Rashba Effect and Spin-Dependent Excitonic Properties in Chiral Two-Dimensional/Three-Dimensional Composite Perovskite Films.

Among various chiral semiconductor materials, chiral two-dimensional (2D)/three-dimensional (3D) composite perovskites (CPs) offer the benefits of strong interface asymmetry and energy transfer between 2D and 3D phases, making the chiral CPs promising for spintronic devices. Therefore, understanding their spintronic properties will be greatly important for expanding their relevant applications. In this work, we synthesized one pair of chiral 2D/3D CP films. Their Rashba effect and spin relaxation process have been investigated by polarization-dependent femtosecond transient absorption spectroscopy. Interestingly, under left- and right-handed circularly polarized light (CPL) excitation, a two-photon emission intensity difference is observed in chiral 2D/3D CP films at 298 K. This work sheds light on the spin-dependent excitonic characteristics of chiral 2D/3D CPs and confirms the feasibility of their application in near-infrared CPL detection.

Improving the Five-Photon Absorption from Core-Shell Perovskite Nanocrystals.

It is necessary to improve the action cross section (η × σn) of high-order multiphoton absorption (MPA) for fundamental research and practical applications. Herein, the core-shell FAPbBr3/CsPbBr3 nanocrystals (NCs) were constructed, and fluorescence induced by up to five-photon absorption was observed. The value of η × σ5 reaches 8.64 × 10-139 cm10 s4 photon-4 nm-3 at 2300 nm, which is nearly an order of magnitude bigger than that of the core-only NCs. It is found that the increased dielectric constant promotes modulation of MPA effects, addressing the electronic distortion in high-order nonlinear behaviors through the local field effect. Meanwhile, the quasi-type-II band alignment suppresses the biexciton Auger recombination, ensuring the stronger MPA induced fluorescence. In addition, the core-shell structure can not only reduce the defect density but also promote the nonradiative energy transfer though the antenna-like effect. This work provides a new avenue for the exploitation of high-performance multiphoton excited nanomaterials for future photonic integration.

Spatially Correlated Chirality in Chiral Two-Dimensional Perovskites Revealed by Second-Harmonic-Generation Circular Dichroism Microscopy.

Understanding the chiral mechanism of chiral hybrid perovskites is a prerequisite for developing relevant chiroptoelectronic applications. Although conventional circular dichroism (CD) spectroscopy can be used to characterize chirality in chiral perovskites, it has a low signal-to-noise ratio and can provide only information about macroscopic chirality. Herein, with the aim of revealing the microscopic chiral mechanism in chiral perovskites, we utilize a spacer cation alloying strategy to construct chiral two-dimensional perovskites. For the first time, we demonstrate second-harmonic-generation CD microarea imaging in chiral perovskite thin films to unveil their spatially correlated chirality. In combination with theoretical calculations, it is revealed that the spatially correlated chirality is caused by localized out-of-plane supramolecular orientations. This work will not only advance the understanding of the mechanism of chiroptical activity in chiral perovskites but also provide inspiration for the rational design and synthesis of perovskites for chirality-related nonlinear optoelectronic devices.

Enhanced Performance of Two-Photon Excited Amplified Spontaneous Emission by Cd-Alloyed CsPbBr3 Nanocrystals.

It has been demonstrated that the alloyed perovskite nanocrystals (NCs) with a small amount of Cd element may passivate the inherent halide vacancies in perovskite NCs and improve their stability. However, the study of the optical properties of such alloyed perovskite NCs still remains essentially untouched, which will seriously hinder relevant applications. Herein, using different amounts of CdBr2 as an alloyed metal precursor, a series of CsPbxCd1-xBr3 NCs (x = 1, 0.93, and 0.88) were synthesized. Compared with bare CsPbBr3 NCs, the Cd-alloyed NCs exhibited a near-unity photoluminescence quantum yield (99%), efficiently improved stability, and enhanced electron-phonon coupling strength. As the Cd-alloyed amount was increased, their hot-carrier cooling time became faster and the exciton-biexciton interaction decreased, causing a decreased threshold of two-photon excited amplified spontaneous emission (ASE) from 1.58 to 1.23 mJ cm-2. In addition, the Cd-alloying method can also improve the photostability of ASE, resulting in the initial ASE intensity remaining at 90% even after 7.5 × 105 pulse shots. This work implies that the Cd-alloyed CsPbBr3 NCs will be promising for application in a laser gain medium.

Regulating Optical Activity and Anisotropic Second-Harmonic Generation in Zero-Dimensional Hybrid Copper Halides.

