Priyank V. Kumar

Scalable enhancement of graphene oxide properties by thermally driven phase transformation

Chemical functionalization of graphene is promising for a variety of next-generation technologies. Although graphene oxide (GO) is a versatile material in this direction, its use is limited by the production of metastable, chemically inhomogeneous and spatially disordered GO structures under current synthetic protocols, which results in poor optoelectronic properties. Here, we present a mild thermal annealing procedure, with no chemical treatments involved, to manipulate as-synthesized GO on a large scale to enhance sheet properties with the oxygen content preserved. Using experiments supported by atomistic calculations, we demonstrate that GO structures undergo a phase transformation into prominent oxidized and graphitic domains by temperature-driven oxygen diffusion. Consequently, as-synthesized GO that absorbs mainly in the ultraviolet region becomes strongly absorbing in the visible region, photoluminescence is blue shifted and electronic conductivity increases by up to four orders of magnitude. Our thermal processing method offers a suitable way to tune and enhance the properties of GO, which creates opportunities for various applications.

The Impact of Functionalization on the Stability, Work Function, and Photoluminescence of Reduced Graphene Oxide

Reduced graphene oxide (rGO) is a promising material for a variety of thin-film optoelectronic applications. Two main barriers to its widespread use are the lack of (1) fabrication protocols leading to tailored functionalization of the graphene sheet with oxygen-containing chemical groups, and (2) understanding of the impact of such functional groups on the stability and on the optical and electronic properties of rGO. We carry out classical molecular dynamics and density functional theory calculations on a large set of realistic rGO structures to decompose the effects of different functional groups on the stability, work function, and photoluminescence. Our calculations indicate the metastable nature of carbonyl-rich rGO and its favorable transformation to hydroxyl-rich rGO at room temperature via carbonyl-to-hydroxyl conversion reactions near carbon vacancies and holes. We demonstrate a significant tunability in the work function of rGO up to 2.5 eV by altering the composition of oxygen-containing functional groups for a fixed oxygen concentration, and of the photoluminescence emission by modulating the fraction of epoxy and carbonyl groups. Taken together, our results guide the application of tailored rGO structures in devices for optoelectronics and renewable energy.

Nanocarbon-Based Photovoltaics

Carbon materials are excellent candidates for photovoltaic solar cells: they are Earth-abundant, possess high optical absorption, and maintain superior thermal and photostability. Here we report on solar cells with active layers made solely of carbon nanomaterials that present the same advantages of conjugated polymer-based solar cells, namely, solution processable, potentially flexible, and chemically tunable, but with increased photostability and the possibility to revert photodegradation. The device active layer composition is optimized using ab initio density functional theory calculations to predict type-II band alignment and Schottky barrier formation. The best device fabricated is composed of PC(70)BM fullerene, semiconducting single-walled carbon nanotubes, and reduced graphene oxide. This active-layer composition achieves a power conversion efficiency of 1.3%-a record for solar cells based on carbon as the active material-and we calculate efficiency limits of up to 13% for the devices fabricated in this work, comparable to those predicted for polymer solar cells employing PCBM as the acceptor. There is great promise for improving carbon-based solar cells considering the novelty of this type of device, the high photostability, and the availability of a large number of carbon materials with yet untapped potential for photovoltaics. Our results indicate a new strategy for efficient carbon-based, solution-processable, thin film, photostable solar cells.

