Bottom-up Synthesis Of Graphene Nanoribbons Research Articles

Polymerization of Brominated Aromatic Compounds within a Metal-Organic Framework toward Bottom-up Synthesis of Graphene Nanoribbons with Either Pyridinic or Tertiary Nitrogen

Polymerization of Brominated Aromatic Compounds within a Metal-Organic Framework toward Bottom-up Synthesis of Graphene Nanoribbons with Either Pyridinic or Tertiary Nitrogen

Living Suzuki-Miyaura Catalyst-Transfer Polymerization for Precision Synthesis of Length-Controlled Armchair Graphene Nanoribbons and Their Block Copolymers.

The bottom-up synthesis of graphene nanoribbons (GNRs) offers a promising approach for designing atomically precise GNRs with tuneable photophysical properties, but controlling their length remains a challenge. Herein, we report an efficient synthetic protocol for producing length-controlled armchair GNRs (AGNRs) through living Suzuki-Miyaura catalyst-transfer polymerization (SCTP) using RuPhos-Pd catalyst and mild graphitization methods. Initially, SCTP of a dialkynylphenylene monomer was optimized by modifying boronates and halide moieties on the monomers, affording poly(2,5-dialkynyl-p-phenylene) (PDAPP) with controlled molecular weight (Mn up to 29.8k) and narrow dispersity (Đ = 1.14-1.39) in excellent yield (>85%). Subsequently, we successfully obtained N = 5 AGNRs by employing a mild alkyne benzannulation reaction on the PDAPP precursor and confirmed their length retention by size-exclusion chromatography. In addition, photophysical characterization revealed that a molar absorptivity was directly proportional to the length of the AGNR, while its highest occupied molecular orbital (HOMO) energy level remained constant within the given AGNR length. Furthermore, we prepared, for the very first time, N = 5 AGNR block copolymers with widely used donor or acceptor-conjugated polymers by taking advantage of the living SCTP. Finally, we achieved the lateral extension of AGNRs from N = 5 to 11 by oxidative cyclodehydrogenation in solution and confirmed their chemical structure and low band gap by various spectroscopic analyses.

Atomically Precise Incorporation of BN-Doped Rubicene into Graphene Nanoribbons.

Substituting heteroatoms and non-benzenoid carbons into nanographene structure offers a unique opportunity for atomic engineering of electronic properties. Here we show the bottom-up synthesis of graphene nanoribbons (GNRs) with embedded fused BN-doped rubicene components on a Au(111) surface using on-surface chemistry. Structural and electronic properties of the BN-GNRs are characterized by scanning tunneling microscopy (STM) and atomic force microscopy (AFM) with CO-terminated tips supported by numerical calculations. The periodic incorporation of BN heteroatoms in the GNR leads to an increase of the electronic band gap as compared to its undoped counterpart. This opens avenues for the rational design of semiconducting GNRs with optoelectronic properties.

Absorption and Emission of Chemically and Electrochemically Doped Graphene Nanoribbons

Graphene nanoribbons (GNRs) are narrow stripes of graphene that exhibit unique optical and electronic properties depending on their width and edge type. Recent advances in the bottom-up synthesis of GNRs have enabled precise control over their structure and thus their bandgap. However, the systematic optical and electrical characterization of GNRs obtained from solution-mediated reactions has so far been prevented by the poor stability and processability of GNR dispersions. Here we employ liquid cascade centrifugation (LCC) to obtain size-selected and stable dispersions of bottom-up synthesized 9-aGNRs in toluene and tetrahydrofuran and investigate their intrinsic optical properties. Dispersions and films of these 9-aGNRs show well-defined absorption and photoluminescence bands between 800 and 1000 nm, with relative intensities depending on the LCC-fraction. The best GNR dispersions show photoluminescence quantum yields of up to 70 %. Trions are charged excitons with red-shifted emission that can be created in doped low-dimensional semiconductors, such as carbon nanotubes. Theoretical studies predict large trion binding energies (> 300 meV) in graphene nanoribbons (depending on their width). Hence their optical properties upon doping and possible new features are of interest. Chemical doping of our 9-aGNR dispersions with the strong molecular p-dopant F4-TCNQ and electrochemical doping of GNR thin films in ambipolar electrolyte-gated field-effect transistors results in the expected bleaching of the main absorption bands but also the emergence of new redshifted, charge-induced absorption peaks that may indicate the existence of trions in GNRs.

