Topological band engineering of graphene nanoribbons.

Topological insulators are an emerging class of materials that host highly robust in-gap surface or interface states while maintaining an insulating bulk1,2. Most advances in this field have focused on topological insulators and related topological crystalline insulators3 in two dimensions4-6 and three dimensions7-10, but more recent theoretical work has predicted the existence of one-dimensional symmetry-protected topological phases in graphene nanoribbons (GNRs)11. The topological phase of these laterally confined, semiconducting strips of graphene is determined by their width, edge shape and terminating crystallographic unit cell and is characterized by a [Formula: see text] invariant12 (that is, an index of either 0 or 1, indicating two topological classes-similar to quasi-one-dimensional solitonic systems13-16). Interfaces between topologically distinct GNRs characterized by different values of [Formula: see text] are predicted to support half-filled, in-gap localized electronic states that could, in principle, be used as a tool for material engineering11. Here we present the rational design and experimental realization of a topologically engineered GNR superlattice that hosts a one-dimensional array of such states, thus generating otherwise inaccessible electronic structures. This strategy also enables new end states to be engineered directly into the termini of the one-dimensional GNR superlattice. Atomically precise topological GNR superlattices were synthesized from molecular precursors on a gold surface, Au(111), under ultrahigh-vacuum conditions and characterized by low-temperature scanning tunnelling microscopy and spectroscopy. Our experimental results and first-principles calculations reveal that the frontier band structure (the bands bracketing filled and empty states) of these GNR superlattices is defined purely by the coupling between adjacent topological interface states. This manifestation of non-trivial one-dimensional topological phases presents a route to band engineering in one-dimensional materials based on precise control of their electronic topology, and is a promising platform for studies of one-dimensional quantum spin physics.

Engineering Robust Metallic Zero-Mode States in Olympicene Graphene Nanoribbons.

Metallic graphene nanoribbons (GNRs) represent a critical component in the toolbox of low-dimensional functional materials technology serving as 1D interconnects capable of both electronic and quantum information transport. The structural constraints imposed by on-surface bottom-up GNR synthesis protocols along with the limited control over orientation and sequence of asymmetric monomer building blocks during the radical step-growth polymerization have plagued the design and assembly of metallic GNRs. Here, we report the regioregular synthesis of GNRs hosting robust metallic states by embedding a symmetric zero-mode (ZM) superlattice along the backbone of a GNR. Tight-binding electronic structure models predict a strong nearest-neighbor electron hopping interaction between adjacent ZM states, resulting in a dispersive metallic band. First-principles density functional theory-local density approximation calculations confirm this prediction, and the robust, metallic ZM band of olympicene GNRs is experimentally corroborated by scanning tunneling spectroscopy.

Synergetic Bottom-Up Synthesis of Graphene Nanoribbons by Matrix-Assisted Direct Transfer.

The scope of graphene nanoribbon (GNR) structures accessible through bottom-up approaches is defined by the intrinsic limitations of either all-on-surface or all-solution-based synthesis. Here, we report a hybrid bottom-up synthesis of GNRs based on a Matrix-Assisted Direct (MAD) transfer technique that successfully leverages technical advantages inherent to both solution-based and on-surface synthesis while sidestepping their drawbacks. Critical structural parameters tightly controlled in solution-based polymerization reactions can seamlessly be translated into the structure of the corresponding GNRs. The transformative potential of the synergetic bottom-up approaches facilitated by the MAD transfer techniques is highlighted by the synthesis of chevron-type GNRs (cGNRs) featuring narrow length distributions and a nitrogen core-doped armchair GNR (N4-7-ANGR) that remains inaccessible using either a solution-based or an on-surface bottom-up approach alone.

Revealing the Local Electronic Structure of a Single-Layer Covalent Organic Framework through Electronic Decoupling.

Covalent organic frameworks (COFs) are molecule-based 2D and 3D materials that possess a wide range of mechanical and electronic properties. We have performed a joint experimental and theoretical study of the electronic structure of boroxine-linked COFs grown under ultrahigh vacuum conditions and characterized using scanning tunneling spectroscopy on Au(111) and hBN/Cu(111) substrates. Our results show that a single hBN layer electronically decouples the COF from the metallic substrate, thus suppressing substrate-induced broadening and revealing new features in the COF electronic local density of states (LDOS). The resulting sharpening of LDOS features allows us to experimentally determine the COF band gap, bandwidths, and the electronic hopping amplitude between adjacent COF bridge sites. These experimental parameters are consistent with the results of first-principles theoretical predictions.

Bottom-up Assembly of Nanoporous Graphene with Emergent Electronic States.

The incorporation of nanoscale pores into a sheet of graphene allows it to switch from an impermeable semimetal to a semiconducting nanosieve. Nanoporous graphenes are desirable for applications ranging from high-performance semiconductor device channels to atomically thin molecular sieve membranes, and their performance is highly dependent on the periodicity and reproducibility of pores at the atomic level. Achieving precise nanopore topologies in graphene using top-down lithographic approaches has proven to be challenging due to poor structural control at the atomic level. Alternatively, atomically precise nanometer-sized pores can be fabricated via lateral fusion of bottom-up synthesized graphene nanoribbons. This technique, however, typically requires an additional high temperature cross-coupling step following the nanoribbon formation that inherently yields poor lateral conjugation, resulting in 2D materials that are weakly connected both mechanically and electronically. Here, we demonstrate a novel bottom-up approach for forming fully conjugated nanoporous graphene through a single, mild annealing step following the initial polymer formation. We find emergent interface-localized electronic states within the bulk band gap of the graphene nanoribbon that hybridize to yield a dispersive two-dimensional low-energy band of states. We show that this low-energy band can be rationalized in terms of edge states of the constituent single-strand nanoribbons. The localization of these 2D states around pores makes this material particularly attractive for applications requiring electronically sensitive molecular sieves.

