The spontaneous organization of multicomponent micrometre-sized colloids or nanocrystals into superlattices is of scientific importance for understanding the assembly process on the nanometre scale and is of great interest for bottom-up fabrication of functional devices. In particular, co-assembly of two types of nanocrystal into binary nanocrystal superlattices (BNSLs) has recently attracted significant attention, as this provides a low-cost, programmable way to design metamaterials with precisely controlled properties that arise from the organization and interactions of the constituent nanocrystal components. Although challenging, the ability to grow and manipulate large-scale BNSLs is critical for extensive exploration of this new class of material. Here we report a general method of growing centimetre-scale, uniform membranes of BNSLs that can readily be transferred to arbitrary substrates. Our method is based on the liquid-air interfacial assembly of multicomponent nanocrystals and circumvents the limitations associated with the current assembly strategies, allowing integration of BNSLs on any substrate for the fabrication of nanocrystal-based devices. We demonstrate the construction of magnetoresistive devices by incorporating large-area (1.5 mm x 2.5 mm) BNSL membranes; their magnetotransport measurements clearly show that device magnetoresistance is dependent on the structure (stoichiometry) of the BNSLs. The ability to transfer BNSLs also allows the construction of free-standing membranes and other complex architectures that have not been accessible previously.

The modular assembly of multicomponent nanocrystal (NC) superlattices enables new metamaterials with programmable properties. While self-assembly of three-dimensional (3D) binary NC superlattices (BNSLs) has advanced significantly in the past decade, limited progress has been made to grow 2D BNSLs such as monolayers and bilayers over extended areas. Here, we report the growth of large-area (∼ 1 cm(2)), transferable BNSL monolayers using the liquid-air interfacial assembly approach. The BNSL monolayers are formed by an entropy-driven assembly process with structures tunable by varying the NC size ratio. We further demonstrate the liquid-air interfacial assembly of BNSL bilayers which exhibit unique superlattice structures that have not been observed in the 3D BNSLs. As a further extension, bilayered ternary NC superlattices (TNSLs) are obtained by the cocrystallization of three types of NCs at the liquid-air interface.

Co-assembly of two types of nanocrystals (NCs) into binary NC superlattices (BNSLs) provides a solution-based, inexpensive way to create novel metamaterials with rationally designed properties. The fundamental challenge is to probe and understand the nature and extent of complex interparticle interactions present in BNSLs, which can lead to collective properties that differ from their dispersed constituents or phase-separated counterparts. Here, we report the growth and magnetic characterization of large-area (∼1 cm(2)) BNSL membranes self-assembled from distinct magnetic NCs at the liquid-air interface. The resulting BNSL membranes exhibit a single-phase-like magnetization alignment process, which is not observed in the phase-separated NC mixtures having the same stoichiometry. This single-phase-like magnetic behavior is attributed to the collective interparticle dipolar interactions between two NC components in BNSLs, corroborated by calculation of the random dipolar fields as well as Monte Carlo simulation. The collective magnetic properties are demonstrated in magnetic BNSL membranes having different structures (stoichiometry) and different NC combinations.

Monodisperse Sn spherical nanocrystals of 10.0 ± 0.2 nm were prepared in dispersible colloidal form. They were used as a model platform to study the impact of size on the accommodation of colossal volume changes during electrochemical lithiation using ex situ transmission electron microscopy (TEM). Significant mechanical damage was observed after full lithiation, indicating that even crystals at these very small dimensions are not sufficient to prevent particle pulverization that compromises electrode durability.

The ability to remove long, insulating ligands from nanocrystal (NC) surfaces without deteriorating the structural integrity of NC films is critical to realizing their electronic and optoelectronic applications. Here we report a nondestructive ligand-exchange approach based on in situ chemical treatment of NCs floating at the liquid-air interface, enabling strongly coupled NC superlattice films that can be directly transferred to arbitrary substrates for device applications. Ligand-exchange-induced structural defects such as cracks and degraded NC ordering that are commonly observed using previous methods are largely prevented by performing ligand exchange at the liquid-air interface. The significantly reduced interparticle spacing arising from ligand replacement leads to highly conductive NC superlattice films, the electrical conductivities and carrier mobilities of which are 1 order of magnitude higher than those of the same NC films subject to substrate-supported exchange using previously reported procedures. The in situ, free-floating exchange approach presented here opens the door for electronically coupled NC superlattices that hold great promise for high-performance, flexible electronic and optoelectronic devices.