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

Journal Article · · Applied Physics Reviews
DOI:https://doi.org/10.1063/5.0039918· OSTI ID:1774766
 [1];  [2];  [3];  [4];  [5];  [3];  [3];  [3];  [3];  [6];  [6];  [3];  [7];  [2];  [8]
  1. Suranaree Univ. of Technology, Nakhon Ratchasima (Thailand); Drexel University
  2. Drexel Univ., Philadelphia, PA (United States)
  3. Suranaree Univ. of Technology, Nakhon Ratchasima (Thailand)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  5. Suranaree Univ. of Technology, Nakhon Ratchasima (Thailand); Fudan Univ., Shanghai (China)
  6. Synchrotron Light Research Inst., Nakhon Ratchasima (Thailand)
  7. Suranaree Univ. of Technology, Nakhon Ratchasima (Thailand); The Inst. for the Promotion of Teaching Science and Technology, Bangkok (Thailand)
  8. Suranaree Univ. of Technology, Nakhon Ratchasima (Thailand); Thailand Center of Excellence in Physics (ThEP), Bangkok (Thailand)
+ Show Author Affiliations
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 about 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 as 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 approximately 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 promoting the available states of Ti atoms for receiving more electron above the Fermi level and leads to the observed NEC. Furthermore, 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.
Research Organization:
Drexel Univ., Philadelphia, PA (United States)
Sponsoring Organization:
Program Management Unit for Human Resources and Institutional Development, Research and Innovation; USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-05CH11231; SC0018618
OSTI ID:
1774766
Journal Information:
Applied Physics Reviews, Journal Name: Applied Physics Reviews Journal Issue: 2 Vol. 8; ISSN 1931-9401
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

2D materials
36 MATERIALS SCIENCE
Chemical bonding
Density functional theory
Electrical conductivity
Electronic structure
Energy storage
Photoelectron spectroscopy