Porous Nanographenes, Graphene Nanoribbons, and Nanoporous Graphene Selectively Synthesized from the Same Molecular Precursor.

We demonstrate a family of molecular precursors based on 7,10-dibromo-triphenylenes that can selectively produce different varieties of atomically precise porous graphene nanomaterials through the use of different synthetic environments. Upon Yamamoto polymerization of these molecules in solution, the free rotations of the triphenylene units around the C-C bonds result in the formation of cyclotrimers in high yields. In contrast, in on-surface polymerization of the same molecules on Au(111) these rotations are impeded, and the coupling proceeds toward the formation of long polymer chains. These chains can then be converted to porous graphene nanoribbons (pGNRs) by annealing. Correspondingly, the solution-synthesized cyclotrimers can also be deposited onto Au(111) and converted into porous nanographenes (pNGs) via thermal treatment. Thus, both processes start with the same molecular precursor and end with a porous graphene nanomaterial on Au(111), but the type of product, pNG or pGNR, depends on the specific coupling approach. We also produced extended nanoporous graphenes (NPGs) through the lateral fusion of highly aligned pGNRs on Au(111) that were grown at high coverage. The pNGs can also be synthesized directly in solution by Scholl oxidative cyclodehydrogenation of cyclotrimers. We demonstrate the generality of this approach by synthesizing two varieties of 7,10-dibromo-triphenylenes that selectively produced six nanoporous products with different dimensionalities. The basic 7,10-dibromo-triphenylene monomer is amenable to structural modifications, potentially providing access to many new porous graphene nanomaterials. We show that by constructing different porous structures from the same building blocks, it is possible to tune the energy band gap in a wide range.

Tunable Magnetic Coupling in Graphene Nanoribbon Quantum Dots.

Carbon-based quantum dots (QDs) enable flexible manipulation of electronic behavior at the nanoscale, but controlling their magnetic properties requires atomically precise structural control. While magnetism is observed in organic molecules and graphene nanoribbons (GNRs), GNR precursors enabling bottom-up fabrication of QDs with various spin ground states have not yet been reported. Here the development of a new GNR precursor that results in magnetic QD structures embedded in semiconducting GNRs is reported. Inserting one such molecule into the GNR backbone and graphitizing it results in a QD region hosting one unpaired electron. QDs composed of two precursor molecules exhibit nonmagnetic, antiferromagnetic, or antiferromagnetic ground states, depending on the structural details that determine the coupling behavior of the spins originating from each molecule. The synthesis of these QDs and the emergence of localized states are demonstrated through high-resolution atomic force microscopy (HR-AFM), scanning tunneling microscopy (STM) imaging, and spectroscopy, and the relationship between QD atomic structure and magnetic properties is uncovered. GNR QDs provide a useful platform for controlling the spin-degree of freedom in carbon-based nanostructures.

Mechanical Stress Modulation of Resistance in MoS2 Junctions.

Strain engineering is a powerful strategy to control the physical properties of material-enabling devices with enhanced functionality and improved performance. Here, we investigate a modulation of the transport behavior of the two-dimensional MoS2 junctions under the mechanical stress induced by a tip of an atomic force microscope (AFM). We show that the junction resistance can be reversibly tuned by up to 4 orders of magnitude by altering a tip-induced force. Analysis of the stress-induced evolution of the I-V characteristics indicates a combined effect of the tip-induced strain and strain gradient on the energy barrier height and profile. In addition, we show that the tip-generated flexoelectric effect leads to significant enhancement of the photovoltaic effect in the MoS2 junctions. A combination of the optical and mechanical stimuli facilitates reversible photomechanical tuning of resistance of the narrow-band 2D semiconductors and development of devices with an enhanced photovoltaic response.

Bifunctional Amine- and Thiol-Modified Ti3C2Tx MXene for Trace Detection of Heavy Metals.

