Spectroscopic signature of negative electronic compressibility from the Ti core-level of titanium carbonitride MXene

Two-dimensional transition metal carbides, carbonitrides, and nitrides, called MXenes, exhibit high metallic conductivity, ion intercalation capability, and reversible redox activity, prompting their applications in energy storage and conversion, electromagnetic interference (EMI) shielding, and electronics, among many other fields. It has been shown that replacement of ∼50% of carbon atoms in the most popular MXene family member, titanium carbide (Ti3C2Tx), by nitrogen atoms, forming titanium carbonitride (Ti3CNTx), leads to drastically different properties. Such properties include very high negative charge in solution and extreme EMI shielding effectiveness, exceeding all known materials, even metals at comparable thicknesses. Here, by using ultraviolet photoemission spectroscopy (UPS), the electronic structures of Ti3CNTx and Ti3C2Tx are systematically investigated and compared as a function of charge carrier density. We observe that, in contrast to Ti3C2Tx, the Ti 3p core-level of Ti3CNTx exhibits a counterintuitive shift to a lower binding energy of up to ∼250 meV upon increasing the electron density, which is a spectroscopic signature of negative electronic compressibility (NEC). These experimentally measured chemical potential shifts are well captured by the density functional theory (DFT) calculation. The DFT results also further suggest that the hybridization of titanium–nitrogen bonding in Ti3CNTx helps to promote the available states of Ti atoms for receiving more electrons above the fermi level and leads to the observed NEC. Our findings explain the differences in electronic properties between the two very important and widely studied MXenes and also suggest a new strategy to apply the NEC effect of Ti3CNTx in energy and charge storage applications.