Phenyl Functionalization of Atomically Precise Graphene Nanoribbons for Engineering Inter-ribbon Interactions and Graphene Nanopores

Graphene nanoribbons (GNRs) attract much attention from researchers due to their tunable physical properties and potential for becoming nanoscale building blocks of electronic devices. GNRs can be synthesized with atomic precision by on-surface approaches from specially designed molecular precursors. While a considerable number of ribbons with very diverse structures and properties have been demonstrated in recent years, there have been only limited examples of on-surface synthesized GNRs modified with functional groups. In this study, we designed a nanoribbon, in which the chevron GNR backbone is decorated with phenyl functionalities, and demonstrate the on-surface synthesis of these GNRs on Au(111). We show that the phenyl modification affects the assembly of the GNR polymer precursors through π–π interactions. Scanning tunneling spectroscopy of the modified GNRs on Au(111) revealed that they have a band gap of 2.50 ± 0.02 eV, which is comparable to that of the parent chevron GNR. The phenyl functionalization leads to a shift of the band edges to lower energies, suggesting that it could be a useful tool for the GNR band structure engineering. We also investigated lateral fusion of the phenyl-modified GNRs and demonstrate that it could be used to engineer different kinds of atomically precise graphene nanopores. A similar functionalization approach could be potentially applied to other GNRs to affect their on-surface assembly, modify their electronic properties, and realize graphene nanopores with a variety of structures

Optoelectrical Molybdenum Disulfide (MoS₂)Ferroelectric Memories

In this study, we fabricated and tested electronic and memory properties of field-effect transistors (FETs) based on monolayer or few-layer molybdenum disulfide (MoS₂) on a lead zirconium titanate (Pb(Zr,Ti)O₃, PZT) substrate that was used as a gate dielectric. MoS₂–PZT FETs exhibit a large hysteresis of electronic transport with high ON/OFF ratios. We demonstrate that the interplay of polarization and interfacial phenomena strongly affects the electronic behavior and memory characteristics of MoS₂–PZT FETs. We further demonstrate that MoS₂–PZT memories have a number of advantages and unique features compared to their graphene-based counterparts as well as commercial ferroelectric random-access memories (FeRAMs), such as nondestructive data readout, low operation voltage, wide memory window and the possibility to write and erase them both electrically and optically. This dual optoelectrical operation of these memories can simplify the device architecture and offer additional practical functionalities, such as an instant optical erase of large data arrays that is unavailable for many conventional memories

Multilayer Graphitic Coatings for Thermal Stabilization of Metallic Nanostructures

We demonstrate that graphitic coatings, which consist of multilayer disordered graphene sheets, can be used for the thermal protection of delicate metal nanostructures. We studied cobalt slanted nanopillars grown by glancing angle deposition that were shown to melt at temperatures much lower than the melting point of bulk cobalt. After graphitic coatings were conformally grown over the surfaces of Co nanopillars by chemical vapor deposition, the resulting carbon-coated Co nanostructures retained their morphology at elevated temperatures, which would damage the uncoated structures. Thermal stabilization is also demonstrated for carbon-coated Ti nanopillars. The results of this study may be extended to other metallic and possibly even nonmetallic nanostructures that need to preserve their morphology at elevated temperatures in a broad range of applications

Solution-Synthesized Chevron Graphene Nanoribbons Exfoliated onto H:Si(100)

There has been tremendous progress in designing and synthesizing graphene nanoribbons (GNRs). The ability to control the width, edge structure, and dopant level with atomic precision has created a large class of accessible electronic landscapes for use in logic applications. One of the major limitations preventing the realization of GNR devices is the difficulty of transferring GNRs onto nonmetallic substrates. In this work, we developed a new approach for clean deposition of solution-synthesized atomically precise chevron GNRs onto H:Si(100) under ultrahigh vacuum. A clean transfer allowed ultrahigh-vacuum scanning tunneling microscopy (STM) to provide high-resolution imaging and spectroscopy and reveal details of the electronic structure of chevron nanoribbons that have not been previously reported. We also demonstrate STM nanomanipulation of GNRs, characterization of multilayer GNR cross-junctions, and STM nanolithography for local depassivation of H:Si(100), which allowed us to probe GNR–Si interactions and revealed a semiconducting-to-metallic transition. The results of STM measurements were shown to be in good agreement with first-principles computational modeling

