Two dimensional soft material: new faces of graphene oxide.

Graphite oxide sheets, now called graphene oxide (GO), can be made from chemical exfoliation of graphite by reactions that have been known for 150 years. Because GO is a promising solution-processable precursor for the bulk production of graphene, interest in this old material has resurged. The reactions to produce GO add oxygenated functional groups to the graphene sheets on their basal plane and edges, and this derivatization breaks the π-conjugated network, resulting in electrically insulating but highly water-dispersible sheets. Apart from making graphene, GO itself has many intriguing properties. Like graphene, GO is a two-dimensional (2D) sheet with feature sizes at two abruptly different length scales. The apparent thickness of the functionalized carbon sheet is approximately 1 nm, but the lateral dimensions can range from a few nanometers to hundreds of micrometers. Therefore, researchers can think of GO as either a single molecule or a particle, depending on which length scale is of greater interest. At the same time, GO can be viewed as an unconventional soft material, such as a 2D polymer, highly anisotropic colloid, membrane, liquid crystal, or amphiphile. In this Account, we highlight the soft material characteristics of GO. GO consists of nanographitic patches surrounded by largely disordered, oxygenated domains. Such structural characteristics effectively make GO a 2D amphiphile with a hydrophilic periphery and largely hydrophobic center. This insight has led to better understanding of the solution properties of GO for making thin films and new applications of GO as a surfactant. Changes in pH and sheet size can tune the amphiphilicity of GO, leading to intriguing interfacial activities. In addition, new all-carbon composites made of only graphitic nanostructures using GO as a dispersing agent have potential applications in photovoltaics and energy storage. On the other hand, GO can function as a 2D random diblock copolymer, one block graphitic and the other heavily hydroxylated. Therefore, GO can guide material assembly through π-π stacking and hydrogen bonding. Additionally, the selective etching of the more reactive sp(3) blocks produces a porous GO network, which greatly enhances interactions with gas molecules in chemical sensors. With their high aspect ratio, GO colloids can readily align to form liquid crystalline phases at high concentration. As single-atomic, water-dispersible, soft carbon sheets that can be easily converted to a conductive form, this 2D material should continue to inspire many curiosity-driven discoveries and applications at the interfaces of chemistry, materials science, and other disciplines.

Sticky interconnect for solution-processed tandem solar cells.

Graphene oxide (GO) can be viewed as a two-dimensional, random diblock copolymer with distributed nanosize graphitic patches and highly oxidized domains, thus capable of guiding the assembly of other materials through both π-π stacking and hydrogen bonding. Upon mixing GO and conducting polymer poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) in water, a dispersion with dramatically increased viscosity is obtained, which turns into sticky thin films upon casting. Surprisingly, the insulating GO makes PEDOT much more conductive by altering its chain conformation and morphology. The GO/PEDOT gel can function as a metal-free solder for creating mechanical and electrical connections in organic optoelectronic devices. As a proof-of-concept, polymer tandem solar cells have been fabricated by a direct adhesive lamination process enabled by the sticky GO/PEDOT film. The sticky interconnect can greatly simplify the fabrication of organic tandem architectures, which has been quite challenging via solution processing. Thus, it could facilitate the construction of high-efficiency tandem solar cells with different combinations of solution-processable materials.

Visualizing graphene based sheets by fluorescence quenching microscopy.

Graphene based sheets have stimulated great interest due to their superior mechanical, electrical, and thermal properties. A general visualization method that allows quick observation of these single atomic layers would be highly desirable as it can greatly facilitate sample evaluation and manipulation, and provide immediate feedback to improve synthesis and processing strategies. Here we report that graphene based sheets can be made highly visible under a fluorescence microscope by quenching the emission from a dye coating, which can be conveniently removed afterward by rinsing without disrupting the sheets. Current imaging techniques for graphene based sheets rely on the use of special substrates. In contrast, the fluorescence quenching mechanism is no longer limited by the type of substrate. Graphene, reduced graphene oxide, or even graphene oxide sheets deposited on arbitrary substrates can now be readily visualized with good contrast for layer counting. Direct observation of suspended sheets in solution was also demonstrated. The fluorescence quenching microscopy offers unprecedented imaging flexibility and could become a general tool for characterizing graphene based materials.

Graphene oxide sheets at interfaces.

Graphite oxide sheet, now called graphene oxide (GO), is the product of chemical exfoliation of graphite and has been known for more than a century. GO has been largely viewed as hydrophilic, presumably due to its excellent colloidal stability in water. Here we report that GO is an amphiphile with hydrophilic edges and a more hydrophobic basal plane. GO can act like a surfactant, as measured by its ability to adsorb on interfaces and lower the surface or interfacial tension. Since the degree of ionization of the edge -COOH groups is affected by pH, GO's amphiphilicity can be tuned by pH. In addition, size-dependent amphiphilicity of GO sheets is observed. Since each GO sheet is a single molecule as well as a colloidal particle, the molecule-colloid duality makes it behave like both a molecular and a colloidal surfactant. For example, GO is capable of creating highly stable Pickering emulsions of organic solvents like solid particles. It can also act as a molecular dispersing agent to process insoluble materials such as graphite and carbon nanotubes in water. The ease of its conversion to chemically modified graphene could enable new opportunities in solution processing of functional materials.

Graphene oxide nanocolloids.

