2D Ruddlesden–Popper Perovskites for Optoelectronics

Conventional 3D organic–inorganic halide perovskites have recently undergone unprecedented rapid development. Yet, their inherent instabilities over moisture, light, and heat remain a crucial challenge prior to the realization of commercialization. By contrast, the emerging 2D Ruddlesden?Popper‐type perovskites have recently attracted increasing attention owing to their great environmental stability. However, the research of 2D perovskites is just in their infancy. In comparison to 3D analogues, they are natural quantum wells with a much larger exciton binding energy. Moreover, their inner structural, dielectric, optical, and excitonic properties remain to be largely explored, limiting further applications. This review begins with an introduction to 2D perovskites, along with a detailed comparison to 3D counterparts. Then, a discussion of the organic spacer cation engineering of 2D perovskites is presented. Next, quasi‐2D perovskites that fall between 3D and 2D perovskites are reviewed and compared. The unique excitonic properties, electron–phonon coupling, and polarons of 2D perovskites are then be revealed. A range of their (opto)electronic applications is highlighted in each section. Finally, a summary is given, and the strategies toward structural design, growth control, and photophysics studies of 2D perovskites for high‐performance electronic devices are rationalized.     

2D Perovskite Sr2Nb3O10 for High-Performance UV Photodetectors

2D perovskites, due to their unique properties and reduced dimension, are promising candidates for future optoelectronic devices. However, the development of stable and nontoxic 2D wide-bandgap perovskites remains a challenge. 2D all-inorganic perovskite Sr₂Nb₃O₁₀ (SNO) nanosheets with thicknesses down to 1.8 nm are synthesized by liquid exfoliation, and for the first time, UV photodetectors (PDs) based on individual few-layer SNO sheets are investigated. The SNO sheet-based PDs exhibit excellent UV detecting performance (narrowband responsivity = 1214 A W⁻¹, external quantum efficiency = 5.6 × 10⁵%, detectivity = 1.4 × 10¹⁴ Jones @270 nm, 1 V bias), and fast response speed (t_rise ≈ 0.4 ms, t_decay ≈ 40 ms), outperforming most reported individual 2D sheet-based UV PDs. Furthermore, the carrier transport properties of SNO and the performance of SNO-based phototransistors are successfully controlled by gate voltage. More intriguingly, the photodetecting performance and carrier transport properties of SNO sheets are dependent on their thickness. In addition, flexible and transparent PDs with high mechanical stability are easily fabricated based on SNO nanosheet film. This work sheds light on the development of high-performance optoelectronics based on low-dimensional wide-bandgap perovskites in the future.     

Comprehensive Passivation for High-Performance Quasi-2D Perovskite LEDs

Quasi-2D perovskites have demonstrated great application potential in light-emitting diodes (LEDs). Defect passivation with chemicals plays a critical role to achieve high efficiency. However, there are still challenges in comprehensively passivating the defects distributed at surface, bulk, and buried interface of quasi-2D perovskite emitting films, hindering the further improvement of device performance. Herein, 9,9-substituted fluorene derivatives with different terminal functional groups are developed tactfully to realize comprehensive passivation, which greatly contributes to reducing nonradiative recombination at surface, suppressing ion migration in bulk, and filling interfacial charge traps at buried interface, respectively. Eventually, quasi-2D perovskite LEDs have an increased external quantum efficiency from 18.2% to 23.2%, improved operation lifetime by more than six times and lower turn-on voltage simultaneously. Here the importance of comprehensive passivation is highlighted and guidelines for the design and application of passivators for perovskite optoelectronics are provided.     

Compositional Control in 2D Perovskites with Alternating Cations in the Interlayer Space for Photovoltaics with Efficiency over 18%

2D perovskites stabilized by alternating cations in the interlayer space (ACI) represent a very new entry as highly efficient semiconductors for solar cells approaching 15% power conversion efficiency (PCE). However, further improvements will require understanding of the nature of the films, e.g., the thickness distribution and charge‐transfer characteristics of ACI quantum wells (QWs), which are currently unknown. Here, efficient control of the film quality of ACI 2D perovskite (GA)(MA)_nPb_nI_3n+1 (〈n〉 = 3) QWs via incorporation of methylammonium chloride as an additive is demonstrated. The morphological and optoelectronic characterizations unambiguously demonstrate that the additive enables a larger grain size, a smoother surface, and a gradient distribution of QW thickness, which lead to enhanced photocurrent transport/extraction through efficient charge transfer between low‐n and high‐n QWs and suppressed nonradiative charge recombination. Therefore, the additive‐treated ACI perovskite film delivers a champion PCE of 18.48%, far higher than the pristine one (15.79%) due to significant improvements in open‐circuit voltage and fill factor. This PCE also stands as the highest value for all reported 2D perovskite solar cells based on the ACI, Ruddlesden–Popper, and Dion–Jacobson families. These findings establish the fundamental guidelines for the compositional control of 2D perovskites for efficient photovoltaics.     

