Photoluminescence Properties of Graphene versus Other Carbon Nanomaterials

Photoluminescent nanomaterials continue to garner research attention because of their many applications. For many years, researchers have focused on quantum dots (QDs) of semiconductor nanocrystals for their excellent performance and predictable fluorescence color variations that depend on the sizes of the nanocrystals. Even with these advantages, QDs can present some major limitations, such as the use of heavy metals in the high-performance semiconductor QDs. Therefore, researchers continue to be interested in developing new QDs or related nanomaterials. Recently, various nanoscale configurations of carbon have emerged as potential new platforms in the development of brightly photoluminescent materials. As a perfect π-conjugated single sheet, graphene lacks electronic bandgaps and is not photoluminescent. Therefore, researchers have created energy bandgaps within graphene as a strategy to impart fluorescence emissions. Researchers have explored many experimental techniques to introduce bandgaps, such as cutting graphene sheets into small pieces or manipulating the π electronic network to form quantum-confined sp(2) "islands" in a graphene sheet, which apparently involve the formation or exploitation of structural defects. In fact, defects in graphene materials not only play a critical role in the creation of bandgaps for emissive electronic transitions, but also contribute directly to the bright photoluminescence emissions observed in these materials. Researchers have found similar defect-derived photoluminescence in carbon nanotubes and small carbon nanoparticles, dubbed carbon "quantum" dots or "carbon dots". However, they have not systematically examined the emissions properties of these different yet related carbon nanomaterials toward understanding their mechanistic origins. In this Account, we examine the spectroscopic features of the observed photoluminescence emissions in graphene materials. We associate the structural characteristics in the underlying graphene materials with those emission properties as a way of classifying them into two primary categories: emissions that originate from created or induced energy bandgaps in a single graphene sheet and emissions that are associated with defects in single- and/or multiple-layer graphene. We highlight the similarities and differences between the observed photoluminescence properties of graphene materials and those found in other carbon nanomaterials including carbon dots and surface defect-passivated carbon nanotubes, and we discuss their mechanistic implications.