Ayrat M. Dimiev

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 °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.

Mechanism of Graphene Oxide Formation

Despite intensive research, the mechanism of graphene oxide (GO) formation remains unclear. The role of interfacial interactions between solid graphite and the liquid reaction medium, and transport of the oxidizing agent into the graphite, has not been well-addressed. In this work, we show that formation of GO from graphite constitutes three distinct independent steps. The reaction can be stopped at each step, and the corresponding intermediate products can be isolated, characterized, and stored under appropriate conditions. The first step is conversion of graphite into a stage-1 graphite intercalation compound (GIC). The second step is conversion of the stage-1 GIC into oxidized graphite, which we define as pristine graphite oxide (PGO). This step involves diffusion of the oxidizing agent into the preoccupied graphite galleries. This rate-determining step makes the entire process diffusive-controlled. The third step is conversion of PGO into conventional GO after exposure to water, which involves hydrolysis of covalent sulfates and loss of all interlayer registry.

Kinetics of Diazonium Functionalization of Chemically Converted Graphene Nanoribbons

We demonstrate that graphene nanoribbons (GNRs) produced by the oxidative unzipping of carbon nanotubes can be chemically functionalized by diazonium salts. We show that functional groups form a thin layer on a GNR and modify its electrical properties. The kinetics of the functionalization can be monitored by probing the electrical properties of GNRs, either in vacuum after the grafting, or in situ in the solution. We derive a simple kinetics model that describes the change in the electrical properties of GNRs. The reaction of GNRs with 4-nitrobenzene diazonium tetrafluoroborate is reasonably fast, such that >60% of the maximum change in the electrical properties is observed after less than 5 min of grafting at room temperature.

Pristine Graphite Oxide

Graphite oxide (GO) is a lamellar substance with an ambiguous structure due to material complexity. Recently published GO-related studies employ only one out of several existing models to interpret the experimental data. Because the models are different, this leads to confusion in understanding the nature of the observed phenomena. Lessening the structural ambiguity would lead to further developments in functionalization and use of GO. Here, we show that the structure and properties of GO depend significantly on the quenching and purification procedures, rather than, as is commonly thought, on the type of graphite used or oxidation protocol. We introduce a new purification protocol that produces a product that we refer to as pristine GO (pGO) in contrast to the commonly known material that we will refer to as conventional GO (cGO). We explain the differences between pGO and cGO by transformations caused by reaction with water. We produce ultraviolet-visible spectroscopic, Fourier transform infrared spectroscopic, solid-state nuclear magnetic resonance spectroscopic, thermogravimetric, and scanning electron microscopic analytical evidence for the structure of pGO. This work provides a new explanation for the acidity of GO solutions and allows us to add critical details to existing GO models.

Layer-by-Layer Removal of Graphene for Device Patterning

Reactions of graphene with zinc enable etching of a single graphene layer. The patterning of graphene is useful in fabricating electronic devices, but existing methods do not allow control of the number of layers of graphene that are removed. We show that sputter-coating graphene and graphene-like materials with zinc and dissolving the latter with dilute acid removes one graphene layer and leaves the lower layers intact. The method works with the four different types of graphene and graphene-like materials: graphene oxide, chemically converted graphene, chemical vapor–deposited graphene, and micromechanically cleaved (“clear-tape”) graphene. On the basis of our data, the top graphene layer is damaged by the sputtering process, and the acid treatment removes the damaged layer of carbon. When used with predesigned zinc patterns, this method can be viewed as lithography that etches the sample with single-atomic-layer resolution.

Graphene nanoribbon devices produced by oxidative unzipping of carbon nanotubes

We demonstrate that graphene nanoribbons (GNRs), produced by the chemical unzipping of carbon nanotubes, can be conveniently used from solution to hand-paint unidirectional arrays of GNRs atop silicon oxide. Through this simple alignment technique, numerous GNR-based devices, including field effect transistors, sensors, and memories can be easily fabricated on a single chip, and then used to generate statistically relevant device assessments. Such studies immediately give insights into, for example, multilayering properties on conductance, the profound effects that atmospheric adsorbates have upon the transfer characteristics of graphene, and other phenomena affecting the performance of GNR devices.

In situ intercalation replacement and selective functionalization of graphene nanoribbon stacks.

A cost-effective and potentially industrially scalable, in situ functionalization procedure for preparation of soluble graphene nanoribbon (GNRs) from commercially available carbon nanotubes is presented. The physical characteristics of the functionalized product were determined using SEM, evolved gas analysis, X-ray diffraction, solid-state (13)C NMR, Raman spectroscopy, and GC-MS analytical techniques. A relatively high preservation of electrical properties in the bulk material was observed. Moreover, replacement of intercalated potassium with haloalkanes was obtained. While carbon nanotubes can be covalently functionalized, the conversion of the sp(2)-hybridized carbon atoms to sp(3)-hybridized atoms dramatically lowers their conductivity, but edge functionalized GNRs permit their heavy functionalization while leaving the basal planes intact.

Direct Real-Time Monitoring of Stage Transitions in Graphite Intercalation Compounds

Graphite intercalation compounds (GIC) possess a broad range of unique properties that are not specific to the parent materials. While the stage transition, changing the number of graphene layers sandwiched between the two layers of intercalant, is fundamentally important and has been theoretically addressed, experimental studies revealed only macroscopic parameters. On the microscale, the phenomenon remains elusive up to the present day. Here we monitor directly in real time the stage transitions using a combination of optical microscopy and Raman spectroscopy. These direct observations yield several mechanistic conclusions. While we obtained strong experimental evidence in support of the Daumas-Herold theory, we find that the conventional interpretation of stage transitions as sliding of the existing intercalant domains does not sufficiently capture the actual phenomena. The entire GIC structure transforms considerably during the stage transition. Among other observations, massive wavefront-like perturbations occur on the graphite surface, which we term the tidal wave effect.

Chemical Mass Production of Graphene Nanoplatelets in ∼100% Yield

Successful application of graphene is hampered by the lack of cost-effective methods for its production. Here, we demonstrate a method of mass production of graphene nanoplatelets (GNPs) by exfoliation of flake graphite in the tricomponent system made by a combination of ammonium persulfate ((NH4)2S2O8), concentrated sulfuric acid, and fuming sulfuric acid. The resulting GNPs are tens of microns in diameter and 10-35 nm in thickness. When in the liquid phase of the tricomponent media, graphite completely loses its interlayer registry. This provides a ∼100% yield of GNPs from graphite in 3-4 h at room temperature or in 10 min at 120 °C.

Low-loss, high-permittivity composites made from graphene nanoribbons.

A new composite material was prepared by incorporation of graphene nanoribbons into a dielectric host matrix. The composite possesses remarkably low loss at reasonably high permittivity values. By varying the content of the conductive filler, one can tune the loss and permittivity to desirable values over a wide range. The obtained data exemplifies how nanoscopic changes in the structure of conductive filler can affect macroscopic properties of composite material.