Surface functionalization of two-dimensional (2D) transition metal carbides, nitrides, and carbonitrides, also known as MXenes, is a powerful approach for modification of their physical and chemical properties for new applications. In this study, we demonstrate the synthesis of a bifunctional Ti3C2Tx MXene modified with amine and thiol groups through a facile condensation reaction. We successfully employed the resulting NH2/SH-Ti3C2Tx MXene as a solid phase in the ultrasonic-assisted dispersive micro solid-phase extraction (d-µ-SPE) method for the analytical determination of heavy metals at trace levels in food and soil samples. The prepared NH2/SH-Ti3C2Tx MXene showed remarkable performance in the ultrasonic-assisted d-µ-SPE method with limits of detection of 0.12 and 2.30 ng mL-1, with linear dynamic ranges of 0.50-90 µg L-1 and 10-120 µg L-1 for cadmium (Cd2+) and lead (Pb2+) ions, respectively. Furthermore, the extraction efficiencies were greater than 97%, with a relative standard deviation of less than 3% for five separate batch experiments in the determination of 5.0 µg L-1 of Cd2+ and Pb2+. This study shows that NH2/SH-Ti3C2Tx can be used as a simple, rapid, reliable, selective, and sensitive material in the d-µ-SPE method for the trace determination of Cd2+ and Pb2+ in soil and agricultural products. This study demonstrates the utility of MXenes for analytical chemistry and suggests that further advances in methods for the functionalization of MXenes can open new applications for these already exciting materials.

Effect of Au/HfS3 interfacial interactions on properties of HfS3-based devices.

X-ray photoemission spectroscopy (XPS) has been used to examine the interaction between Au and HfS3 at the Au/HfS3 interface. XPS measurements reveal dissociative chemisorption of O2, leading to the formation of an oxide of Hf at the surface of HfS3. This surface hafnium oxide, along with the weakly chemisorbed molecular species, such as O2 and H2O, are likely responsible for the observed p-type characteristics of HfS3 reported elsewhere. HfS3 devices exhibit n-type behaviour if measured in vacuum but turn p-type in air. Au thickness-dependent XPS measurements provide clear evidence of band bending as the S 2p and Hf 4f core-level peak binding energies for Au/HfS3 are found to be shifted to higher binding energies. This band bending implies formation of a Schottky-barrier at the Au/HfS3 interface, which explains the low measured charge carrier mobilities of HfS3-based devices. The transistor measurements presented herein also indicate the existence of a Schottky barrier, consistent with the XPS core-level binding energy shifts, and show that the bulk of HfS3 is n-type.

UV-Light-Tunable p-/n-Type Chemiresistive Gas Sensors Based on Quasi-1D TiS3 Nanoribbons: Detection of Isopropanol at ppm Concentrations.

The growing demand of society for gas sensors for energy-efficient environmental sensing stimulates studies of new electronic materials. Here, we investigated quasi-one-dimensional titanium trisulfide (TiS3) crystals for possible applications in chemiresistors and on-chip multisensor arrays. TiS3 nanoribbons were placed as a mat over a multielectrode chip to form an array of chemiresistive gas sensors. These sensors were exposed to isopropanol as a model analyte, which was mixed with air at low concentrations of 1-100 ppm that are below the Occupational Safety and Health Administration (OSHA) permissible exposure limit. The tests were performed at room temperature (RT), as well as with heating up to 110 °C, and under an ultraviolet (UV) radiation at λ = 345 nm. We found that the RT/UV conditions result in a n-type chemiresistive response to isopropanol, which seems to be governed by its redox reactions with chemisorbed oxygen species. In contrast, the RT conditions without a UV exposure produced a p-type response that is possibly caused by the enhancement of the electron transport scattering due to the analyte adsorption. By analyzing the vector signal from the entire on-chip multisensor array, we could distinguish isopropanol from benzene, both of which produced similar responses on individual sensors. We found that the heating up to 110 °C reduces both the sensitivity and selectivity of the sensor array.

Structure Formation and Coupling Reactions of Hexaphenylbenzene and Its Brominated Analog.

The on-surface coupling of the prototypical precursor molecule for graphene nanoribbon synthesis, 6,11-dibromo-1,2,3,4-tetraphenyltriphenylene (C42 Br2 H26 , TPTP), and its non-brominated analog hexaphenylbenzene (C42 H30 , HPB), was investigated on coinage metal substrates as a function of thermal treatment. For HPB, which forms non-covalent 2D monolayers at room temperature, a thermally induced transition of the monolayer's structure could be achieved by moderate annealing, which is likely driven by π-bond formation. It is found that the dibrominated carbon positions of TPTP do not guide the coupling if the growth occurs on a substrate at temperatures that are sufficient to initiate C-H bond activation. Instead, similar one-dimensional molecular structures are obtained for both types of precursors, HPB and TPTP.