Super-Resolution Imaging of Clickable Graphene Nanoribbons Decorated with Fluorescent Dyes.

The functional integration of atomically defined graphene nanoribbons (GNRs) into single-ribbon electronic device architectures has been limited by access to nondestructive high-resolution imaging techniques that are both compatible with common supports such as Si or Si/SiO2 wafers and capable of resolving individual ribbons in dilute samples. Conventional techniques such as scanning probe (AFM, STM) or electron microscopy (SEM, TEM) have been restricted by requisite sample preparation techniques that are incompatible with lithographic device fabrication. Here we report the design and synthesis of ultralong (∼10 µm) cove-type GNRs (cGNRs) featuring azide groups along the edges that can serve as a universal handle for late-stage functionalization with terminal alkynes. Copper-catalyzed click-chemistry with Cy5 fluorescent dyes gives rise to cGNRs decorated along the edges with fluorescent tags detectable by optical microscopy. The structures of individual dye-functionalized cGNRs spin-coated from a dilute solution onto transparent and opaque insulating substrates were resolved using diffraction-limited fluorescence microscopy and super-resolution microscopy (SRM) imaging techniques. Analysis of SRM images reveals an apparent width of cGNRs in the range 40-50 nm and lengths in excess of 10 µm, the longest GNRs imaged to date. Isolated cGNRs can even be distinguished from bundles and larger aggregates as long as the center-to-center distance is greater than the apparent width.

Synergistic Enhancement of Electrocatalytic CO2 Reduction with Gold Nanoparticles Embedded in Functional Graphene Nanoribbon Composite Electrodes.

Regulating the complex environment accounting for the stability, selectivity, and activity of catalytic metal nanoparticle interfaces represents a challenge to heterogeneous catalyst design. Here we demonstrate the intrinsic performance enhancement of a composite material composed of gold nanoparticles (AuNPs) embedded in a bottom-up synthesized graphene nanoribbon (GNR) matrix for the electrocatalytic reduction of CO2. Electrochemical studies reveal that the structural and electronic properties of the GNR composite matrix increase the AuNP electrochemically active surface area (ECSA), lower the requisite CO2 reduction overpotential by hundreds of millivolts (catalytic onset > -0.2 V versus reversible hydrogen electrode (RHE)), increase the Faraday efficiency (>90%), markedly improve stability (catalytic performance sustained over >24 h), and increase the total catalytic output (>100-fold improvement over traditional amorphous carbon AuNP supports). The inherent structural and electronic tunability of bottom-up synthesized GNR-AuNP composites affords an unrivaled degree of control over the catalytic environment, providing a means for such profound effects as shifting the rate-determining step in the electrocatalytic reduction of CO2 to CO, and thereby altering the electrocatalytic mechanism at the nanoparticle surface.

Rationally Designed Topological Quantum Dots in Bottom-Up Graphene Nanoribbons.

Bottom-up graphene nanoribbons (GNRs) have recently been shown to host nontrivial topological phases. Here, we report the fabrication and characterization of deterministic GNR quantum dots whose orbital character is defined by zero-mode states arising from nontrivial topological interfaces. Topological control was achieved through the synthesis and on-surface assembly of three distinct molecular precursors designed to exhibit structurally derived topological electronic states. Using a combination of low-temperature scanning tunneling microscopy and spectroscopy, we have characterized two GNR topological quantum dot arrangements synthesized under ultrahigh vacuum conditions. Our results are supported by density-functional theory and tight-binding calculations, revealing that the magnitude and sign of orbital hopping between topological zero-mode states can be tuned based on the bonding geometry of the interconnecting region. These results demonstrate the utility of topological zero modes as components for designer quantum dots and advanced electronic devices.

Inducing metallicity in graphene nanoribbons via zero-mode superlattices.

The design and fabrication of robust metallic states in graphene nanoribbons (GNRs) are challenging because lateral quantum confinement and many-electron interactions induce electronic band gaps when graphene is patterned at nanometer length scales. Recent developments in bottom-up synthesis have enabled the design and characterization of atomically precise GNRs, but strategies for realizing GNR metallicity have been elusive. Here we demonstrate a general technique for inducing metallicity in GNRs by inserting a symmetric superlattice of zero-energy modes into otherwise semiconducting GNRs. We verify the resulting metallicity using scanning tunneling spectroscopy as well as first-principles density-functional theory and tight-binding calculations. Our results reveal that the metallic bandwidth in GNRs can be tuned over a wide range by controlling the overlap of zero-mode wave functions through intentional sublattice symmetry breaking.

Gas phase synthesis of [4]-helicene.

A synthetic route to racemic helicenes via a vinylacetylene mediated gas phase chemistry involving elementary reactions with aryl radicals is presented. In contrast to traditional synthetic routes involving solution chemistry and ionic reaction intermediates, the gas phase synthesis involves a targeted ring annulation involving free radical intermediates. Exploiting the simplest helicene as a benchmark, we show that the gas phase reaction of the 4-phenanthrenyl radical ([C14H9]•) with vinylacetylene (C4H4) yields [4]-helicene (C18H12) along with atomic hydrogen via a low-barrier mechanism through a resonance-stabilized free radical intermediate (C18H13). This pathway may represent a versatile mechanism to build up even more complex polycyclic aromatic hydrocarbons such as [5]- and [6]-helicene via stepwise ring annulation through bimolecular gas phase reactions in circumstellar envelopes of carbon-rich stars, whereas secondary reactions involving hydrogen atom assisted isomerization of thermodynamically less stable isomers of [4]-helicene might be important in combustion flames as well.