Photonics and Optoelectronics of 2D Metal‐Halide Perovskites

In the growing list of 2D semiconductors as potential successors to silicon in future devices, metal‐halide perovskites have recently joined the family. Unlike other conversional 2D covalent semiconductors such as graphene, transition metal dichalcogenides, black phosphorus, etc., 2D perovskites are ionic materials, affording many distinct properties of their own, including high photoluminescence quantum efficiency, balanced large exciton binding energy and oscillator strength, and long carrier diffusion length. These unique properties make 2D perovskites potential candidates for optoelectronic and photonic devices such as solar cells, light‐emitting diodes, photodetectors, nanolasers, waveguides, modulators, and so on, which represent a relatively new but exciting and rapidly expanding area of research. In this Review, the recent advances in emerging 2D metal‐halide perovskites and their applications in the fields of optoelectronics and photonics are summarized and insights into the future direction of these fields are offered.     

原位矿化复合对HDPE/HAP复合材料结晶形态与结晶动力学的影响

研究了原位矿化复合方法对HDPE/HAP复合材料中HDPE的结晶形态及结晶动力学的影响,结果表明,原位矿化复合方法制备的复合材料中HDPE主要以放射状伸直晶形式存在,HDPE晶粒细小,结晶度高,且HAP与HDPE界面结合紧密。结晶动力学结果表明,由于矿化复合体系中界面粘接牢固,HDPE熔体在冷却过程中受收缩应力的牵伸和取向作用加快了HDPE的结晶速率,并诱导HDPE以放射状伸直晶形式结晶,矿化复合材料中HAP颗粒以纳米尺度均匀分布于HDPE基体中,在冷却过程中能诱导形成更多的晶核,故生成的HDPE晶粒细小。     

Manipulating the Mixed‐Perovskite Crystallization Pathway Unveiled by In Situ GIWAXS

Mixed perovskites have achieved substantial successes in boosting solar cell efficiency, but the complicated perovskite crystal formation pathway remains mysterious. Here, the detailed crystallization process of mixed perovskites (FA_0.83MA_0.17Pb(I_0.83Br_0.17)₃) during spin‐coating is revealed by in situ grazing‐incidence wide‐angle X‐ray scattering measurements, and three phase‐formation stages are identified: I) precursor solution; II) hexagonal δ‐phase (2H); and III) complex phases including hexagonal polytypes (4H, 6H), MAI–PbI₂–DMSO intermediate phases, and perovskite α‐phase. The correlated device performance and ex situ characterizations suggest the existence of an “annealing window” covering the duration of stage II. The spin‐coated film should be annealed within the annealing window to avoid the formation of hexagonal polytypes during the perovskite crystallization process, thus achieving a good device performance. Remarkably, the crystallization pathway can be manipulated by incorporating Cs⁺ ions in mixed perovskites. Combined with density functional theory calculations, the perovskite system with sufficient Cs⁺ will bypass the formation of secondary phases in stage III by promoting the formation of α‐phase both kinetically and thermodynamically, thereby significantly extending the annealing window. This study provides underlying reasons of the time sensitivity of fabricating mixed‐perovskite devices and insightful guidelines for manipulating the perovskite crystallization pathways toward higher performance.     