Nanodomain Engineering for Programmable Ferroelectric Devices.

We introduce a concept of programmable ferroelectric devices composed of two-dimensional (2D) and ferroelectric (FE) materials. It enables precise modulation of the in-plane conductivity of a 2D channel material through nanoengineering FE domains with out-of-plane polarization. The functionality of these new devices has been demonstrated using field-effect transistors (FETs) fabricated with monolayer molybdenum disulfide (MoS2) channels on the Pb(Zr,Ti)O3 substrates. Using piezoresponse force microscopy (PFM), we show that local switching of FE polarization by a conductive probe can be used to tune the conductivity of the MoS2 channel. Specifically, patterning of the nanoscale domains with downward polarization creates conductive paths in a resistive MoS2 channel so that the conductivity of an FET is determined by the number and length of the paths connecting source and drain electrodes. In addition to the device programmability, we demonstrate the device ON/OFF cyclic endurance by successive writing and erasing of conductive paths in a MoS2 channel. These findings may inspire the development of advanced energy-efficient programmable synaptic devices based on a combination of 2D and FE materials.

On-Surface Synthesis and Spectroscopic Characterization of Laterally Extended Chevron Graphene Nanoribbons.

We report the on-surface synthesis and spectroscopic study of laterally extended chevron graphene nanoribbons (GNRs) and compare them with the established chevron GNRs, emphasizing the consistency of bandgap reduction of semiconducting GNRs with increased width. The laterally extended chevron GNRs grown on Au(111) exhibit a bandgap of about 2.2 eV, which is considerably smaller than the values reported for chevron GNRs in similar studies.

Chemical vapor deposition and characterization of two-dimensional molybdenum dioxide (MoO2) nanoplatelets.

We report on the chemical vapor deposition synthesis of MoO2 nanoplatelets by sublimation of MoO3 and its reduction in a hydrogen atmosphere at 750 °C. When grown on Si/SiO2 substrates, the platelets primarily assume a rhomboidal shape and have thicknesses ranging from several to tens of nm. The morphology of MoO2 crystals was found to depend on the chemical nature of substrates. MoO2 platelets on Si/SiO2 were characterized by a number of microscopic and spectroscopic techniques, and the electrical measurements revealed the metallic nature of their conductivity averaging at 2400 ± 1000 S cm-1. Raman spectroscopy of MoO2 platelets on graphene indicates their strong hole injection property. Small thickness, planar morphology, high chemical stability and metallic conductivity of ultrathin MoO2 platelets make them potentially interesting for integration different other two-dimensional materials in a variety of electronic structures and devices.

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.

Polarization-Mediated Modulation of Electronic and Transport Properties of Hybrid MoS2-BaTiO3-SrRuO3 Tunnel Junctions.

Hybrid structures composed of ferroelectric thin films and functional two-dimensional (2D) materials may exhibit unique characteristics and reveal new phenomena due to the cross-interface coupling between their intrinsic properties. In this report, we demonstrate a symbiotic interplay between spontaneous polarization of the ultrathin BaTiO3 ferroelectric film and conductivity of the adjacent molybdenum disulfide (MoS2) layer, a 2D narrow-bandgap semiconductor. Polarization-induced modulation of the electronic properties of MoS2 results in a giant tunneling electroresistance effect in the hybrid MoS2-BaTiO3-SrRuO3 ferroelectric tunnel junctions (FTJs) with an OFF-to-ON resistance ratio as high as 104, a 50-fold increase in comparison with the same type of FTJs with metal electrodes. The effect stems from the reversible accumulation-depletion of the majority carriers in the MoS2 electrode in response to ferroelectric switching, which alters the barrier at the MoS2-BaTiO3 interface. Continuous tunability of resistive states realized via stable sequential domain structures in BaTiO3 adds memristive functionality to the hybrid FTJs. The use of narrow band 2D semiconductors in conjunction with ferroelectric films provides a novel pathway for development of the electronic devices with enhanced performance.

Imaging and Analysis of Encapsulated Objects through Self-Assembled Electron and Optically Transparent Graphene Oxide Membranes.

