Prospect for detecting magnetism in two-dimensional perovskite oxides by electron magnetic circular dichroism.

Two-dimensional (2D) magnets, especially strongly correlated 2D transition-metal perovskite oxides, have attracted significant attention due to their intriguing electromagnetic properties for potential applications in spintronic devices. Potentially electron magnetic circular dichroism (EMCD) under zone axis conditions can provide three-dimensional components of magnetic moments in 2D materials, but the collection efficiency and the signal-to-noise ratio for out-of-plane (OOP) components is limited due to the limited collection angle. Here we conducted a comprehensive computational simulation to optimize the experimental setting of EMCD for detecting the OOP components of magnetic moments in three beam conditions (3BCs) on 2D perovskite oxides La1-xSrxMnO3 (LSMO) in a TEM. The key parameters are sample thickness, accelerating voltage, Sr doping concentration, collection semi-angle and position, and sample orientation including systematic reflections excited and tilt angle. Our simulation results demonstrate that the relative dynamical diffraction coefficients of Mn OOP EMCD of LaMnO3 with a thickness ranging from 1 unit cell (uc) to 4 uc can be optimized in a 3BC with (110) systematic reflections excited and a relatively large collection semi-angle of 19 mrad at the relatively low accelerating voltage of 80 kV. In most cases, the relative dynamic diffraction coefficients for La1-xSrxMnO3 with the thickness ranging from 1 uc to 4 uc decrease with the increase of the Sr doping concentrations. The optimal tilt angle from a zone axis to a 3BC is 18° for the cases of the LSMO thickness of 2 uc, 3 uc and 4 uc, and 22° for the monolayer LSMO. Our work provides the theoretical simulation foundation for optimized EMCD experiments for measuring OOP components of magnetic moments in 2D transition-metal perovskite oxides.

Phonon Directionality Impacts Electron-Phonon Coupling and Polarization of the Band-Edge Emission in Two-Dimensional Metal Halide Perovskites.

Two-dimensional metal halide perovskites are highly versatile for light-driven applications due to their exceptional variety in material composition, which can be exploited for the tunability of mechanical and optoelectronic properties. The band-edge emission is defined by the structure and composition of both organic and inorganic layers, and electron-phonon coupling plays a crucial role in the recombination dynamics. However, the nature of the electron-phonon coupling and what kind of phonons are involved are still under debate. Here we investigate the emission, reflectance, and phonon response from single two-dimensional lead iodide microcrystals with angle-resolved polarized spectroscopy. We find an intricate dependence of the emission polarization with the vibrational directionality in the materials, which reveals that several bands of low-frequency phonons with nonorthogonal directionality contribute to the band-edge emission. Such complex electron-phonon coupling requires adequate models to predict the thermal broadening of the emission and provides opportunities to design polarization properties.

Theoretical Design of Tellurium-Based Two-Dimensional Perovskite Photovoltaic Materials.

In recent years, the photoelectric conversion efficiency of three-dimensional (3D) perovskites has seen significant improvements. However, the commercial application of 3D perovskites is hindered by stability issues and the toxicity of lead. Two-dimensional (2D) perovskites exhibit good stability but suffer from low efficiency. Designing efficient and stable lead-free 2D perovskite materials remains a crucial unsolved scientific challenge. This study, through structural prediction combined with first-principles calculations, successfully predicts a 2D perovskite, CsTeI5. Theoretical calculations indicate that this compound possesses excellent stability and a theoretical efficiency of up to 29.3%, showing promise for successful application in thin-film solar cells. This research provides a new perspective for the design of efficient and stable lead-free 2D perovskites.

Modulation of Charge Transport from Two-Dimensional Perovskites to Industrial Charge Transport Layers by the Organic Spacer-Dependent Exciton-Phonon Interactions.