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.

Transfer-Free Synthesis of Atomically Precise Graphene Nanoribbons on Insulating Substrates.

The rational bottom-up synthesis of graphene nanoribbons (GNRs) provides atomically precise control of widths and edges that give rise to a wide range of electronic properties promising for electronic devices such as field-effect transistors (FETs). Since the bottom-up synthesis commonly takes place on catalytic metallic surfaces, the integration of GNRs into such devices requires their transfer onto insulating substrates, which remains one of the bottlenecks in the development of GNR-based electronics. Herein, we report on a method for the transfer-free placement of GNRs on insulators. This involves growing GNRs on a gold film deposited onto an insulating layer followed by gentle wet etching of the gold, which leaves the nanoribbons to settle in place on the underlying insulating substrate. Scanning tunneling microscopy and Raman spectroscopy confirm that atomically precise GNRs of high density uniformly grow on the gold films deposited onto SiO2/Si substrates and remain structurally intact after the etching process. We have also demonstrated transfer-free fabrication of ultrashort channel GNR FETs using this process. A very important aspect of the present work is that the method can scale up well to 12 in. wafers, which is extremely difficult for previous techniques. Our work here thus represents an important step toward large-scale integration of GNRs into electronic devices.

Small bandgap in atomically precise 17-atom-wide armchair-edged graphene nanoribbons

Bottom-up synthesis of graphene nanoribbons (GNRs) may open new possibilities in future electronic devices owing to their tunable electronic structure, which depends strongly on their well-defined width and edge geometry. For instance, armchair-edged GNRs (AGNRs) exhibit width-dependent bandgaps. However, the bandgaps of AGNRs synthesized experimentally so far are relatively large, well above 1 eV. Such a large bandgap may deteriorate device performance due to large Schottky barriers and carrier effective masses. Here, we describe the bottom-up synthesis of AGNRs with smaller bandgaps, using dibromobenzene-based precursors. Two types of AGNRs with different widths, namely 17 and 13 carbon atoms, were synthesized on Au(111), and their atomic and electronic structures were investigated by scanning probe microscopy and spectroscopy. We reveal that 17-AGNRs have the smallest bandgap, as well as the smallest electron/hole effective mass, among bottom-up AGNRs reported so far. The successful synthesis of 17-AGNRs is a significant step toward the development of GNR-based electronic devices.

Liquid-phase bottom-up synthesis of graphene nanoribbons

This review summarises the development of bottom-up synthesis of graphene nanoribbons in liquid phase and provides views on challenges in the field and the future outlook.

CVD Synthesis of Armchair Graphene Nanoribbons on Ge/Si(001)

Bottom-up synthesis of graphene nanoribbons on semiconducting, CMOS-compatible substrates is a promising and scalable route to exploiting graphene in next-generation nanoelectronics. In this study we demonstrate synthesis of semiconducting, graphene nanoribbons on Ge/Si(001) substrates, using CVD. We study the growth evolution and kinetics of nanoribbons and show that by tailoring the partial pressure of growth precursor, highly anisotropic, self-defining, and oriented nanoribbons with aspect ratio > 50 and smooth armchair edges can be synthesized, while avoiding bulk Si diffusion. We also investigate the presence of threading dislocations and show that neither nanoribbon nucleation nor growth is sensitive to presence or location of these dislocations. Our results indicate that Ge/Si(001) can be a promising platform for synthesis and fabrication of graphene nanoribbon devices.

