (CW) optically pumped lasing has yet to be achieved with near-infrared (NIR) quasi-2D perovskites due to the challenges in obtaining high-quality quasi-2D films with suitable phase distribution and morphology. This study regulates the crystallization of a NIR quasi-2D perovskite ((NMA)₂FA_n−1Pb_nI_3n+1) using an 18-crown-6 additive, resulting in a compact and smooth film with a largely improved carrier cascade efficiency. The amplified spontaneous emission threshold of the film is reduced from 47.2 to 35.9 µJ cm⁻². Furthermore, by combining the film with a high-quality distributed feedback grating, this study successfully realizes a CW NIR laser of 809 nm at 110 K, with a high Q-factor of 4794 and a low threshold of 911.6 W cm⁻². These findings provide an important foundation for achieving electrically pumped laser diodes based on the unique quasi-2D perovskites.     

Side-Chain Functionalized Polymer Hole-Transporting Materials with Defect Passivation Effect for Highly Efficient Inverted Quasi-2D Perovskite Solar Cells

Compared with inverted 3D perovskite solar cell (PSCs), inverted quasi-2D PSCs have advantages in device stability, but the device efficiency is still lagging behind. Constructing polymer hole-transporting materials (HTMs) with passivation functions to improve the buried interface and crystallization properties of perovskite films is one of the effective strategies to improve the performance of inverted quasi-2D PSCs. Herein, two novel side-chain functionalized polymer HTMs containing methylthio-based passivation groups are designed, named PVCz-SMeTPA and PVCz-SMeDAD, for inverted quasi-2D PSCs. Benefited from the non-conjugated flexible backbone bearing functionalized side-chain groups, the polymer HTMs exhibit excellent film-forming properties, well-matched energy levels and improved charge mobility, which facilitates the charge extraction and transport between HTM and quasi-2D perovskite layer. More importantly, by introducing methylthio units, the polymer HTMs can enhance the contact and interactions with quasi-2D perovskite, and further passivating the buried interface defects and assisting the deposition of high-quality perovskite. Due to the suppressed interfacial non-radiative recombination, the inverted quasi-2D PSCs using PVCz-SMeTPA and PVCz-SMeDAD achieve impressive power conversion efficiency (PCE) of 21.41% and 20.63% with open-circuit voltage of 1.23 and 1.22 V, respectively. Furthermore, the PVCz-SMeTPA based inverted quasi-2D PSCs also exhibits negligible hysteresis and considerably improved thermal and long-term stability.     

In Situ Growth of 2D Perovskite Capping Layer for Stable and Efficient Perovskite Solar Cells

2D halide perovskites have recently been recognized as a promising avenue in perovskite solar cells (PSCs) in terms of encouraging stability and defect passivation effect. However, the efficiency (less than 15%) of ultrastable 2D Ruddlesden–Popper PSCs still lag far behind their traditional 3D perovskite counterparts. Here, a rationally designed 2D‐3D perovskite stacking‐layered architecture by in situ growing 2D PEA₂PbI₄ capping layers on top of 3D perovskite film, which drastically improves the stability of PSCs without compromising their high performance, is reported. Such a 2D perovskite capping layer induces larger Fermi‐level splitting in the 2D‐3D perovskite film under light illumination, resulting in an enhanced open‐circuit voltage (V_oc) and thus a higher efficiency of 18.51% in the 2D‐3D PSCs. Time‐resolved photoluminescence decay measurements indicate the facilitated hole extraction in the 2D‐3D stacking‐layered perovskite films, which is ascribed to the optimized energy band alignment and reduced nonradiative recombination at the subgap states. Benefiting from the high moisture resistivity as well as suppressed ion migration of the 2D perovskite, the 2D‐3D PSCs show significantly improved long‐term stability, retaining nearly 90% of the initial power conversion efficiency after 1000 h exposure in the ambient conditions with a high relative humidity level of 60 ± 10%.     

Domain Distribution Management of Quasi-2D Perovskites toward High-Performance Blue Light-Emitting Diodes

Quasi-2D perovskites, as one of the promising materials applied in perovskite light-emitting diodes (PeLEDs), have attracted great attention for their superior semiconductor properties. The inherent multiquantum well structure can induce a strong confinement effect, which is especially suitable for blue emission. However, compared to their green counterparts, blue emitters constructed from quasi-2D perovskites are more sensitive to n domain distribution (where n represents the number of PbX₆ inorganic layers). Suffering from inefficient domain distribution management, blue PeLEDs now face a variety of negative issues, including color instability, multipeak emission, and poor fluorescence yield. In this review, the development of blue PeLEDs and the optical properties of quasi-2D perovskites are overviewed. Then, a classification and summary of strategies for domain distribution management are proposed. Finally, the challenges and potential directions of domain distribution management in quasi-2D perovskites are summarized. This review is expected to provide a comprehensive perspective and reference on domain distribution management toward efficient blue quasi-2D PeLEDs.     