In the past decade, two-dimensional (2D) perovskite surface treatment has emerged as a promising strategy to improve the performance of three-dimensional (3D) perovskite solar cells (PSCs). However, systematic studies on the impact of organic spacers of 2D perovskites on charge transport in 2D/3D PSCs are still lacking. Here, using 2D perovskite film/C60 heterostructures with different organic spacers [butylamine (BA), phenylethylamine (PEA), and 3-fluorophenethylamine (m-F-PEA)], we systematically investigated the carrier diffusion and interfacial transfer process. Using a 2D perovskite film with a thickness of ∼7 nm, we observed subtle differences in electron transfer time between 2D perovskites and C60 layers, which can be attributed to limited thickness and similar electron coupling strength. However, with the thickness of 2D perovskite increasing, electron transfer efficiency in the (BA)2PbI4/C60 heterostructure exhibits the most rapid decrease due to poor carrier diffusion of (BA)2PbI4 caused by stronger exciton-phonon interactions compared to (PEA)2PbI4 and (m-F-PEA)2PbI4 in thickness-dependent charge transfer research. Meanwhile, the fill factor of 2D/3D PSC treated with BAI exhibits the most rapid decrease compared to PEAI- and m-F-PEAI-treated 2D/3D PSCs with the concentration increase of passivators. This study indicates that it is easier to enhance open-circuit voltages and minimize the decrease of fill factor by increasing the concentration of passivators in 2D/3D PSCs when using passivators with a rigid molecular structure.

Photo- and Thermal-Induced Ion Migration and Phase Separation in Mn-Doped Two-Dimensional PEA2PbX4 Perovskite.

Ion migration and phase separation in perovskite materials have negatively affected the solid-state lighting and display. Studying photo- and thermal-induced degradation is considered as a promising approach to understanding the luminescence mechanism and promoting practical applications. Herein, the Mn-doped two-dimensional PEA2PbX4 (X = Cl, Br, I) microcrystals with changing halogen composition were synthesized by an acid-assisted post-processing strategy. Then, photo- and thermal-induced degradation was studied by using steady-state and time-resolved photoluminescence (PL) spectroscopy. The band edge exciton PL peak of Mn-doped 2D PEA2PbX4 microcrystals was adjusted from 397 to 500 nm. The reduced Mn PL lifetime (1.37 to 0.21 ms) was monitored under ion exchange from Cl to Br to I. The degradation mechanism could be divided into two cases: (i) The halide ion migration in Mn-doped 2D perovskite under continuous illumination was revealed, suggesting that the migration of Cl ions was more accessible than that of Br and I. (ii) The PL redshift and lifetime reduction were observed after annealing at 420 K, which means that thermally induced aggregation of Mn ions resulted in the formation of Mn2+-Mn2+ dimers. In addition, the experimental results indicated that the induced B-site phase separation at high temperature annealing made the mixed perovskite phase of Pb and Mn ultimately transform into pure PEA2PbBr4 and PEA2MnBr4.

Direct Fast-Neutron Detection by 2D Perovskite Semiconductor.

Fast-neutrons play a critical role in a range of applications, including medical imaging, therapy, and nondestructive inspection. However, direct detecting fast-neutrons by semiconductors has proven to be challenging due to their weak interaction with most matter and the requirement of high carrier mobility-lifetime (µτ) product for efficient charge collection. Herein, a novel approach is presented to direct fast-neutron detection using 2D Dion-Jacobson perovskite semiconductor BDAPbBr4 . This material features a high fast-neutron caption cross-section, good electrical stability, high resistivity, and, most importantly, a record-high µτ product of 3.3 × 10-4 cm2 V-1 , outperforming most reported fast-neutron detection semiconductors. As a result, BDAPbBr4 detector exhibited good response to fast-neutrons, not only achieving fast-neutron energy spectra in counting mode, but also obtaining linear and fast response in integration mode. This work provides a paradigm-shifting strategy for designing materials that efficiently detect fast-neutrons and paves the way toward exciting applications in fast-neutron imaging and therapy.

Two-Dimensional Metal Halides for X-Ray Detection Applications.

