Frontiers in Energy Research: Fall 2016

The Metamorphosis of Metastable Metal Nitrides

Scientists create materials for evolving applications, from coatings to explosives to solar cells, and beyond

The top image shows the crystal structure of TiN2. The bottom image gives a zoomed in view of the unique nitrogen-nitrogen bond character in the crystal.

Imagine yourself and a group of friends on a ski trip. While making your way down the mountain, your ski group decides to stop half way down the slope to take a break and have lunch instead of finishing the run and resting in the cozy ski lodge. This strange group is representative of an exciting class of materials called metastable metal nitrides being explored by scientists at the Center for Next Generation of Materials by Design: Incorporating Metastability (CNGMD) and Energy Frontier Research in Extreme Environments (EFree), two Energy Frontiers Research Centers (EFRCs).

These metastable materials contain nitrogen and common metals such as tin or titanium, yet their structures and properties are still relatively unknown and unexplored. Most common materials are very stable and unchanging. The atoms in these stable materials have locked themselves into a crystal structure that scientists describe as their lowest energy minimum (relaxing in the ski lodge). However, metastable materials have crystal structures that are not found at the lowest energy minimum but are still stable in their current structures (relaxing halfway down the mountain). As such, metastable materials are difficult to predict and are a curiosity among researchers.

Titanium pernitride (TiN2), discovered by scientists at the EFree EFRC, is one of these exciting new metastable materials. This metal pernitride marks both the first non-noble metal pernitride and the lowest density metal pernitride synthesized to date.

The material’s most interesting feature is found in the single bond between two nitrogen atoms (nitrogen-nitrogen, or N-N) within the structure. The bond makes the material highly resistant to external pressure (only 18 percent less effective compared to diamond). This property makes the material useful as a hard coating for cutting and drilling applications.

Additionally, N-N stores large amounts of chemical energy. If ignited, this energy can be released from this metastable material to form highly stable molecular nitrogen (N≡N) and titanium, the highly stable, lowest energy minimums. Because of this, scientists may consider TiN2 as a future energetic material for use in explosives with some modifications to the material.

The metastable structures of Sn3N4 and the unexpected, higher energy SnN1-δ.

Scientists at CNGMD have been investigating new metastable tin nitride (abbreviated SnxNy) materials. Recently, they synthesized Sn3N4 along with the unexpectedly higher energy, SnN1-δ. Both materials exhibit both semiconductor and metal characteristics. An energy gap, known as the band gap, between the excited and stable energy levels for the electrons in the metastable, semiconducting S3N4 and its moderate free electron concentration makes it an interesting candidate for use in solar water splitting cells. In solar water splitting cells, the sun’s energy breaks down water into energy sources such as hydrogen fuel or electricity. The team tested Sn3N4 for this application and found it showed a moderate ability to produce an electric current when irradiated by light. With the addition of silicon, germanium, tin variants such as in SnN1-δ, or other elements, the activity of Sn3N4 can be tuned to better carry out this reaction.

In summary, the field of metastable metal nitrides is at the tip of the iceberg. Scientists have created a variety of exciting materials. These materials share the high incompressibility of their predecessors useful for hard coatings. They offer new realms to explore beyond their possible future usage in explosives, electronics, light-driven reactions, solar cells, and more.

Acknowledgments: 

Bhardam et al. 2016. This work was supported by Energy Frontier Research in Extreme Environments (EFree) Center, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, under award DE-SC0001057. Portions of this work were performed at High Pressure Collaborative Access Team (HPCAT) (Sector 16), Advanced Photon Source (APS), Argonne National Laboratory. HPCAT operations are supported by DOE National Nuclear Security Administration under award DE-NA0001974 and DOE, Office of Science, Basic Energy Sciences under award DE-FG02- 99ER45775, with partial instrumentation funding by the National Science Foundation (NSF). This research used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science user facility supported by the DOE Office of Science under contract DE-AC02-05CH11231 and the Extreme Science and Engineering Discovery Environments, which is supported by NSF grant ACI- 1053575.

Caskey et al. 2016a. This work is supported by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences, under contract DEAC36-08GO28308 to National Renewable Energy Laboratory (NREL) as a part of the Energy Frontier Research Center called Center for Next Generation of Materials by Design: Incorporating Metastability. X-ray absorption measurements were performed at Stanford Synchrotron Radiation Lightsource at SLAC National Accelerator Laboratory, supported by the DOE, Office of Science, Basic Energy Sciences under contract DE-AC02-76SF00515. The authors acknowledge the use of instruments at the Electron Imaging Center for NanoMachines supported by the National Institutes of Health (1S10RR23057) and the California NanoSystems Institute at the University of California Los Angeles, with raw data taken by Chilan Ngo, who gratefully acknowledges support from the National Science Foundation through grant CMMI-1200547. Amir Natan acknowledges financial support from the Israeli National Nanotechnology Initiative (INNI, FTA project). The X-ray diffraction peak search-match algorithm used in this work was developed as a part of a Laboratory Directed Research and Development project at NREL.

Caskey et al. 2016b. This work is supported by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences, under contract DEAC36-08GO28308 to National Renewable Energy Laboratory as a part of the Energy Frontier Research Center called Center for Next Generation of Materials by Design: Incorporating Metastability. J.A.S. and N.R.N. were supported by the DOE, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences under contract DE-AC36- 08GO28308.

Zakutayev 2016. The writing of this review article was supported by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences, as a part of the Energy Frontier Research Center called Center for Next Generation of Materials by Design: Incorporating Metastability. The author's part of work on the tin nitrides reviewed here was also supported from this funding source. The author's work on the copper nitrides reviewed here was supported by the DOE, Office of Energy Efficiency and Renewable Energy (EERE), as a part of the Ternary Copper Nitride Absorbers Next Generation PV II project within the SunShot Initiative. The author's part of work on the zinc tin nitride was supported by the DOE EERE, as a part of the Non-Proprietary Partnering Opportunity project within the SunShot Initiative. All these projects have been performed under DOE contract DE-AC36-08GO28308 to National Renewable Energy Laboratory.

More Information: 

Bhardam VS, DY Kim, and TA Strobel. 2016. “High-Pressure Synthesis and Characterization of Incompressible Titanium Pernitride.” Chemistry of Materials 28:1616-1620. DOI: 10.1021/acs.chemmater.6b00042

Caskey CM, A Holder, S Shulda, ST Christensen, D Diercks, C P Schwartz, D Biagioni, D Norlund, A Kukliansky, A Natan, D Prendergast, B Orvananos, W Sun, X Zhang, G Ceder, DS Ginley, W Tumas, JD Perkins, V Stevanoic, X Pylypenko, S Lany, RM Richards, and A Zakutayev. 2016a. “Synthesis of a Mixed-Valent Tin Nitride and Considerations of Its Possible Crystal Structures.” Journal of Chemical Physics 144:144201. DOI: 10.1063/1.4945561

Caskey CM, JA Seabold, V Stevanovic, M Ma, WA Smith, DS Ginley, NR Neale, RM Richards, S Lany, and A Zakutayev. 2016. “Semiconducting Properties of Spinel Tin Nitride and Other IV3N4 Polymorphs.” Journal of Materials Chemistry C 3:1389-1396. DOI: 10.1039/C4TC02528H

Zakutayev A. 2016. “Design of Nitride Semiconductors for Solar Energy Conversion.” Journal of Materials Chemistry A 4:6742. DOI: 10.1039/C5TA09446A

Disclaimer: The opinions in this newsletter are those of the individual authors and do not represent the views or position of the Department of Energy.

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