2D Ruddlesden–Popper Perovskites Microring Laser Array

3D organic–inorganic hybrid perovskites have featured high gain coefficients through the electron–hole plasma stimulated emission mechanism, while their 2D counterparts of Ruddlesden–Popper perovskites (RPPs) exhibit strongly bound electron–hole pairs (excitons) at room temperature. High‐performance solar cells and light‐emitting diodes (LEDs) are reported based on 2D RPPs, whereas light‐amplification devices remain largely unexplored. Here, it is demonstrated that ultrafast energy transfer along cascade quantum well (QW) structures in 2D RPPs concentrates photogenerated carriers on the lowest‐bandgap QW state, at which population inversion can be readily established enabling room‐temperature amplified spontaneous emission and lasing. Gain coefficients measured for 2D RPP thin‐films (≈100 nm in thickness) are found about at least four times larger than those for their 3D counterparts. High‐density large‐area microring arrays of 2D RPPs are fabricated as whispering‐gallery‐mode lasers, which exhibit high quality factor (Q ≈ 2600), identical optical modes, and similarly low lasing thresholds, allowing them to be ignited simultaneously as a laser array. The findings reveal that 2D RPPs are excellent solution‐processed gain materials potentially for achieving electrically driven lasers and ideally for on‐chip integration of nanophotonics.     

氧化锆对聚丙烯非等温结晶动力学的影响

以不同含量的氧化锆(ZrO2)作为成核剂对聚丙烯进行改性,通过差示扫描量热(DSC)方法研究改性聚丙烯的非等温结晶动力学,对所得数据分别用修正Avrami方程、Jeziorny法进行处理。实验结果表明:氧化锆的加入使聚丙烯在较高的温度下就可以产生结晶现象,氧化锆具有明显的成核作用;氧化锆的加入并未改变聚丙烯的成核和生长机理,但降低了聚丙烯的结晶活化能。     

Non‐Preheating Processed Quasi‐2D Perovskites for Efficient and Stable Solar Cells

Although the hot‐casting (HC) technique is prevalent in developing preferred crystal orientation of quasi‐2D perovskite films, the difficulty of accurately controlling the thermal homogeneity of substrate is unfavorable for the reproducibility of device fabrication. Herein, a facile and effective non‐preheating (NP) film‐casting method is proposed to realize highly oriented quasi‐2D perovskite films by replacing the butylammonium (BA⁺) spacer partially with methylammonium (MA⁺) cation as (BA)_2?x(MA)_3+xPb₄I₁₃ (x = 0, 0.2, 0.4, and 0.6). At the optimal x‐value of 0.4, the resultant quasi‐2D perovskite film possesses highly orientated crystals, associated with a dense morphology and uniform grain‐size distribution. Consequently, the (BA)_1.6(MA)_3.4Pb₄I₁₃‐based solar cells yield champion efficiencies of 15.44% with NP processing and 16.29% with HC processing, respectively. As expected, the HC‐processed device shows a poor performance reproducibility compared with that of the NP film‐casting method. Moreover, the unsealed device (x = 0.4) displays a better moisture stability with respect to the x = 0 stored in a 65% ± 5% relative humility chamber.     

The Role of Graphene and Other 2D Materials in Solar Photovoltaics

2D materials have attracted considerable attention due to their exciting optical and electronic properties, and demonstrate immense potential for next‐generation solar cells and other optoelectronic devices. With the scaling trends in photovoltaics moving toward thinner active materials, the atomically thin bodies and high flexibility of 2D materials make them the obvious choice for integration with future‐generation photovoltaic technology. Not only can graphene, with its high transparency and conductivity, be used as the electrodes in solar cells, but also its ambipolar electrical transport enables it to serve as both the anode and the cathode. 2D materials beyond graphene, such as transition‐metal dichalcogenides, are direct‐bandgap semiconductors at the monolayer level, and they can be used as the active layer in ultrathin flexible solar cells. However, since no 2D material has been featured in the roadmap of standard photovoltaic technologies, a proper synergy is still lacking between the recently growing 2D community and the conventional solar community. A comprehensive review on the current state‐of‐the‐art of 2D‐materials‐based solar photovoltaics is presented here so that the recent advances of 2D materials for solar cells can be employed for formulating the future roadmap of various photovoltaic technologies.     