Metal halide perovskites have recently emerged as promising candidates for the next generation of X-ray detectors due to their excellent optoelectronic properties. Especially, two-dimensional (2D) perovskites afford many distinct properties, including remarkable structural diversity, high generation energy, and balanced large exciton binding energy. With the advantages of 2D materials and perovskites, it successfully reduces the decomposition and phase transition of perovskite and effectively suppresses ion migration. Meanwhile, the existence of a high hydrophobic spacer can block water molecules, thus making 2D perovskite obtain excellent stability. All of these advantages have attracted much attention in the field of X-ray detection. This review introduces the classification of 2D halide perovskites, summarizes the synthesis technology and performance characteristics of 2D perovskite X-ray direct detector, and briefly discusses the application of 2D perovskite in scintillators. Finally, this review also emphasizes the key challenges faced by 2D perovskite X-ray detectors in practical application and presents our views on its future development.

Ionic Liquid Assisted Imprint for Efficient and Stable Quasi-2D Perovskite Solar Cells with Controlled Phase Distribution.

Although two-dimensional perovskite devices are highly stable, they also lead to a number of challenges. For instance, the introduction of large organic amines makes crystallization process complicated, causing problems such as generally small grain size and blocked charge transfer. In this work, imprint assisted with methylamine acetate were used to improve the morphology of the film, optimize the internal phase distribution, and enhance the charge transfer of the perovskite film. Specifically, imprint promoted the dispersion of spacer cations in the recrystallization process with the assistance of methylamine acetate, thus inhibited the formation of low-n phase induced by the aggregation of spacer cations and facilitated the formation of 3D-like phase. In this case, the corresponding quasi-2D perovskite solar cells delivered improved efficiency and exhibited superior stability. Our work provides an effective strategy to obtain uniform phase distribution for quasi-2D perovskite.

Self-healing 2D/3D perovskite for efficient and stable p-i-n perovskite solar cells.

Beyond the p-i-n perovskite solar cell's high-power conversion efficiency (PCE), its moisture instability is the most challenging factor in its commercialization. Recently, the innovative use of three and two-dimensional multi-structures, by creating a barrier against the penetration of moisture and oxygen, has played a very influential role in improving the PSC's long-term stability. Here, a new strategy, the anti-solvent quenching method, is used to construct multi-structure perovskite by involving cetyltrimethylammonium bromide (CTAB) as an active agent. The solar cell efficiency is significantly improved during the perovskite formation on the substrate by creating a multidimensional (2D/3D) heterojunction perovskite. The synergistic role of using 2D/3D heterojunction perovskite structures led to the 29.2% improvement (14.58-18.84) in the PCE. The attractive ability of the 2D/3D active layer in self-healing has increased the perovskite's long-term stability under harsh environmental conditions.

Two-Dimensional (PEA)2PbBr4 Perovskites Sensors for Highly Sensitive Ethanol Vapor Detection.

Two-dimensional (2D) perovskite have been widely researched for solar cells, light-emitting diodes, photodetectors because of their excellent environmental stability and optoelectronic properties in comparison to three-dimensional (3D) perovskite. In this study, we demonstrate the high response of 2D-(PEA)2PbBr4 perovskite of the horizontal vapor sensor was outstandingly more superior than 3D-MAPbBr3 perovskite. 2D transverse perovskite layer have the large surface-to-volume ratio and reactive surface, with the charge transfer mechanism, which was suitable for vapor sensing and trapping. Thus, 2D perovskite vapor sensors demonstrate the champion current response ratio R of 107.32 under the ethanol vapors, which was much faster than 3D perovskite (R = 2.92).

In Situ Observing and Tuning the Crystal Orientation of Two-Dimensional Layered Perovskite via the Chlorine Additive.