We demonstrate a technique for facile encapsulation and adhesion of micro- and nano objects on arbitrary substrates, stencils, and micro structured surfaces by ultrathin graphene oxide membranes via a simple drop casting of graphene oxide solution. A self-assembled encapsulating membrane forms during the drying process at the liquid-air and liquid-solid interfaces and consists of a water-permeable quasi-2D network of overlapping graphene oxide flakes. Upon drying and interlocking between the flakes, the encapsulating coating around the object becomes mechanically robust, chemically protective, and yet highly transparent to electrons and photons in a wide energy range, enabling microscopic and spectroscopic access to encapsulated objects. The characteristic encapsulation scenarios were demonstrated on a set of representative inorganic and organic micro and nano-objects and microstructured surfaces. Different coating regimes can be achieved by controlling the pH of the supporting solution, and the hydrophobicity and morphology of interfaces. Several specific phenomena such as compression of encased objects by contracting membranes as well as hierarchical encapsulations were observed. Finally, electron as well as optical microscopy and analysis of encapsulated objects along with the membrane effect on the image contrast formation, and signal attenuation are discussed.

Nanodomain Engineering in Ferroelectric Capacitors with Graphene Electrodes.

Polarization switching in ferroelectric capacitors is typically realized by application of an electrical bias to the capacitor electrodes and occurs via a complex process of domain structure reorganization. As the domain evolution in real devices is governed by the distribution of the nucleation centers, obtaining a domain structure of a desired configuration by electrical pulsing is challenging, if not impossible. Recent discovery of polarization reversal via the flexoelectric effect has opened a possibility for deterministic control of polarization in ferroelectric capacitors. In this paper, we demonstrate mechanical writing of arbitrary-shaped nanoscale domains in thin-film ferroelectric capacitors with graphene electrodes facilitated by a strain gradient induced by a tip of an atomic force microscope (AFM). A phase-field modeling prediction of a strong effect of graphene thickness on the threshold load required to initiate mechanical switching has been confirmed experimentally. Deliberate voltage-free domain writing represents a viable approach for development of functional devices based on domain topology and electronic properties of the domains and domain walls.

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.

Graphene substrate for inducing neurite outgrowth.

A few recent studies demonstrated that graphene may have cytocompatibility with several cell types. However, when assessing cell behavior on graphene, there has been no precise control over the quality of graphene, number of graphene layers, and substrate surface coverage by graphene. In this study, using well-controlled monolayer graphene film substrates we tested the cytocompatibility of graphene for human neuroblastoma (SH-SY5Y) cell culture. A large-scale monolayer graphene film grown on Cu foils by chemical vapor deposition (CVD) could be successfully transferred onto glass substrates by wet transfer technique. We observed that graphene substrate could induce enhanced neurite outgrowth, both in neurite length and number, compared with control glass substrate. Interestingly, the positive stimulatory effect by graphene was achieved even in the absence of soluble neurogenic factor, retinoic acid (RA). Key genes relevant to cell neurogenesis, e.g., neurofilament light chain (NFL), were also upregulated on graphene. Inhibitor studies suggested that the graphene stimulation of cellular neurogenesis may be achieved through focal adhesion kinase (FAK) and p38 mitogen-activated protein kinase (MAPK) cascades. Our data indicate that graphene may be exploited as a platform for neural regenerative medicine, and the suggested molecular mechanism may provide an insight into the graphene control of neural cells.

Longitudinal unzipping of carbon nanotubes to form graphene nanoribbons.

Graphene, or single-layered graphite, with its high crystallinity and interesting semimetal electronic properties, has emerged as an exciting two-dimensional material showing great promise for the fabrication of nanoscale devices. Thin, elongated strips of graphene that possess straight edges, termed graphene ribbons, gradually transform from semiconductors to semimetals as their width increases, and represent a particularly versatile variety of graphene. Several lithographic, chemical and synthetic procedures are known to produce microscopic samples of graphene nanoribbons, and one chemical vapour deposition process has successfully produced macroscopic quantities of nanoribbons at 950 degrees C. Here we describe a simple solution-based oxidative process for producing a nearly 100% yield of nanoribbon structures by lengthwise cutting and unravelling of multiwalled carbon nanotube (MWCNT) side walls. Although oxidative shortening of MWCNTs has previously been achieved, lengthwise cutting is hitherto unreported. Ribbon structures with high water solubility are obtained. Subsequent chemical reduction of the nanoribbons from MWCNTs results in restoration of electrical conductivity. These early results affording nanoribbons could eventually lead to applications in fields of electronics and composite materials where bulk quantities of nanoribbons are required.