Structural engineering permits the introduction of chirality into organic-inorganic hybrid metal halides (HMHs), which creates a promising and exclusive material for applications in various optoelectronics. However, the optical activity regulation of chiral HMHs remains largely unexplored. In this work, we have synthesized two pairs of lead-free chiral HMHs with a zero-dimensional tetrahedral arrangement, i.e., (R- and S-1-(1-naphthyl)ethylammonium)2CuCl4 and (R- and S-1-(2-naphthyl)ethylammonium)2CuCl4. The magnitude of optical activity in these HMHs can be efficiently modulated as a result of the different magnetic transition dipole moments. Furthermore, these HMHs exhibited effective second-harmonic generation (SHG) and distinct SHG-circular dichroism (CD), with (R-1-(1-naphthyl)ethylammonium)2CuCl4 having an anisotropy factor (gSHG-CD) of up to 0.41. This work not only provides insights into regulating the optical activity and anisotropic SHG effect of lead-free chiral HMHs but also confirms the feasibility of SHG-CD spectroscopy as a promising tool for characterizing the intrinsic optical activity of chiral materials.

Strong two-photon absorption induced by energy funneling in chiral quasi-2D perovskites.

Quasi-2D Ruddlesden-Popper-type perovskites (RPPs) exhibit excellent nonlinear optical properties due to their multiple quantum well structures with large exciton binding energy. Herein, we introduce chiral organic molecules into RPPs and investigate their optical properties. It is found that the chiral RPPs possess effective circular dichroism in the ultraviolet to visible wavelengths. Two-photon absorption (TPA)-induced efficient energy funneling from small- to large-n domains is observed in the chiral RPP films, which induces strong TPA with a coefficient up to 4.98 cm MW-1. This work will broaden the application of quasi-2D RPPs in chirality-related nonlinear photonic devices.

Quasi-Type II Core-Shell Perovskite Nanocrystals for Improved Structural Stability and Optical Gain.

In recent years, core-shell lead halide perovskite nanocrystals (PeNCs) and their devices have attracted intensive attention owing to nearly perfect optoelectronic properties. However, the complex photophysical mechanism among them is still unclear. Herein, monodispersed core-shell PeNCs coated with an all-inorganic cesium lead bromide (CsPbBr3) shell epitaxially grown on the surface of formamidinium lead bromide (FAPbBr3) PeNCs were synthesized. Through power- and temperature-dependent photoluminescence (PL) measurements, it is found that the electronic structure of the core-shell FAPbBr3/CsPbBr3 PeNCs has a quasi-type II band alignment. The presence of Cs+ in the shell limits ion migration and helps to stabilize structural and optical properties. On this basis, after being exposed to pulsed nanosecond laser for a period, an amplified spontaneous emission (ASE) can be observed, which is attributed to the effective passivation induced by laser irradiation on defects at the interface. The ASE threshold of the core-shell PeNCs showing high structural and optical stability is 447 nJ/cm2 under pulsed nanosecond optical pumping. The results that are demonstrated here provide a new idea and perspective for improving the stability of perovskite and can be of practical interest for the utilization of the core-shell PeNCs in optoelectronic devices.

Giant Optical Activity and Second Harmonic Generation in 2D Hybrid Copper Halides.

Hybrid organic-inorganic metal halides have emerged as highly promising materials for a wide range of applications in optoelectronics. Incorporating chiral organic molecules into metal halides enables the extension of their unique optical and electronic properties to chiral optics. By using chiral (R)- or (S)-methylbenzylamine (R-/S-MBA) as the organic component, we synthesized chiral hybrid copper halides, (R-/S-MBA)2 CuCl4 , and investigated their optical activity. Thin films of this material showed a record anisotropic g-factor as high as approximately 0.06. We discuss the origin of the giant optical activity observed in (R-/S-MBA)2 CuCl4 by theoretical modeling based on density functional theory (DFT) and demonstrate highly efficient second harmonic generation (SHG) in these samples. Our study provides insight into the design of chiral materials by structural engineering, creating a new platform for chiral and nonlinear photonic device applications of the chiral hybrid copper halides.

All-inorganic copper(i)-based ternary metal halides: promising materials toward optoelectronics.

All-inorganic lead halides, including CsPbX3 (X = Cl, Br, I), have become important candidate materials in the field of optoelectronics. However, the inherent toxicity of metal lead and poor material stability have hindered further applications of traditional metal halides, CsPbX3. Therefore, copper(i)-based ternary metal halides are expected to become promising substitutes for traditional metal halides because of their nontoxicity, excellent optical properties and good stability under ambient conditions. This article reviews the recent development of all-inorganic low-dimensional copper(i)-based ternary metal halides by introducing their various synthesis methods, crystal structures, properties and their optoelectronic applications. In addition, the prospects for future challenges and the potential significance of copper(i)-based ternary metal halides in optoelectronic fields are presented.