Precursor design for bottom-up synthesis of graphene nanoribbons

Precursor design for bottom-up synthesis of graphene nanoribbons

Tuning the morphology of chevron-type graphene nanoribbons by choice of annealing temperature

Bottom-up synthesis of graphene nanoribbons (GNRs) by surface-assisted polymerization and cyclodehydrogenation of specifically designed precursor monomers has been shown to yield precise edges and doping. Here we use a precursor monomer containing sulfur atoms to fabricate nanostructures on a Au(111) surface at different annealing temperatures. The nanostructures have distinct configurations, varying from sulfur-doped polymers to sulfur-doped chevron-type GNRs (CGNRs) and, finally, pristine graphene nanoribbons with specific edges of periodic five-member carbon rings. Non-contact atomic force microscopy provides clear evidence for the cleavage of C–S bonds and formation of pristine CGNRs at elevated annealing temperatures. First-principles calculations show that the CGNRs exhibit negative differential resistance.

Bottom-Up Synthesis of Heteroatom-Doped Chiral Graphene Nanoribbons.

Bottom-up synthesis of graphene nanoribbons (GNRs) has significantly advanced during the past decade, providing various GNR structures with tunable properties. The synthesis of chiral GNRs, however, has been underexplored and only limited to (3,1)-GNRs. We report herein the surface-assisted synthesis of the first heteroatom-doped chiral (4,1)-GNRs from the rationally designed precursor 6,16-dibromo-9,10,19,20-tetraoxa-9a,19a-diboratetrabenzo[ a, f, j, o]perylene. The structure of the chiral GNRs has been verified by scanning tunneling microscopy, noncontact atomic force microscopy, and Raman spectroscopy in combination with theoretical modeling. Due to the presence of oxygen-boron-oxygen (OBO) segments on the edges, lateral self-assembly of the GNRs has been observed, realizing well-aligned GNR arrays with different modes of homochiral and heterochiral inter-ribbon assemblies.

Controllable conversion of quasi-freestanding polymer chains to graphene nanoribbons

In the bottom-up synthesis of graphene nanoribbons (GNRs) from self-assembled linear polymer intermediates, surface-assisted cyclodehydrogenations usually take place on catalytic metal surfaces. Here we demonstrate the formation of GNRs from quasi-freestanding polymers assisted by hole injections from a scanning tunnelling microscope (STM) tip. While catalytic cyclodehydrogenations typically occur in a domino-like conversion process during the thermal annealing, the hole-injection-assisted reactions happen at selective molecular sites controlled by the STM tip. The charge injections lower the cyclodehydrogenation barrier in the catalyst-free formation of graphitic lattices, and the orbital symmetry conservation rules favour hole rather than electron injections for the GNR formation. The created polymer–GNR intraribbon heterostructures have a type-I energy level alignment and strongly localized interfacial states. This finding points to a new route towards controllable synthesis of freestanding graphitic layers, facilitating the design of on-surface reactions for GNR-based structures.

Graphene Nanoribbons via Crystal Engineering

In this issue of Chem , Rubin and coworkers have developed a new approach for the bottom-up synthesis of graphene nanoribbons by efficiently combining crystal engineering and topochemical polymerization.

Deposition, characterization, and thin-film-based chemical sensing of ultra-long chemically synthesized graphene nanoribbons.

Bottom-up synthesis of graphene nanoribbons (GNRs) is an essential step toward utilizing them in electronic and sensing applications due to their defined edge structure and high uniformity. Recently, structurally perfect GNRs with variable lengths and edge structures were created using various chemical synthesis techniques. Nonetheless, issues like GNR deposition, characterization, electronic properties, and applications are not fully explored. Here we report optimized conditions for deposition, characterization, and device fabrication of individual and thin films of ultra-long chemically synthesized GNRs. Moreover, we have demonstrated exceptional NO2 gas sensitivity of the GNR film devices down to parts per billion (ppb) levels. The results lay the foundation for using chemically synthesized GNRs for future electronic and sensing applications.