Kinetic Stabilization of the Sol–Gel State in Perovskites Enables Facile Processing of High‐Efficiency Solar Cells

Perovskite solar cells increasingly feature mixed‐halide mixed‐cation compounds (FA_1?x?yMA_xCs_yPbI_3?zBr_z) as photovoltaic absorbers, as they enable easier processing and improved stability. Here, the underlying reasons for ease of processing are revealed. It is found that halide and cation engineering leads to a systematic widening of the anti‐solvent processing window for the fabrication of high‐quality films and efficient solar cells. This window widens from seconds, in the case of single cation/halide systems (e.g., MAPbI₃, FAPbI₃, and FAPbBr₃), to several minutes for mixed systems. In situ X‐ray diffraction studies reveal that the processing window is closely related to the crystallization of the disordered sol–gel and to the number of crystalline byproducts; the processing window therefore depends directly on the precise cation/halide composition. Moreover, anti‐solvent dripping is shown to promote the desired perovskite phase with careful formulation. The processing window of perovskite solar cells, as defined by the latest time the anti‐solvent drip yields efficient solar cells, broadened with the increasing complexity of cation/halide content. This behavior is ascribed to kinetic stabilization of sol–gel state through cation/halide engineering. This provides guidelines for designing new formulations, aimed at formation of the perovskite phase, ultimately resulting in high‐efficiency perovskite solar cells produced with ease and with high reproducibility.     

Efficient Energy Funneling in Quasi-2D Perovskites: From Light Emission to Lasing

Quasi-2D Ruddlesden–Popper halide perovskites with a large exciton binding energy, self-assembled quantum wells, and high quantum yield draw attention for optoelectronic device applications. Thin films of these quasi-2D perovskites consist of a mixture of domains having different dimensionality, allowing energy funneling from lower-dimensional nanosheets (high-bandgap domains) to 3D nanocrystals (low-bandgap domains). High-quality quasi-2D perovskite (PEA)₂(FA)₃Pb₄Br₁₃ films are fabricated by solution engineering. Grazing-incidence wide-angle X-ray scattering measurements are conducted to study the crystal orientation, and transient absorption spectroscopy measurements are conducted to study the charge-carrier dynamics. These data show that highly oriented 2D crystal films have a faster energy transfer from the high-bandgap domains to the low-bandgap domains (<0.5 ps) compared to the randomly oriented films. High-performance light-emitting diodes can be realized with these highly oriented 2D films. Finally, amplified spontaneous emission with a low threshold 4.16 µJ cm⁻² is achieved and distributed feedback lasers are also demonstrated. These results show that it is important to control the morphology of the quasi-2D films to achieve efficient energy transfer, which is a critical requirement for light-emitting devices.     

Unusual Pressure-Driven Phase Transformation and Band Renormalization in 2D vdW Hybrid Lead Halide Perovskites

The application of high pressure allows control over the unit cell and interatomic spacing of materials without any need for new growth methods or processing while accessing their materials properties in situ. Under these extreme pressures, materials may assume new structural phases and reveal novel properties. Here, unusual phase transition and band renormalization effects in 2D van der Waals Ruddlesden−Popper hybrid lead halide perovskites, which have shown extraordinary optical properties and immense potential in light emission and conversion technologies, are reported. The results show that (CH₃(CH₂)₃NH₃)₂(CH₃NH₃)Pb₂Br₇ (n = 2) layers undergo two distinct phase transitions related to PbBr₆ octahedra, butylammonium (BA), and methylammonium (MA) molecule tilting motion that leads to rather unique/anomalous bandgap variation with pressure. In contrast, (CH₃(CH₂)₃NH₃)PbBr₄ (n = 1) lacks MA molecules and possesses only one pressure-induced phase transition related to PbBr₆ octahedra and BA tilting. In this range, the bandgap reduces monotonically, much similar to other inorganic semiconductors and display surprisingly large redshift from 3 to 2.4 eV. Together with theoretical calculations, this study offers unique insights into these pressure-induced changes and extends the understanding of these highly anisotropic layered soft organic perovskite materials under extreme conditions.     

2D Perovskites with Giant Excitonic Optical Nonlinearities for High‐Performance Sub‐Bandgap Photodetection

Two‐dimensional (2D) perovskites have proved to be promising semiconductors for photovoltaics, photonics, and optoelectronics. Here, a strategy is presented toward the realization of highly efficient, sub‐bandgap photodetection by employing excitonic effects in 2D Ruddlesden–Popper‐type halide perovskites (RPPs). On near resonance with 2D excitons, layered RPPs exhibit degenerate two‐photon absorption (D‐2PA) coefficients as giant as 0.2–0.64 cm MW^?1. 2D RPP‐based sub‐bandgap photodetectors show excellent detection performance in the near‐infrared (NIR): a two‐photon‐generated current responsivity up to 1.2 × 10⁴ cm² W^?2 s^?1, two orders of magnitude greater than InAsSbP‐pin photodiodes; and a dark current as low as 2 pA at room temperature. More intriguingly, layered‐RPP detectors are highly sensitive to the light polarization of incoming photons, showing a considerable anisotropy in their D‐2PA coefficients (β_[001]/β_[011] = 2.4, 70% larger than the ratios reported for zinc‐blende semiconductors). By controlling the thickness of the inorganic quantum well, it is found that layered RPPs of (C₄H₉NH₃)₂(CH₃NH₃)Pb₂I₇ can be utilized for three‐photon photodetection in the NIR region.     