Graphene Oxide as a Promising Hole Injection Layer for MoS2-Based Electronic Devices

The excellent physical and semiconducting properties of transition metal dichalcogenide (TMDC) monolayers make them promising materials for many applications. The TMDC monolayer MoS2 has gained significant attention as a channel material for next-generation transistors. However, while n-type single-layer MoS2 devices can be made with relative ease, fabrication of p-type transistors remains a challenge as the Fermi-level of elemental metals used as contacts are pinned close to the conduction band leading to large p-type Schottky barrier heights (SBH). Here, we propose the utilization of graphene oxide (GO) as an efficient hole injection layer for single-layer MoS2-based electronic and optoelectronic devices. Using first-principles computations, we demonstrate that GO forms a p-type contact with monolayer MoS2, and that the p-type SBH can be made smaller by increasing the oxygen concentration and the fraction of epoxy functional groups in GO. Our analysis shows that this is possible due to the high work function of GO and the relatively weak Fermi-level pinning at the MoS2/GO interfaces compared to traditional MoS2/metal systems (common metals are Ag, Al, Au, Ir, Pd, Pt). The combination of easy-to-fabricate and inexpensive GO with MoS2 could be promising for the development of hybrid all-2D p-type electronic and optoelectronic devices on flexible substrates.

Enhanced Cell Capture on Functionalized Graphene Oxide Nanosheets through Oxygen Clustering

With the global rise in incidence of cancer and infectious diseases, there is a need for the development of techniques to diagnose, treat, and monitor these conditions. The ability to efficiently capture and isolate cells and other biomolecules from peripheral whole blood for downstream analyses is a necessary requirement. Graphene oxide (GO) is an attractive template nanomaterial for such biosensing applications. Favorable properties include its two-dimensional architecture and wide range of functionalization chemistries, offering significant potential to tailor affinity toward aromatic functional groups expressed in biomolecules of interest. However, a limitation of current techniques is that as-synthesized GO nanosheets are used directly in sensing applications, and the benefits of their structural modification on the device performance have remained unexplored. Here, we report a microfluidic-free, sensitive, planar device on treated GO substrates to enable quick and efficient capture of Class-II MHC-positive cells from murine whole blood. We achieve this by using a mild thermal annealing treatment on the GO substrates, which drives a phase transformation through oxygen clustering. Using a combination of experimental observations and MD simulations, we demonstrate that this process leads to improved reactivity and density of functionalization of cell capture agents, resulting in an enhanced cell capture efficiency of 92 ± 7% at room temperature, almost double the efficiency afforded by devices made using as-synthesized GO (54 ± 3%). Our work highlights a scalable, cost-effective, general approach to improve the functionalization of GO, which creates diverse opportunities for various next-generation device applications.

Graphene Oxide Nanosheets Modified with Single-Domain Antibodies for Rapid and Efficient Capture of Cells

Peripheral blood can provide valuable information on an individuals immune status. Cell-based assays typically target leukocytes and their products. Characterization of leukocytes from whole blood requires their separation from the far more numerous red blood cells.1 Current methods to classify leukocytes, such as recovery on antibody-coated beads or fluorescence-activated cell sorting require long sample preparation times and relatively large sample volumes.2 A simple method that enables the characterization of cells from a small peripheral whole blood sample could overcome limitations of current analytical techniques. We describe the development of a simple graphene oxide surface coated with single-domain antibody fragments. This format allows quick and efficient capture of distinct WBC subpopulations from small samples (∼30 μL) of whole blood in a geometry that does not require any specialized equipment such as cell sorters or microfluidic devices.

Enhanced Osteogenic Differentiation of Stem Cells on Phase-Engineered Graphene Oxide

Graphene oxide (GO) has attracted significant interest as a template material for multiple applications due to its two-dimensional nature and established functionalization chemistries. However, for applications toward stem cell culture and differentiation, GO is often reduced to form reduced graphene oxide, resulting in a loss of oxygen content. Here, we induce a phase transformation in GO and demonstrate its benefits for enhanced stem cell culture and differentiation while conserving the oxygen content. The transformation results in the clustering of oxygen atoms on the GO surface, which greatly improves its ability toward substance adherence and results in enhanced differentiation of human mesenchymal stem cells toward the osteogenic lineage. Moreover, the conjugating ability of modified GO strengthened, which was examined by auxiliary osteogenic growth peptide conjugation. Overall, our work demonstrates GOs potential for stem cell applications while maintaining its oxygen content, which could enable further functionalization and fabrication of novel nano-biointerfaces.