The ability to rationally manipulate plasmonic nanoparticles into well‐defined hierarchically patterned arrays is crucial for exploiting the property of novel optical metamaterials and is of significance for designing plasmonic devices. Before the benefits offered by hybridized plasmon modes may be fully utilized in practice, programmable plasmonic nanostructures with preset morphology and composition should be developed in advance. However, it remains a grand challenge to fabricate large‐area patterned array with highly ordered nanostructure in a low‐expertise and straightforward route. Here, high‐throughput fabrication of multiscale patterned plasmonic arrays of macroscopic surfaces and nanoscale ordering is reported. The bottom‐up ligand‐guided crystallization of nanoparticles takes place upon drying‐mediated self‐assembly at air/solution/substrate interfaces, while the macroscopic topography is regulated by rational control over local nucleation in microwrinkles. Using bimetallic nanobricks as meta‐atoms, it is demonstrated that the configuration of patterned arrays can be finely engineered as required by simply customizing the wrinkled template. It is also proved that the fabricated plasmonic arrays exhibit nearly uniform hot‐spot distribution across the entire surface, which makes them as practical substrates for the surface‐enhanced Raman scattering (SERS) applications. This facile yet efficient methodology suggests a versatile step toward the fabricating of hierarchically patterned architectures for practical device construction.

The self-assembly of plasmonic building blocks into superlattices has emerged as a promising route to fabricate metamaterials with customizable nanoscale architecture and collective properties. However, self-assembly of such plasmonic superlattice has proven challenging, owing to the low packing fraction, complex interparticle forces, and local heterogeneity. Besides, the conventional assembly of small nanoparticles usually exhibits localized defects and uncontrollable electromagnetic field distribution, limiting its functionality for real-world application. Here, we report on the self-assembly of multifacet gold nanopolyhedron (AuNPH) into high-quality giant plasmonic superlattice sheets. This bottom-up method involves soft ligandbalanced crystallization of AuNPHs in conjunction with drying-mediated self-assembly. Such AuNPHs superlattice sheets exhibit macroscopic surface area while maintaining a highly ordered nanoscopic structure. We also demonstrate by both experiment and theoretical simulation that the surface-plasmon-induced hotspots are uniformly distributed across the sheet surface, facilitating its application as flexible surface-enhanced Raman scattering (SERS) sensors for detection of 4-aminothiophenol. The Raman enhancement factor (EF) of this flexible SERS sensor can reach 1.7 × 10 6 with a detection limit reaching the nanomolar scale. Moreover, the Raman signals exhibited high homogeneity across the superlattice sheets with a low relative standard deviation of 4.3%. Such flexible AuNPHs superlattice sheets can be applied as nonconventional SERS platforms with well-defined customizability, suggesting a robust and efficient avenue for real-world applications in high-sensitive inspection of drugs, explosives, and environmental pollutants.

On the basis of an abundance of elemental plasmonic nanocrystals identifiable by their unique morphology and intrinsic optoelectronic properties, it is necessary to rationally tailor the structural parameters to optimize the functionalities of nanoassemblies for application as plasmonic circuits/devices. Among them, the plasmonic superlattice membrane has emerged as a novel optically active metamaterial, which is constructed by nanocrystals at a twodimensional (2D) plane with a highly ordered structure and strong plasmonic coupling interactions. Here, we report on the fabrication of a novel plasmonic superlattice membrane using bimetallic core−shell nano-sea urchins (Nano-SEUs) as meta-atoms. Under the guidance of soft-ligand balancing in conjugation with drying-mediated self-assembly at the air/water interface, well-defined giant 2D superlattices with total lateral dimensions of up to 5 mm wide and 80 nm thick have been synthesized, corresponding to an aspect ratio of 62 500. Programmable morphology control over the Nano-SEUs has been achieved in high yield by rationally tuning the spiky branches as well as the thickness of the silver shell, allowing systematic variation of the plasmonic properties of the membrane. Such superlattice membranes exhibited a strong and reproducible surface-enhanced Raman spectroscopy (SERS) signal that originates from interparticle coupling and electric (E)-field enhancement, enabling an enhancement factor of up to 10 6 . We also demonstrated that the fabricated membrane allows the label-free SERS detection of dopamine from 0.1 nM to 1 μM. Thus, this giant Nano-SEU assembled superlattice membrane can be used as a SERS substrate for on-spot biomarker detection, which paves a robust and inexpensive avenue for highly sensitive and reliable biomedical sensing and diagnostics.

Stretchable electronics (i.e., Elastronics) are essential to the realization of next‐generation wearable bioelectronics for personalized medicine, due to their unique skin‐conformal features ideal for seamless integration with the human body. Significant progress has been made to nanowire‐based elastronics with promising applications ranging from electronic‐skin to advanced energy harvest systems. However, it remains a key challenge to rationally control over the nanowire morphology and configurations to achieve desired multifunctionality. Herein, a stretchable jellyfish‐like gold nanowires film with high conductivity and stretchability is presented by using gold nanostar‐seeded nanowire growth method. They exhibit unique hierarchically oriented structure with gold nanostars as the multi‐branched active sites (top layer) and vertically intertwined nanowires (bottom layer) trailing below the nanostars. Such nanowires film can be stretched up to 200% with a retaining low normalized resistance of 13.8 due to the unique hierarchical structure. Furthermore, the film can be used as stretchable supercapacitor with a 92% capacitance retention and superior durability even after 5000 electrochemical scanning cycles. The method is general, which can be further expanded to other metallic seeds, hence, representing a low‐cost yet efficient strategy for the fabrication of stretchable elastronics and robust energy storage devices for on‐body biosensing and bioelectronics.

Magnetic soft robots featuring untethered actuation and high mechanical compliance have promising applications ranging from bionics to biomedicine. However, their fixed magnetization profiles pose a challenge for adaptive shape transformation in unpredictable environments and dynamic tasks. Herein, a reprogrammable magnetic soft composite is reported by encapsulating magnetic neodymium–iron–boron microparticles with low melting alloy (LMA) and embedding them into the elastomer. Utilizing the phase transition of the LMA, the magnetic microparticles can be reoriented under an external magnetic field and they can be immobilized through LMA solidification, allowing the robot to obtain a new magnetization profile corresponding to its temporary shape. By changing the LMA composition, the robot with multiple programming temperatures can be fabricated and its local magnetization profiles can be selectively programmed in different temperature ranges. A bioinspired crawler with multimode locomotion, a reconfigurable robotic gripper capable of adaptable grasping, and reconfigurable electronic circuits are also demonstrated. This work may pave the way for the next‐generation magnetic soft robots and reconfigurable devices.