Band Edge Control of Quasi-2D Metal Halide Perovskites for Blue Light-Emitting Diodes with Enhanced Performance

Perovskite light-emitting diodes (PeLEDs) have received great attention for their potential as next-generation display technology. While remarkable progress has been achieved in green, red, and near-infrared PeLEDs with external quantum efficiencies (EQEs) exceeding 20%, obtaining high performance blue PeLEDs remains a challenge. Poor charge balance due to large charge injection barriers in blue PeLEDs has been identified as one of the major roadblocks to achieve high efficiency. Here band edge control of perovskite emitting layers for blue PeLEDs with enhanced charge balance and device performance is reported. By using organic spacer cations with different dipole moments, that is, phenethyl ammonium (PEA), methoxy phenethyl ammonium (MePEA), and 4-fluoro phenethyl ammonium (4FPEA), the band edges of quasi-2D perovskites are tuned without affecting their band gaps. Detailed characterization and computational studies have confirmed the effect of dipole moment modification to be mostly electrostatic, resulting in changes in the ionization energies of ≈0.45 eV for MePEA and ≈ −0.65 eV for 4FPEA based thin films relative to PEA-based thin films. With improved charge balance, blue PeLEDs based on MePEA quasi-2D perovskites show twofold increase of the EQE as compared to the control PEA based devices.     

Multi-Site Intermolecular Interaction for In Situ Formation of Vertically Orientated 2D Passivation Layer in Highly Efficient Perovskite Solar Cells

Surface passivation via 2D perovskite is critical for perovskite solar cells (PSCs) to achieve remarkable performances, in which the applied spacer cations play an important role on structural templating. However, the random orientation of 2D perovskite always hinder the carrier transport. Herein, multiple nitrogen sites containing organic spacer molecule (1H-Pyrazole-1-carboxamidine hydrochloride, PAH) is introduced to form 2D passivation layer on the surface of formamidinium based (FAPbI₃) perovskite. Deriving from the interactions between PAH and PbI₂, the defects of FAPbI₃ perovskite are effectively passivated. Interestingly, due to the multiple-site interactions, the 2D nanosheets are found to grow perpendicularly to the substrate for promotion of charge transfer. Therefore, an impressive power conversion efficiency of 24.6% and outstanding long-term stability are achieved for the 2D/3D perovskite devices. The findings further provide a perspective in structure design of novel organic halide salts for the fabrication of efficient and stable PSCs.     

Holy Water: Photo-Brightening in Quasi-2D Perovskite Films under Ambient Enables Highly Performing Light-Emitting Diodes

Quasi-2D perovskites provide new opportunities for lighting and display applications due to their high radiative recombination and excellent stability. However, seldom attention has been placed on their self-stability/working operation under ambient storage. Herein, quasi-2D perovskites/Polyethylene oxide (PEO) films are studied, showing an unforeseen photo-brightening effect under ambient storage (i.e., an increase of the photoluminescence quantum yield from 55% to 74% after 100 days). In stark contrast, those stored under a dark/inert atmosphere show a significant decrease down to 38%. This counterintuitive phenomenon responds to the increasing radiative recombination rate caused by the passivation of the surface Br vacancies in the presence of physically adsorbed water molecules, as corroborated by in situ/ex situ X-ray photoelectron spectroscopy and density functional theory calculations. Capitalizing on this surprising effect, stable light-emitting diodes (LEDs) using quasi-2D perovskites/PEO color filters are fabricated, realizing high stabilities of ≈400 h@10 mA under operating ambient conditions, representing a 20-fold enhancement compared to LEDs with 3D counter partners. Hence, this study reveals a unique insight into the impact of water passivation on the optical/structural properties of quasi-2D perovskite films, broadening their applications under operating ambient conditions.     

Highly Efficient Blue Light-Emitting Diodes Based on Perovskite Film with Vertically Graded Bandgap and Organic Grain Boundary Passivation Shells

Metal halide perovskite materials have emerged as a promising class of semiconductors for high-performance optoelectronic applications, particularly for light-emitting diodes (LEDs), due to their high quantum efficiency, facile color tunability, narrow emission line widths, as well as cost-effectiveness. Despite the great successes on green and red perovskite LEDs (PeLEDs), the external quantum efficiency (EQE) of blue PeLEDs still lags far behind that of green and red counterparts. Here, wavelength tunable pure and deep blue PeLEDs with high EQE are presented, achieving 17.5% and 10.8% for emission wavelengths of 472 and 461 nm, respectively. The wavelength tenability and high EQE are attributed to the unique vertically graded bandgaps and grain boundary organic shells in the perovskite films. The results demonstrate a significant performance improvement in blue PeLEDs, provide a novel route to fabricate high-performance pure and deep blue PeLEDs that can match the performance of the green and red PeLEDs for future lighting and display applications.     

