Optical Imaging of Redox and Molecular Diffusion in 2D van der Waals Space

Understanding charge transfer (CT) between two chemical entities and the subsequent change in their charge densities is essential not only for molecular species but also for various low-dimensional materials. Because of their extremely high fraction of surface atoms, two-dimensional (2-D) materials are most susceptible to charge exchange and exhibit drastically different physicochemical properties depending on their charge density. In this regard, spontaneous and uncontrollable ionization of graphene in the ambient air has caused much confusion and technical difficulty in achieving experimental reproducibility since its first report in 2004. Moreover, the same ambient hole doping was soon observed in 2-D semiconductors, which implied that a common mechanism should be operative and apply to other low-dimensional materials universally. Notably, a similar CT reaction has long been known for carbon nanotubes but is still controversial in its mechanism.In this Account, we review our breakthroughs in unraveling the chemical origin and mechanistic requirements of the hidden CT reactions using 2-D crystals. As a first step, we have developed in situ optical methods to quantify charge density using Raman and photoluminescence (PL) spectroscopy and imaging. To overcome the multimodal sensitivity of Raman frequencies, we established a novel analytical method based on theory and experiments with excellent resolution for the charge density (∼1 × 10¹² cm^-2) and lattice strain (∼0.02%) of graphene. For 2-D transition-metal dichalcogenides, PL spectroscopy and imaging provided a high precision and sensitivity that enabled rapid kinetic measurements in a spatially resolved manner.Using gas- and temperature-controlled in situ measurements, we revealed that the electrical holes are injected by the oxygen reduction reaction (ORR) O₂ + 4H⁺ + 4e^- ⇄ 2H₂O, which was independently verified by the pH dependence in HCl solutions. In addition to oxygen and water vapor, the overall CT reaction requires hydrophilic dielectric substrates, which assist the hydration of the sample-substrate interface. We also found that the CT reaction is substantially enhanced when samples are thermally annealed. The amplification is due to the interfacial hydrophilicity increased by the thermal hydroxylation of substrates, which indicates that the CT reaction is localized at the interface and boosted by interfacial water.The interface-localized CT allowed us to study and control molecular diffusion through the 2-D van der Waals space between samples and substrates. Wide-field PL imaging showed how fast oxygen molecules diffuse through the interfacial space, subsequently inducing the CT reaction. By increasing the 2-D gap spacing, the diffusion kinetics could be accelerated. The rate of CT could also be enhanced by introducing defects on the basal plane of 2-D crystals, which demonstrates the decisive role of defects as CT centers.Because of their unique geometry, low-dimensional materials are highly susceptible to external perturbation including charge exchange. Because the vulnerability can be exploited to modify material properties, the complete mechanism of the fundamental charge exchange summarized in this Account will be essential to exploring material and device properties of other low-dimensional materials.