Graphene oxide (GO) nanocolloids-sheets with lateral dimension smaller than 100 nm-were synthesized by chemical exfoliation of graphite nanofibers, in which the graphene planes are coin-stacked along the length of the nanofibers. Since the upper size limit is predetermined by the diameter of the nanofiber precursor, the size distribution of the GO nanosheets is much more uniform than that of common GO synthesized from graphite powders. The size can be further tuned by the oxidation time. Compared to the micrometer-sized, regular GO sheets, nano GO has very similar spectroscopic characteristics and chemical properties but very different solution properties, such as surface activity and colloidal stability. Due to higher charge density originating from their higher edge-to-area ratios, aqueous GO nanocolloids are significantly more stable. Dispersions of GO nanocolloids can sustain high-speed centrifugation and remain stable even after chemical reduction, which would result in aggregates for regular GO. Therefore, nano GO can act as a better dispersing agent for insoluble materials (e.g., carbon nanotubes) in water, creating a more stable colloidal dispersion.

Langmuir-Blodgett assembly of graphite oxide single layers.

Single-layer graphite oxide can be viewed as an unconventional type of soft material and has recently been recognized as a promising material for composite and electronics applications. It is of both scientific curiosity and technical importance to know how these atomically thin sheets assemble. There are two fundamental geometries of interacting single layers: edge-to-edge and face-to-face. Such interactions were studied at the air-water interface by Langmuir-Blodgett assembly. Stable monolayers of graphite oxide single layers were obtained without the need for any surfactant or stabilizing agent, due to the strong electrostatic repulsion between the 2D confined layers. Such repulsion also prevented the single layers from overlapping during compression, leading to excellent reversibility of the monolayers. In contrast to molecular and hard colloidal particle monolayers, the single layers tend to fold and wrinkle at edges to resist collapsing into multilayers. The monolayers can be transferred to a substrate, readily creating a large area of flat graphite oxide single layers. The density of such films can be continuously tuned from dilute, close-packed to overpacked monolayers of interlocking single layers. For size-mismatched single layers, face-to-face interaction caused irreversible stacking, leading to double layers. The graphite oxide monolayers can be chemically reduced to graphene for electronic applications such as transparent conducting thin films.

Flash reduction and patterning of graphite oxide and its polymer composite.

Graphite oxide (GO) is a promising precursor for the bulk production of graphene-based materials due to its relatively low cost of synthesis. The superior solvent processability of GO makes it particularly attractive for making composites by premixing with other materials. Typically, the reduction of GO has relied on either chemical agents or high temperature treatment. Here we report a room temperature, chemical-free flash reduction process where a photographic camera flash instantaneously triggers the deoxygenation reaction of GO by photothermal heating. Flash irradiation also rapidly creates a fused polymer composite from a random mixture of GO and polymer particles. Using a photomask, conducting patterns such as interdigitated electrode arrays can be readily made on flexible substrates.

Graphene oxide windows for in situ environmental cell photoelectron spectroscopy.

The performance of new materials and devices often depends on processes taking place at the interface between an active solid element and the environment (such as air, water or other fluids). Understanding and controlling such interfacial processes require surface-specific spectroscopic information acquired under real-world operating conditions, which can be challenging because standard approaches such as X-ray photoelectron spectroscopy generally require high-vacuum conditions. The state-of-the-art approach to this problem relies on unique and expensive apparatus including electron analysers coupled with sophisticated differentially pumped lenses. Here, we develop a simple environmental cell with graphene oxide windows that are transparent to low-energy electrons (down to 400 eV), and demonstrate the feasibility of X-ray photoelectron spectroscopy measurements on model samples such as gold nanoparticles and aqueous salt solution placed on the back side of a window. These proof-of-principle results show the potential of using graphene oxide, graphene and other emerging ultrathin membrane windows for the fabrication of low-cost, single-use environmental cells compatible with commercial X-ray and Auger microprobes as well as scanning or transmission electron microscopes.

Drop-casted self-assembling graphene oxide membranes for scanning electron microscopy on wet and dense gaseous samples.

Graphene oxide sheets dispersed in water and many other solvents can spontaneously assemble into a surface film covering an evaporating droplet due to their amphiphilicity. Thus, graphene oxide membranes with controllable thickness suspended over an orifice have been directly fabricated using a simple drop-cast approach. Mechanical properties and electron transparency tests of these membranes show their use as electron transparent, but molecularly impenetrable, windows for environmental electron microscopy in liquids and dense gaseous media. The foreseeable, broader application of this drop-cast window methodology is the creation of access spots for electron probes to study isolated microsamples in their natural, undisrupted state within the interior of prefabricated devices (such as microfluidic chips or sealed containers of biological, chemically reactive, toxic, or forensic materials).

Graphene oxide: surface activity and two-dimensional assembly.

Graphene oxide (GO) is a promising precursor for preparing graphene-based composites and electronics applications. Like graphene, GO is essentially one-atom thick but can be as wide as tens of micrometers, resulting in a unique type of material building block, characterized by two very different length scales. Due to this highly anisotropic structure, the collective material properties are highly dependent on how these sheets are assembled. Therefore, understanding and controlling the assembly behavior of GO has become an important subject of research. In this Research News article the surface activity of GO and how it can be employed to create two-dimensional assemblies over large areas is discussed.