Halide double perovskites present a new branch for versatile optoelectronic devices because of their huge structural compatibility and environmental friendliness, whereas nonlinear optics (NLO) devices remain blank for this fascinating family. Simultaneously, the precise patterning of single-crystalline perovskite microwire arrays remains a challenge for the integration of NLO devices. Herein, we designed lead-free chiral 2D double perovskites with the nonsymmetrical structure presenting second-harmonic generation (SHG). Furthermore, perovskite single-crystalline arrays with regulated geometry, pure orientation, and high crystallinity are prepared using the capillary-bridge confined assembly technique. The efficient SHG originates from the asymmetric crystal structure and high crystallinity of the microwire arrays. Compared with their polycrystalline thin-film counterparts, linearly polarized SHG and a higher SHG conversion efficiency are demonstrated based on microwire arrays. The results not only expand the applications of lead-free double perovskites in the NLO-integrated fields but also provide a viable way for lead-free optoelectronic devices.

The realization of polarized photodetection vigorously accelerates the development of applications in quantum communication, medicine, imaging, and sensing. Polarized light detection has been realized based on chiral perovskites, but the high concentrations of toxic lead and instability in those reported perovskites impose difficulties for their commercial applications. Furthermore, the precise patterning of perovskite arrays with high crystallinity is in high demand for the integration of optoelectronic devices. Herein, pure (001)‐orientated lead‐free chiral 2D double perovskite single‐crystalline microwire arrays are fabricated by the capillary‐bridge confined assembly technique. Perovskite microwire arrays present remarkable environmental stability under ambient conditions. With the synergy of the excellent crystallinity and sensitive circular‐polarization absorption of chiral perovskite microwire arrays, outstanding circularly polarized light photodetectors are realized, with responsivity exceeding 52 mA W−1 and detectivity exceeding 3.9 × 1011 Jones.

Color-cognitive detection plays an important role in many developing applications such as optical sensing, high-solution imaging, wearable biometric monitoring, and human visual cognitive system. Although color-cognitive devices have been demonstrated, the large size, complex manufacturing, high cost, and non-flexible processing impede their applications for distinguishing color information. Herein, gradient bandgap-tunable perovskite microwire arrays with excellent crystallinity and pure crystallographic orientation are realized by the synergy of the capillary-bridge assembly method and mild component engineering processing, yielding high-performance integrated color-cognitive devices with the spectral resolution of 14 nm ranging from 405 nm to 760 nm, responsivities over 10 3 A W −1 , and detectivities over 10 15 Jones. Furthermore, the integrated flexible color-cognitive devices are demonstrated for accurately recognizing similar colors, which can be applied in color blindness correction. The efficient color recognition performances, together with the flexible processing, open new opportunities for the on-chip integration of wearable devices based on microwire arrays.

Chiral hybrid halide perovskites have attracted considerable attention in optoelectronics and spintronics owing to their unique optical, electric, and spin–orbit coupling (SOC) properties. In this article, with focus on the design scheme to increase the nonlinear optical (NLO) circular dichroism (CD) and spin selectivity effects by assembling chlorine-modified chiral R-/S-CLPEA [CLPEA = 1-(4-chlorophenyl)ethylamine] into bismuth-based perovskites, a pair of chiral hybrid perovskites (R-/S-CLPEA)4Bi2I10 were synthesized and characterized experimentally. A large NLO CD effect and strong spin-dependent charge transport were confirmed by the experimental measurements. The unique chirality-induced spin textures were illustrated in the SOC band structures from first-principles simulations. The combined theoretical and experimental results demonstrate that it is the synergic effect of large chirality of CLPEA and strong SOC effect of the Bi2I10 dimer that endows these perovskites with unique chiral spin textures, strong NLO CD effect, and remarkable spin-dependent charge transport properties, which are of importance for the functional design of chiral perovskites in nonlinear optics and spintronics.

Organic nonlinear optical (NLO) crystals play an indispensable role in high‐performance photonic devices due to their large nonlinear coefficient, fast response time, and low dielectric constant. However, in contrast to the strides of bulk crystals, researches on the next generation of nanophotonic devices are ignored to some extent. One of the bottlenecks is the controllable manufacturing and patterning of high‐quality organic NLO crystals with the nanometer‐scale thickness. Herein, a confined assembly method for fabricating the microwire arrays of organic NLO crystal OH1 and DAT2 with precise position, flat morphology, high crystallinity, and consistent crystallographic orientation is reported. Two strong NLO effects observed in the experiments are comprehensively studied, including second harmonic generation (SHG) and two‐photon excited fluorescence. Furthermore, it is demonstrated that the anisotropic SHG effect depends on both the polarization of incident light and the crystallographic orientation of microwire arrays. Microwire arrays can exhibit large in‐plane anisotropy with the polarization ratio up to 0.95 and second‐order nonlinear coefficient up to 55.1 pm V−1. This work provides new insights into the potential applications of organic NLO crystals in integrated optical devices.