Domain Controlling by Compound Additive toward Highly Efficient Quasi-2D Perovskite Light-Emitting Diodes

Quasi-2D perovskites with enlarged exciton binding energy and tunable bandgap are appealing for application in perovskite light-emitting diodes (PeLEDs). However, wide n domains distribution is commonly formed in solution-processed quasi-2D perovskite films due to the uncontrollable crystallization behavior, which leads to low device performance. Here, the crystallization process is successfully regulated to narrow the n domains distribution by introducing compound additive of ZrO₂ nanoparticles (NPs) and Cryptand complexant. ZrO₂ NPs can avoid the segregation of organic large and small cations by strengthening the solvent extraction capacity of antisolvent, while Cryptand offsets the poor solubility of PbBr₂ by forming an intermediate state to slow down the crystallization of high-n domains. Consequently, both high photoluminescence quantum yields over 90% and a high external quantum efficiency of 21.2% are obtained in the optimized green quasi-2D PeLEDs. Moreover, the lifetime extends about four times compared with control devices. The strategy of domain controlling by compound additive provides a powerful way to develop high-performance quasi-2D perovskite optoelectrical devices.     

Enabling Efficient Blue-Emissive Circularly Polarized Luminescence by In Situ Crafting of Chiral Quasi-2D Perovskite Nanosheets within Polymer Nanofibers

Chiral perovskite materials have intrigued enormous interests because of their appealing chiroptical properties and tailorable non-centrosymmetric structures. However, it remains challenging to realize high-efficiency blue emissive circularly polarized luminescence (CPL) of intrinsic chiral perovskite nanomaterials at room temperature. Herein, a robust and versatile electrospinning strategy is reported for in situ construction of chiral 2D and quasi-2D perovskite nanosheets (PNSs) protected in polymer hybrid nanofibers. It is found that quasi-2D chiral PNS/polymer possesses inherent chirality and enhanced CPL properties at room temperature compared to 2D counterparts. Notably, CPL emission color of chiral quasi-2D PNS/polymer can be tuned from deep blue to sky blue, and a high luminescence dissymmetry values up to −8.0 × 10⁻³ can be achieved. Different perovskites, polymers, and nanofibrous structures are expanded to explore the universality of polymer protected PNSs. Significantly, compared to spin-coated film, the stabilities of quasi-2D PNS/polymer film are greatly improved due to the effective protection of polymer. The obtained PNS/polymer hybrid nanofiber films can be conveniently implemented for circularly polarized light emitting diode devices. This study may open up a new avenue for the scalable fabrication of chiral perovskite nanomaterials of interest and their applications in the CPL related fields.     

High-Performing Quasi-2D Perovskite Photodetectors with Efficient Charge Transport Network Built from Vertically Orientated and Evenly Distributed 3D-Like Phases

Quasi-two-dimensional (Q-2D) perovskites are emerging as one of the most promising materials for photodetectors. However, a significant challenge to Q-2D perovskites for photodetection is their insufficient charge transport ability, which is mainly attributed to their hybrid low-dimensional n-phase structure. This study demonstrates that evenly-distributed 3D-like phases with vertical orientation throughout the film can greatly facilitate charge transport and suppress charge recombination, outperforming the prevalent phase structure with a vertical dimension gradient. Based on such a phase structure, a Q-2D Ruddlesden−Popper perovskite self-powered photodetector achieving a combination of exceptional figures-of-merit is realized, including a responsivity of 0.45 AW⁻¹, a peak specific detectivity of 2.3 × 10¹³ Jones, a 156 dB linear dynamic range, and a rise/fall time of 2.89 µs/1.93 µs. The desired phase structure is obtained by utilizing a double-hole transport layer (HTL), combining hydrophobic PTAA and hydrophilic PEDOT: PSS. Besides, the dependence of the hybrid low-dimensional phase structure is also identified on the surface energy of the buried HTL substrate. This study gives insight into the correlation between Q-2D perovskites’ phase structure and performance, providing a valuable design guide for Q-2D perovskite-based photodetectors.     