Hybrid Edge Results in Narrowed Band Gap: Bottom-up Liquid-Phase Synthesis of Bent N = 6/8 Armchair Graphene Nanoribbons.

Scalable fabrication of graphene nanoribbons with narrow band gaps has been a nontrivial challenge. Here, we have developed a simple approach to access narrow band gaps using hybrid edge structures. Bottom-up liquid-phase synthesis of bent N = 6/8 armchair graphene nanoribbons (AGNRs) has been achieved in high efficiency through copolymerization between an o-terphenyl monomer and a naphthalene-based monomer, followed by Scholl oxidation. An unexpected 1,2-aryl migration has been discovered, which is responsible for introducing kinked structures into the GNR backbones. The N = 6/8 AGNRs have been fully characterized to support the proposed structure and show a narrow band gap and a relatively high electrical conductivity. In addition, their application in efficient gas sensing has also been demonstrated.

Interlayer Incorporation of A-Elements into MXenes Via Selective Etching of A' from Mn+1A'1-xA″xCn MAX Phases.

MXenes are a large family of two-dimensional materials with a general formula Mn+1XnTz, where M is a transition metal, X = C and/or N, and Tz represents surface functional groups. MXenes are synthesized by etching A-elements from layered MAX phases with a composition of Mn+1AXn. As over 20 different chemical elements were shown to form A-layers in various MAX phases, we propose that they can provide an abundant source of very diverse MXene-based materials. The general strategy for A-modified MXenes relies on the synthesis of Mn+1A'1-xA″xXn MAX phase, in which the higher reactivity of the A'-element compared to that of A″ enables its selective etching, resulting in A″-modified Mn+1XnTz. In general, the A″-element could modify the interlayer spaces of MXene flakes in a form of metallic or oxide species, depending on its chemical identity and synthetic conditions. We demonstrate this strategy by synthesizing Sn-modified Ti3C2Tz MXene from the Ti3Al0.75Sn0.25C2 MAX phase, which was used as a model system. Although the incorporation of Sn in the A-layer of Ti3AlC2 decreases the MAX phase reactivity, we developed an etching procedure to completely remove Al and produce Sn-modified Ti3C2Tz MXene. The resulting MXene sheets were of very high quality and exhibited improved environmental stability, which we attribute to the effect of a uniform Sn modification. Finally, we demonstrate a peculiar electrostatic expansion of Sn-modified Ti3C2Tz accordions, which may find interesting applications in MXene-based nano-electromechanical systems. Overall, these results demonstrate that in addition to different combinations of M and X elements in MAX phases, an A-layer also provides opportunities for the synthesis of MXene-based materials.

High-yield fabrication of electromechanical devices based on suspended Ti3C2Tx MXene monolayers.

MXenes, two-dimensional transition metal carbides, nitrides, and carbonitrides, are known for their exceptional electronic and mechanical properties. Yet, the experimental efforts toward the realization of MXene-based nanoelectromechanical systems (NEMS) combining electrical and mechanical functionalities of MXenes at the nanoscale remain very limited. Here, we demonstrate a high-yield fabrication of the electromechanical devices based on individual suspended monolayer MXene flakes. We employed Ti3C2Tx, the most popular MXene material to date, that can be produced as high-quality micrometer-scale monolayer flakes with a high electrical conductivity of over 10 000 S cm-1 and a high effective Young's modulus of about 330 GPa. These Ti3C2Tx flakes can be transferred over prefabricated trenches in a Si/Si3N4 substrate at a high yield, potentially enabling fabrication of hundreds of electromechanical devices based on suspended MXene monolayers. We demonstrate very clean, uniform, and well-stretched membranes with different dimensions, with Ti3C2Tx flakes suspended over trenches with gaps ranging from 200 nm to 2 µm. The resulting Ti3C2Tx monolayer membranes were electrostatically actuated, while their vertical displacement was monitored using a tip of an atomic force microscope (AFM). The devices reliably responded to the electrostatic actuation in ambient conditions over multiple cycles and with different measurement parameters, such as AC frequency, AC voltage amplitude, and AFM tip loading force. The demonstration of the high-yield fabrication of working electromechanical devices based on suspended Ti3C2Tx MXene membranes at the ultimate monolayer limit paves the way for the future exploration of the potential of MXenes for NEMS applications.