Precise control of crystal orientation in two-dimensional (2D) layered perovskites (LPs) is vital for their optoelectronic applications due to the structure-induced anisotropy in optical and electrical properties. Herein, we directly observe and control the crystal orientation of the butylammonium-based 2D LP films. Employing the synchrotron-based in situ grazing-incidence X-ray diffraction technique, we reveal the orientation modulation mechanism of the Cl additive by following the crystallization dynamics and chemical conversion pathways during film formation. Two new Cl-related intermediates are identified which serve as templates directing the orientational growth of the 2D LP films. We fine-tune the crystal orientation of 2D LP films through the Cl additive and incorporate the films with the requisite crystal orientations in solar cells and photodetectors. The optoelectronic performances of the devices show a strong correlation with the crystal orientation of the 2D LP films.

Highly Efficient and Stable 2D Dion Jacobson/3D Perovskite Heterojunction Solar Cells.

Heterostructures involving two-dimensional/three-dimensional (2D/3D) perovskites have recently attracted increased attention due to their ability to combine the high photovoltaic performance of 3D perovskites with the increased stability of 2D perovskites. Here we report ammonium thiocyanate (NH4SCN) passivated 3D methylammonium lead triiodide (MAPbI3) perovskite active layer and deposition of 2D perovskite capping layer using xylylene diammonium iodide (XDAI) organic cation. The 2D/3D perovskite heterojunction formation is probed by using FESEM and UPS spectroscopy. The NH4SCN passivated MAPbI3 perovskite has shown 19.6% PCE compared to the 17.18% PCE of pristine MAPbI3 perovskite solar cells (PSCs). Finally, the champion 2D/3D perovskite heterojunction based solar cells have achieved the remarkable PCE of 20.74%. The increased PCE in 2D/3D PSCs is mainly attributed to the reduced defect density and suppressed nonradiative recombination losses. Moreover, the hydrophobic 2D capping layer endows the 2D/3D heterojunction perovskites with exceptional moisture, thermal and UV stability, highlighting the promise of highly stable and efficient 2D/3D PSCs.

Highly Emissive Quasi-2D Perovskites Enabled by a Multifunctional Molecule for Bright Light-Emitting Diodes.

Quasi-two-dimensional (quasi-2D) perovskite has exhibited great potential to be an ideal luminescent material for perovskite light-emitting diodes (PeLEDs). However, the low-order phases (especially n = 1 phase) and the inevitable defects result in massive nonradiative recombination and poor emission efficiency. Herein, a multifunctional molecule of tetrabutylammonium dihydrogen phosphate (TDP) is introduced to simultaneously suppress the low-n phase, passivate the defects, and increase the exciton binding energy of the quasi-2D perovskite for massive radiative recombination and thus high emission efficiency. The multifunctional roles of TDP are realized by the synergistic effects of tetrabutylammonium cation and dihydrogen phosphate anion, both of which show strong interaction with the lead bromide octahedron of the perovskite. As a result, the TDP-incorporated perovskite films show a great enhancement of the emission efficiency with a remarkable increase in photoluminescence quantum yield (PLQY) from 34.6 to 96.9% at the wavelength of 522 nm. The strengthened radiative recombination promotes efficient emission efficiency with over 2.5-fold improvement in external quantum efficiency (EQE) and current efficiency (CE) from 3.27% and 10.83 cd A-1 to 9.25% and 28.35 cd A-1, respectively, as well as high brightness with over 37% enhancement from 12713 to 17536 cd m-2. Consequently, this work contributes to an efficient approach to employ a multifunctional molecule for highly emissive quasi-2D perovskites and enhanced quasi-2D PeLED performances.

Internal Built-In Electric Fields at Organic-Inorganic Interfaces of Two-Dimensional Ruddlesden-Popper Perovskite Single Crystals.

