Using a first-principles total energy methodology, we investigated the properties of graphene-like carbon mono and bilayers, functionalized with nitrogen and boron atoms. The resulting stable structures were explored in terms of their potential use as nanoscale two-dimensional building blocks for self-assembly of macroscopic structures. We initially considered graphene monolayers functionalized with nitrogen and boron, but none of them was dynamically stable, in terms of the respective layer phonon spectra. Then, we considered the functionalized graphene-like bilayers (labeled as NCCN, NCNC, BCCB, and NCCB), analyzing their stability, electronic and mechanical properties, and chemical reactivity. We found that while the NCCN, NCNC, and NCCB bilayers were stable, the BCCB one was not. Additionally, the NCCN and NCCB bilayers were explored as potential two-dimensional building blocks for nanostructure self-assembly, which could form stable bulk structures. Particularly, the NCCB bilayer seemed the best choice as a building block, since the resulting 3D crystals, formed by stacking NCCB bilayers, were energetically stable.
Intricate biomineralization processes in molluscs engineer hierarchical structures with meso-, nano-, and atomic architectures that give the final composite material exceptional mechanical strength and optical iridescence on the macroscale. This multiscale biological assembly inspires new synthetic routes to complex materials. Our investigation of the prism-nacre interface reveals nanoscale details governing the onset of nacre formation using high-resolution scanning transmission electron microscopy. A wedge polishing technique provides unprecedented, large-area specimens required to span the …
Endohedral lanthanide ions packed inside carbon nanotubes (CNTs) in a one-dimensional assembly have been studied with a combination of high resolution transmission electron microscopy (HRTEM), scanning transmission X-ray microscopy (STXM), and X-ray magnetic circular dichroism (XMCD). By correlating HRTEM and STXM images we show that structures down to 30 nm are resolved with chemical contrast and record X-ray absorption spectra from endohedral lanthanide ions embedded in individual nanoscale CNT bundles. XMCD measurements of an Er$_3$N@C$_{80}$ bulk sample and a macroscopic assembly of filled…
Understanding and controlling self-assembly processes at multiple length scales is vital if we are to design and create advanced materials. In particular, our ability to organise matter on the nanoscale has advanced considerably, but still lags far behind our skill in manipulating individual molecules. New tools allowing controlled nanoscale assembly are sorely needed, as well as the physical understanding of how they work. Here, we report a new method for the production of highly anisotropic nanoparticles with controlled dimensions based on a morphological transformation process (MORPH for sh…
The colloidal processing of nearly monodisperse and highly crystalline single-domain ferroelectric or ferromagnetic nanocubes is a promising route to produce superlattice structures for integration into next-generation devices, whereas controlling the local behaviour of nanocrystals is imperative for fabricating highly-ordered assemblies. The current picture of nanoscale polarization in individual nanocrystals suggests a potential presence of a significant dipolar interaction, but its role in the condensation of nanocubes is unknown. We simulate the self-assembly of colloidal dipolar nanocubes…
Rigid, cage-like molecules, like diamondoids, show unique self-assembly behavior, such as templating 1-D nanomaterial assembly via pathways that are typically blocked for such bulky substituents. We investigate molecular forces between diamondoids to explore why molecules with high structural rigidity exhibit these novel assembly pathways. The rigid nature of diamondoids significantly lowers configurational entropy, and we hypothesize that this influences molecular interaction forces. To test this concept, we calculated the distance-dependent impact of entropy on assembly using molecular dynam…
Efforts aimed at large-scale integration of nanoelectronic devices that exploit the superior electronic and mechanical properties of single-walled carbon nanotubes (SWCNTs) remain limited by the difficulties associated with manipulation and packaging of individual SWNTs. Alternative approaches based on ultra-thin carbon nanotube networks (CNNs) have enjoyed success of late with the realization of several scalable device applications. However, precise control over the network electronic transport is challenging due to i) an often uncontrollable interplay between network coverage and its topolog…
The generation of nanoscale square and stripe patterns is of major technological importance since they are compatible with industry-standard electronic circuitry. Recently, a blend of diblock copolymer interacting via hydrogen-bonding was shown to self-assemble in square arrays. Motivated by those experiments we study, using Monte Carlo simulations, the pattern formation in a two-dimensional binary mixture of colloidal particles interacting via isotropic core-corona potentials. We find a rich variety of patterns that can be grouped mainly in aggregates that self-assemble in regular square latt…
In this work we seek to understand some of the fundamental processes that govern self-assembly at the nanoscale in the context of the formation of metallic structures on patterned co-polymer templates. To this end we focus on the experiments conducted by Lopes {\it et al} (Nature, 2001), where morphologies resulting from the evaporation-deposition of different metals on PS-b-PMMA phase separated templates were studied. We show that the different morphologies obtained can be understood in terms of the relative importance of the energetics and kinetics. We then focus on a particular morphology: …
DNA is an ideal candidate to organize matter on the nanoscale, primarily due to the specificity and complexity of DNA based interactions. Recent advances in this direction include the self-assembly of colloidal crystals using DNA grafted particles. In this article we theoretically study the self-assembly of DNA-caged particles. These nanoblocks combine DNA grafted particles with more complicated purely DNA based constructs. Geometrically the nanoblock is a sphere (DNA grafted particle) inscribed inside a polyhedron (DNA cage). The faces of the DNA cage are open, and the edges are made from dou…
