Fluorescein Images Graphene

It’s been used to dye the Chicago River green on St. Patrick’s Day. It’s been used to find latent bloodstains at crime scenes. And now researchers at Northwestern University have used it to examine the thinnest material in the world.

Materials scientists Jaemyung Kim and Jiaxing Huang of Northwestern University’s McCormick School of Engineering and Applied Science. (Photos: Northwestern University)

This useful tool is the dye fluorescein, and Jiaxing Huang, assistant professor of materials science and engineering at McCormick School of Engineering and Applied Science, and his research group have used the dye to create an imaging technique to view graphene, a one-atom-thick sheet that scientists believe could be used to produce low-cost carbon-based transparent and flexible electronics.

As the world’s thinnest materials, graphene and its derivatives, such as graphene oxide, are quite challenging to see. Current imaging methods for graphene materials typically involve expensive and time-consuming techniques.

For example, atomic force microscopy (AFM), which scans materials with a tiny tip, frequently is used to obtain images of graphene materials. But it is a slow process that can look only at small areas on smooth surfaces. Scanning electron microscopy (SEM), which scans a surface with high-energy electrons, works only if the material is placed in vacuum. Some optical microscopy methods are available, but they also require the use of special substrates.

“There are really no good techniques that are general enough to meet the diverse imaging needs in the research and development of this group of new materials,” Huang said. “For example, people have proposed putting graphene materials on plastic sheets for flexible electronics, but seeing them on plastic has been very challenging. If one cannot exam these materials, quality control is going to be difficult.”

Fluorescent labeling has been used routinely to image biological samples, typically by using fluorescent dyes that make the objects of interest light up under a fluorescence microscope. But such a technique doesn’t work for graphene materials because of a mechanism called fluorescence quenching: They can “turn off” the fluorescence of nearby dye molecules.

“So we thought, how about we just put dye everywhere?” Huang said. “That way, the whole background lights up, and wherever you have graphene will be dark. It’s an inverse strategy that turns out to work beautifully.”

Images of graphene oxide sheets deposited on an SiO₂/Si substrate acquired by atomic force microscopy, scanning electron microscopy, optical microscopy in reflectance mode and by the new fluorescence quenching microscopy (FQM). FQM offers contrast and layer resolutions comparable to AFM and SEM.

When Huang and his group coated a graphene sample with fluorescein and put it under a fluorescence microscope – a much cheaper, readily available instrument – they obtained images as clear as those acquired with AFM and SEM.

The team named its new technique fluorescence quenching microscopy (FQM).

“When Jaemyung [Kim] first showed me the FQM images of graphene materials,” Huang explained, “I was tricked by the vivid details and thought they were SEM or AFM images.”

In addition, the group found that FQM can visualize graphene materials in solution. “No one has been able to demonstrate this before,” Huang said. The dye also can be added to photoresist materials so that graphene sheets can be seen during photolithography. The researchers also found that the dye could be washed off easily without disrupting the sheets themselves.

“It’s a simple and dirt-cheap method that works surprisingly well in many situations,” Huang said.

Their results were published recently in the Journal of the American Chemical Society.

Lead author of the paper, Jaemyung Kim, is a cluster fellow with the Initiative for Sustainability and Energy at Northwestern University. Other authors include Laura J. Cote and Franklin Kim, both of Northwestern. The work was supported by a seed grant from the Northwestern Nanoscale Science and Engineering Center.

For more information, visit: www.northwestern.edu