Two-dimensional (2D) organic-inorganic hybrid Ruddlesden-Popper perovskites (OIRPPs), which consist of naturally formed "multiple quantum well (MQW)-like" structure, have received considerable interest in optoelectronic applications, owing to their outstanding optical properties and tailorable functionalities. While the quantum-confined electrons and holes at an MQW structure are under an applied electric field, the tilt of the energy bands may cause a significant influence on their optical properties. This work demonstrates the presence of internal built-in electric fields (BIEFs) at the as-synthesized 2D OIRPP single crystals. Spontaneous Franz-Keldysh oscillations, which usually act as the fingerprint to account for the presence of BIEFs in the MQW-like structures, are observed at 2D OIRPPs by the highly sensitive differential technique of modulated thermoreflectance spectroscopy. The strength of BIEFs at 2D OIRPP single crystals reduces with increased n values due to the increased width of the quantum well. The origin of the presence of BIEFs at 2D OIRPPs is further unveiled by atomically resolved scanning tunneling microscopy on their electronic band structures at organic-inorganic interfaces. Unlike the conventional III-V MQW semiconductors with the BIEFs, which are dominated by the spatial concentration gradients at heterointerfaces, the presence of BIEFs at the 2D OIRPP single crystals is attributed to the molecular dipoles within organic spacers pointing to the organic-inorganic interfaces. The discovery of internal BIEFs at the 2D OIRPPs may provide deep insight into understanding the fundamental optical properties for the future design of large-area and low-cost perovskite optoelectronic devices.

CsPbI3-Based Phase-Stable 2D Ruddlesden-Popper Perovskites for Efficient Solar Cells.

Inorganic CsPbI3 perovskite has shown great promise in highly stable perovskite solar cells due to the lack of volatile organic components. However, the inferior phase stability in ambient conditions resulted from the very small Cs+, limiting their practical applications. Here, CsPbI3-based 2D Ruddlesden-Popper (RP) perovskites were developed using two thiophene-based aromatic spacers, namely, 2-thiophenemethylamine hydroiodide (ThMA) and 2-thiopheneformamidine hydroiodide (ThFA), which significantly improved the phase stability by releasing the large inner stress of black-phase CsPbI3. The optimized ThFA-based 2D RP perovskite (n = 5, ThFA-Cs) device achieves a record efficiency of 16.00%. Importantly, the ThFA-Cs devices could maintain an average of 98% of their initial efficiencies after being stored in N2 at room temperature for 3000 h and 92% of their initial value at 80 °C for 960 h. This work provides a new perspective for exploration of the phase-stable CsPbI3-based perovskite with reduced dimensions for high-performance solar cells.

Van der Waals MoS2/Two-Dimensional Perovskite Heterostructure for Sensitive and Ultrafast Sub-Band-Gap Photodetection.

Two-dimensional (2D) hybrid perovskites have been extensively studied as the promising light-sensitive materials in the photodetectors owing to their improved structural stability over that of their three-dimensional counterparts. However, the application of the 2D perovskite-based photodetector in the near-infrared (NIR) region is obstructed by the large intrinsic optical band gap. Herein, we develop a novel van der Waals heterostructure composed of few-layer 2D perovskite/MoS2 nanoflakes, which exhibits high-sensitivity detection performance over a broad spectral region, from the visible region to the telecommunication wavelength (i.e., 1550 nm). In particular, the photoresponsivity and specific detectivity under an 860 nm laser reach 121 A W-1 and 4.3 × 1014 Jones, respectively, whereas the individual nanoflakes show no response under the same wavelength. Meanwhile, the response time at the microsecond (µs) level is obtained, shortened by around 3 orders of magnitude compared to that of the constituting layers. The sensitive and ultrafast photoresponse at the NIR wavelength stems from the strong interlayer transition of sub-band-gap photons and the rapid separation of the photogenerated carriers by the built-in field within the heterojunction area. Our results not only provide an effective approach to achieve sub-band-gap photodetection in 2D perovskite-based structures but also suggest a universal strategy to fabricate high-performance optoelectronic devices.

Flexible SnO Optoelectronic Memory Based on Light-Dependent Ionic Migration in Ruddlesden-Popper Perovskite.