Enhancing Crystallization in Hybrid Perovskite Solar Cells Using Thermally Conductive 2D Boron Nitride Nanosheet Additive

Controlling crystallization and grain growth is crucial for realizing highly efficient hybrid perovskite solar cells (PSCs). In this work, enhanced PSC photovoltaic performance and stability by accelerating perovskite crystallization and grain growth via 2D hexagonal boron nitride (hBN) nanosheet additives incorporated into the active perovskite layer are demonstrated. In situ X-ray scattering and infrared thermal imaging during the perovskite annealing process revealed the highly thermally conductive hBN nanosheets promoted the phase conversion and grain growth in the perovskite layer by facilitating a more rapid and spatially uniform temperature rise within the perovskite film. Complementary structural, physicochemical, and electrical characterizations further showed that the hBN nanosheets formed a physical barrier at the perovskite grain boundaries and the interfaces with charge transport layers, passivating defects, and retarding ion migration. As a result, the power conversion efficiency of the PSC is improved from 17.4% to 19.8%, along with enhanced device stability, retaining ≈90% of the initial efficiency even after 500 h ambient air storage. The results not only highlight 2D hBN as an effective additive for PSCs but also suggest enhanced thermal transport as one of the pathways for improved PSC performance by 2D material additives in general.     

PP／s-1，2PB共混物的非等温结晶动力学

用DSC方法研究了聚丙烯(PP)、PP与间同1,2-聚丁二烯(s-1,2 PB)共混物的非等温结晶行为,结果表明:Mo法处理PP及PP/s-1,2 PB(90/10)共混物是非常适宜的,而用Ozawa法处理则存在缺陷.用Jeziorny法处理共混物也是适宜的,但对PP处理存在缺陷;s-1,2 PB对PP有加速结晶的作用; s-1,2 PB使PP的结晶活化能降低,s-1,2 PB在PP结晶过程中起到异相成核的作用.     

In Situ Grazing-Incidence Wide-Angle Scattering Reveals Mechanisms for Phase Distribution and Disorientation in 2D Halide Perovskite Films

2D hybrid halide perovskites with the formula (A′)₂(A)_n-1Pb_nI_3n+1 have remarkable stability and promising efficiency in photovoltaic and optoelectronic devices, yet fundamental understanding of film formation, key to optimizing these devices, is lacking. Here, in situ grazing-incidence wide-angle X-ray scattering (GIWAXS) is used to monitor film formation during spin-coating. This elucidates the general film formation mechanism of 2D halide perovskites during one-step spin-coating. There are three stages of film formation: sol–gel, oriented 3D, and 2D. Three precursor phases form during the sol–gel stage and transform to perovskite, first giving a highly oriented 3D-like phase at the air/liquid interface followed by subsequent nucleations forming slightly less oriented 2D perovskite. Furthermore, heating before crystallization leads to fewer nucleations and faster removal of the precursors, improving orientation. This outlines the primary causes of phase distribution and perpendicular orientation in 2D perovskite films and paves the way for rationally designed film fabrication techniques.     

氟锆酸盐玻璃析晶动力学研究

本文用差示热分析ＤＴＡ研究了ＮａＦ和ＮａＣｌ的引入对氟锆酸盐玻璃析晶动力学参数的影响，指出ＮａＦ和ＮａＣｌ的引入使氟锆酸盐玻璃析晶活化能下降，Ｔｘ－Ｔｇ增加，改善了玻璃形成能力。用Ａｕｇｉｓ－Ｂｅｎｎｅｔｔ法及修正Ｋｉｓｓｉｎｇｅｒ法处理实验结果，所得析晶活化能基本一致，而由Ａｕｇｉｓ－Ｂｅｎｎｅｔｔ法及修正Ｋｉｓｓｉｎｇｅｒ法处理实验结果，所得析晶活化能基本一致，而由Ａｕｇｉｓ－Ｂｅｎｎｅｔｔ法