Interfacial Self-Assembly of Atomically Precise Graphene Nanoribbons into Uniform Thin Films for Electronics Applications

Because of their intriguing electronic and optical properties, atomically precise graphene nanoribbons (GNRs) are considered to be promising materials for electronics and photovoltaics. However, significant aggregation and low solubility of GNRs in conventional solvents result in their poor processability for materials characterization and device studies. In this paper, we demonstrate a new fabrication approach for large-scale uniform thin films of nonfunctionalized atomically precise chevron-type GNRs. The method is based on (1) the exceptional solubility of graphitic materials in chlorosulfonic acid and (2) the original interfacial self-assembly approach by which uniform films that are single-GNR (∼2 nm) thick can be routinely prepared. These films can be transferred to various substrates including Si/SiO₂ and used for the streamlined fabrication of arrays of GNR-based devices. The described self-assembly approach should be applicable to other types of solution-synthesized atomically precise GNRs as well as large polyaromatic hydrocarbon (PAH) molecules and therefore should facilitate and streamline their device characterization

Spin Dynamics and Relaxation in Graphene Nanoribbons: Electron Spin Resonance Probing

Here we report the results of a multifrequency (∼9, 20, 34, 239.2, and 336 GHz) variable-temperature continuous wave (cw) and X-band (∼9 GHz) pulse electron spin resonance (ESR) measurement performed at cryogenic temperatures on potassium split graphene nanoribbons (GNRs). Important experimental findings include the following: (a) The multifrequency cw ESR data infer the presence of only carbon-related paramagnetic nonbonding states, at any measured temperature, with the <i>g</i> value independent of microwave frequency and temperature. (b) A linear broadening of the ESR signal as a function of microwave frequency is noticed. The observed linear frequency dependence of ESR signal width points to a distribution of <i>g</i> factors causing the non-Lorentzian line shape, and the <i>g</i> broadening contribution is found to be very small. (c) The ESR process is found to be characterized by slow and fast components, whose temperature dependences could be well described by a tunneling level state model. This work not only could help in advancing the present fundamental understanding on the edge spin (or magnetic)-based properties of GNRs but also pave the way to GNR-based spin devices

Time-Resolved Measurements of Photocarrier Dynamics in TiS₃ Nanoribbons

We report synthesis and time-resolved transient absorption measurements of TiS₃ nanoribbons. TiS₃ nanoribbons were fabricated by direct reaction of titanium and sulfur. Dynamics of the photocarriers in these samples were studied by transient absorption measurements. It was found that following ultrafast injection of nonequilibrium and hot photocarriers, the thermalization, energy relaxation, and exciton formation all occur on a subpicosecond time scale. Several key parameters describing the dynamical properties of photocarriers, including their recombination lifetime, diffusion coefficient, mobility, and diffusion length, were deduced

Nitrogen-Doping Induced Self-Assembly of Graphene Nanoribbon-Based Two-Dimensional and Three-Dimensional Metamaterials

Narrow graphene nanoribbons (GNRs) constructed by atomically precise bottom-up synthesis from molecular precursors have attracted significant interest as promising materials for nanoelectronics. But there has been little awareness of the potential of GNRs to serve as nanoscale building blocks of novel materials. Here we show that the substitutional doping with nitrogen atoms can trigger the hierarchical self-assembly of GNRs into ordered metamaterials. We use GNRs doped with eight N atoms per unit cell and their undoped analogues, synthesized using both surface-assisted and solution approaches, to study this self-assembly on a support and in an unrestricted three-dimensional (3D) solution environment. On a surface, N-doping mediates the formation of hydrogen-bonded GNR sheets. In solution, sheets of side-by-side coordinated GNRs can in turn assemble via van der Waals and π-stacking interactions into 3D stacks, a process that ultimately produces macroscopic crystalline structures. The optoelectronic properties of these semiconducting GNR crystals are determined entirely by those of the individual nanoscale constituents, which are tunable by varying their width, edge orientation, termination, and so forth. The atomically precise bottom-up synthesis of bulk quantities of basic nanoribbon units and their subsequent self-assembly into crystalline structures suggests that the rapidly developing toolset of organic and polymer chemistry can be harnessed to realize families of novel carbon-based materials with engineered properties