Additive manufacturing at the micro- and nanoscale has seen a recent upsurge to suit the increasing demand for more elaborate structures. However, the integration and precise placement of multiple distinct materials at small scales remain a challenge. To this end, we combine here the directed capillary assembly of colloidal particles and two-photon direct laser writing (DLW) to realize a new class of multi-material microstructures. We use DLW both to fabricate 3D micro-templates to guide the capillary assembly of soft- and hard colloids, and to link well-defined arrangements of polystyrene or …
Stress resulting from mismatch between a substrate and an adsorbed material has often been thought to be the driving force for the self-assembly of nanoscale structures. Bi nanolines self-assemble on Si(001), and are remarkable for their straightness and length -- they are often more than 400 nm long, and a kink in a nanoline has never been observed. Through electronic structure calculations, we have found an energetically favourable structure for these nanolines that agrees with our scanning tunneling microscopy and photoemission experiments; the structure has an extremely unusual subsurface …
Although common in nature, the self-assembly of small molecules at sold-liquid interfaces is difficult to control in artificial systems. The high mobility of dissolved small molecules limits their residence at the interface, typically restricting the self-assembly to systems under confinement or with mobile tethers between the molecules and the surface. Small hydrogen-bonding molecules can overcome these issues by exploiting group-effect stabilization to achieve non-tethered self-assembly at hydrophobic interfaces. Significantly, the weak molecular interactions with the solid makes it possible…
Artificially ordered Ge quantum dot (QD) arrays, where confined carriers can interact via exchange coupling, may create unique functionalities such as cluster qubits and spintronic bandgap systems. Development of such arrays for quantum computing requires fine control over QD size and spatial arrangement on the sub-35 nm length scale. We employ fine-probe electron-beam irradiation to locally decompose ambient hydrocarbons onto a bare Si (001) surface. These carbonaceous patterns are annealed in UHV, forming ordered arrays of nanoscale SiC precipitates that serve as templates for subsequent Ge …
Singlet fission (SF), an exciton multiplication process occurring in organic semiconductors, offers a way to break the Shockley-Queisser limit in single-bandgap photovoltaics (PV). If the triplet excitons generated by SF can be transferred to inorganic quantum dots (QDs), where they radiatively recombine, SF based photon multiplication is achieved, converting a single high-energy photon into two low-energy photons. Such a SF photon multiplication film (SF-PMF) could raise the efficiency of the best Si-PV from 26.7% to 32.5%. But a precise nanoscale morphology is required within such a film con…
The programmable assembly of DNA strands is a promising tool for building tailored bottom-up nanostructures. Here, we present a plasmonic nanosystem obtained by the base-pairing mediated aggregation of gold nanoparticles (NPs) which are separately functionalized with two different single-stranded DNA chains. Their controlled assembly is mediated by a complementary DNA "bridge" sequence. We monitor the formation of DNA assembled NP aggregates in solution, and we study their Surface Enhanced Raman Scattering (SERS) response by comparison with the single NP constituents. We interpret the revealed…
Surface plasmon resonances generated in metallic nanostructures can be utilized to tailor electromagnetic fields. The precise spatial arrangement of such structures can result in surprising optical properties that are not found in any naturally occurring material. Here, the designed activity emerges from collective effects of singular components equipped with limited individual functionality. Top-down fabrication of plasmonic materials with a predesigned optical response in the visible range by conventional lithographic methods has remained challenging due to their limited resolution, the comp…
Graphene has been reported with record-breaking properties which have opened up huge potential applications. Considerable amount of researches have been devoted to manipulating or modify the properties of graphene to target a more smart nanoscale device. Graphene and carbon nanotube hybrid structure (GNHS) is one of the promising graphene derivate. The synthesis process and the mechanical properties are essential for the GNHS based devices. Therefore, this review will summarise the recent progress of the highly ordered GNHS synthesis/assembly, and discuss the mechanical properties of GNHS unde…
Origins of suppressed self-diffusion of nanoscale constituents of a complex liquid
University of California, Berkeley（加州大学伯克利分校）；University of Chicago（芝加哥大学）；Arizona State University（亚利桑那州立大学）；Sorbonne Université（索邦大学）；CNRS（法国国家科学研究中心）；California Institute of Technology（加州理工学院）；Brookhaven National Laboratory（布鲁克海文国家实验室）；SLAC National Accelerator Laboratory（斯坦福直线加速器中心）
Molecular self-assembly, the function of biomembranes, and the performance of organic solar cells rely on molecular interactions on the nanoscale. The understanding and design of such intrinsic or engineered heterogeneous functional soft matter has long been impeded by a lack of spectroscopic tools with sufficient nanometer spatial resolution, attomolar sensitivity, and intermolecular spectroscopic specificity. We implement vibrational scattering-scanning near-field optical microscopy ($s$-SNOM) in a multi-spectral modality with unprecedented spectral precision to investigate the structure-fun…
The synthesis of single-wall carbon nanotubes (SWCNTs) of desired diameters and chiralities is critical to the design of nanoscale electronic devices with desired properties.1-6 The existing methods are based on self-assembly, 7-16 therefore lacking the control over their diameters and chiralities. The present work reports a direct route to roll graphene. Specifically, we found that the electrostatic deposition of graphene yielded: (i) flat graphene layers under high vacuum (10-7 Torr), (ii) completely scrolled graphene under hydrogen atmosphere, (iii) partially scrolled graphene under nitroge…