Efficient and Ambient‐Air‐Stable Solar Cell with Highly Oriented 2D@3D Perovskites

3D organic–inorganic lead halide perovskites have shown great potential in efficient photovoltaic devices. However, the low stability of the 3D perovskite layer and random arrangement of the perovskite crystals hinder its commercialization road. Herein, a highly oriented 2D@3D ((AVA)₂PbI₄@MAPbI₃) perovskite structure combining the advantages of both 2D and 3D perovskite is fabricated through an in situ route. The highest power conversion efficiency (PCE) of 18.0% is observed from a 2D@3D perovskite solar cell (PSC), and it also shows significantly enhanced device stability under both inert (90% of initial PCE for 32 d) and ambient conditions (72% of initial PCE for 20 d) without encapsulation. The high efficiency of 18.0% and nearly twofold improvement of device stability in ambient compared with pure 3D PSCs confirm that such 2D@3D perovskite structure is an effective strategy for high performance and increasing stability and thus will enable the timely commercialization of PSCs.     

Expanded Phase Distribution in Low Average Layer-Number 2D Perovskite Films: Toward Efficient Semitransparent Solar Cells

The application of low average layer-number (〈n〉 ≤ 2) 2D perovskites in semitransparent photovoltaics (ST-PVs) has been hindered by their strong exciton binding energy and high electrical anisotropy. Here, the phase distribution is expanded fully and orderly to enable efficient charge transport in 2D (NMA)₂(MA)Pb₂I₇ (NMA: 1-naphthylmethylammonium, MA: CH₃NH₃⁺) perovskite films by regulating the sedimentation dynamics of organic cation-based colloids. Ammonium chloride is synergistically introduced to enhance the phase separation further and construct a favorable out-of-plane orientation. The wide and graded phase distribution well aligns the energy level to facilitate charge transfer. As a result, the first application of an average 〈n〉 = 2 2D perovskite is implemented in ST-PVs with visible power conversion efficiency (PCE) of 7.52% and high average visible transmittance (AVT) of 40.5%. This study offers a new candidate and an effective strategy for efficient and stable ST-PVs and is relevant to other perovskite optoelectronic devices.     

Introduction of Hydrophobic Ammonium Salts with Halogen Functional Groups for High‐Efficiency and Stable 2D/3D Perovskite Solar Cells

2D perovskites have attracted extensive attention due to their excellent stability compared with 3D perovskites. However, the intrinsic hydrophilicity of introduced alkylammonium salts effects the humidity stability of 2D/3D perovskites. Devices based on longer chain alkylammonium salts show improvement in hydrophobicity but lower efficiency due to the poorer charge transport among various layers. To solve this issue, two hydrophobic short‐chain alkylammonium salts with halogen functional groups (2‐chloroethylamine, CEA⁺ and 2‐bromoethylamine, BEA⁺) are introduced into (Cs_0.1FA_0.9)Pb(I_0.9Br_0.1)₃ 3D perovskites to form 2D/3D perovskite structure, which achieve high‐quality perovskite films with better crystallization and morphology. The optimal 2D/3D perovskite solar cells (PSCs) with 5% CEA⁺ display a power conversion efficiency (PCE) as high as 20.08% under 1 sun irradiation. Because of the notable hydrophobicity of alkylammonium cations with halogen functional groups and the formed 2D/3D perovskite structure, the optimal PSCs exhibit superior moisture resistance and retain 92% initial PCE after aging at 50 ± 5% relative humidity for 2400 h. This work opens up a new direction for the design of new‐type 2D/3D PSCs with improved performance by employing proper alkylammonium salts with different functional groups.     

Combination of Hybrid CVD and Cation Exchange for Upscaling Cs‐Substituted Mixed Cation Perovskite Solar Cells with High Efficiency and Stability

Mixed cation hybrid perovskites such as Cs_xFA_1?xPbI₃ are promising materials for solar cell applications, due to their excellent photoelectronic properties and improved stability. Although power conversion efficiencies (PCEs) as high as 18.16% have been reported, devices are mostly processed by the anti‐solvent method, which is difficult for further scaling‐up. Here, a method to fabricate Cs_xFA_1?xPbI₃ by performing Cs cation exchange on hybrid chemical vapor deposition grown FAPbI₃ with the Cs⁺ ratio adjustable from 0 to 24% is reported. The champion perovskite module based on Cs_0.07FA_0.93PbI₃ with an active area of 12.0 cm² shows a module PCE of 14.6% and PCE loss/area of 0.17% cm^?2, demonstrating the significant advantage of this method toward scaling‐up. This in‐depth study shows that when the perovskite films prepared by this method contain 6.6% Cs⁺ in bulk and 15.0% at the surface, that is, Cs_0.07FA_0.93PbI₃, solar cell devices show not only significantly increased PCEs but also substantially improved stability, due to favorable energy level alignment with TiO₂ electron transport layer and spiro‐MeOTAD hole transport layer, increased grain size, and improved perovskite phase stability.