Nonvolatile optoelectronic memories based on organic-inorganic hybrid perovskites have appeared as powerful candidates for next-generation soft electronics. Here, ambipolar SnO transistor-based nonvolatile memories with multibit memory behavior (11 storage states, 120 nC state-1) and ultralong retention time (>105 s) are demonstrated for which an Al2O3/two-dimensional Ruddlesden-Popper perovskite (2D PVK) heterostructure dielectric architecture is employed. The unique storage features are attributed to suppressed gate leakage by Al2O3 layer and hopping-like ionic transport in 2D PVK with varying activation energy under different light intensities. The photoinduced field-effect mechanism enables top-gated transistor operation under illumination, which would not be achieved under dark. As a result, the device exhibits remarkable photoresponsive characteristics, including ultrahigh specific detectivity (2.7 × 1015 Jones) and broadband spectrum distinction capacity (375-1064 nm). This study offers valuable insight on the PVK-based dielectric engineering for information storage and paves the way toward multilevel broadband-response optoelectronic memories.

Drop-Casting Method to Screen Ruddlesden-Popper Perovskite Formulations for Use in Solar Cells.

Small-area metal-halide perovskite solar cells (PSCs) having power-conversion efficiencies (PCEs) of greater than 25% can be prepared by using a spin-coated perovskite layer, but this technique is not readily transferrable to large-scale manufacturing. Drop-casting is a simple alternative method for film formation that is more closely aligned to industry-relevant coating processes. In the present work, drop-casting was used to prepare films for screening two-dimensional Ruddlesden-Popper (2DRP) metal-halide perovskite formulations for potential utility in PSCs, without additional processing steps such as inert-gas blowing or application of antisolvent. The composition of the 2DRP formulation used for drop-casting was found to have a profound effect on optical, spectroscopic, morphological, and phase-distribution properties of the films as well as the photovoltaic performance of related PSC devices. This facile method for screening film quality greatly assists in speeding up the identification of perovskite formulations of interest. The optimal 2DRP perovskite formulation identified from screening was utilized for industry-relevant one-step roll-to-roll slot-die coating on a flexible plastic substrate, producing PSCs having PCEs of up to 8.8%. A mechanism describing film formation and phase distribution in the films is also proposed.

Dimensional structure regulation of organic-inorganic hybrid perovskite and its application in thin film transistors.

The effects of dimensional structure on the properties of lead iodide perovskite (C8H9NH3)2(CH3NH3)n-1PbnI3n+1were investigated. Furthermore, perovskite thin films with different dimensionalities were applied as the channel layer of thin film transistors (TFT). The electrical performance and stability of TFT devices were significantly improved through the regulation of dimensional microstructure of the perovskites. As a result, the quasi-2D (n = 6) perovskite TFTs achieved a field-effect mobility (µFE) of 3.90 cm2V-1s-1, with 104on-off current ratio and -1.85 V threshold voltage, which can be maintained well after 4 days without degradation at 30% ambient humidity. Moreover, the electrical performance of the TFTs based on Pure-2D and Quasi-2D perovskite also exhibited a good bias stability.

Fabricating efficient and stable quasi-3D and 3D/2D perovskite solar cells with 2D-sheets connected by inorganic type ionic-bond.

In this work, we report a novel two-dimensional (2D) (SrBr)2PbI4perovskite layered architecture, which were formed by the reaction of strontium bromide (SrBr2), strontium iodide (SrI2) and lead iodide (PbI2). Formation of 2D (SrBr)2PbI4was verified by small angle XRD peak at 6.4°, which corresponds to the layer distance of 13.78 Å. The best one of solar cells fabricated with Quasi-3D perovskite, (SrBr)2FA59Pb60I181(n= 60), showed a power conversion efficiency (PCE) of 18.46% and retained 95% of the initial PCE at 1000 h in the dry air. Further, the 2D (SrBr)2PbI4as the surface passivation layer on the 3D FAPbI3perovskite greatly reduced the defects at the perovskite/Spiro-OMeTAD interface, and the corresponding solar cells with FAPbI3/(SrBr)2PbI43D/2D structure achieved a PCE of 22.14% and over 90% retention of the original PCE at 1000 h. In short, this work provides an example of inorganic complex cations that can form 2D perovskites and achieve perovskite solar cells with high PCE and stabilization at the same time.