Semiconducting cubic titanium nitride in the Th3P4 structure

Bhadram, Venkata S.; Liu, Hanyu; Xu, Enshi; Li, Tianshu; Prakapenka, Vitali B.; Hrubiak, Rostislav; Lany, Stephan; Strobel, Timothy A.

doi:10.1103/PhysRevMaterials.2.011602

Semiconducting cubic titanium nitride in the ${Th}_{3} P_{4}$ structure

Journal Article · Mon Jan 01 04:00:00 UTC 2018 · Physical Review Materials

DOI:https://doi.org/10.1103/PhysRevMaterials.2.011602· OSTI ID:1418047

Bhadram, Venkata S.; Liu, Hanyu; Xu, Enshi; Li, Tianshu; Prakapenka, Vitali B.; Hrubiak, Rostislav; Lany, Stephan; Strobel, Timothy A.

We report the discovery of a long-sought-after phase of titanium nitride with stoichiometry Ti 3 N 4 using diamond anvil cell experiments combined with in situ high-resolution x-ray diffraction and Raman spectroscopy techniques, supported by ab initio calculations. Ti 3 N 4 crystallizes in the cubic Th 3 P 4 structure [space group I ¯ 4 3 d (220)] from a mixture of TiN and N 2 above ≈ 75 GPa and ≈ 2400 K. The density ( ≈ 5.22 g/cc) and bulk modulus ( K 0 = 290 GPa) of cubic- Ti 3 N 4 ( c - Ti 3 N 4 ) at 1 atm, estimated from the pressure-volume equation of state, are comparable to rocksalt TiN. Ab initio calculations based on the GW approximation and using hybrid functionals indicate that c - Ti 3 N 4 is a semiconductor with a direct band gap between 0.8 and 0.9 eV, which is larger than the previously predicted values. The c - Ti 3 N 4 phase is not recoverable to ambient pressure due to dynamic instabilities, but recovery of Ti 3 N 4 in the defect rocksalt (or related) structure may be feasible.

Research Organization:: Advanced Photon Source (APS), Argonne National Laboratory (ANL), Argonne, IL (US); Energy Frontier Research Centers (EFRC) (United States). Center for Next Generation of Materials by Design: Incorporating Metastability (CNGMD); Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research in Extreme Environments (EFree)

Sponsoring Organization:: DOE - BASIC ENERGY SCIENCESNSFDOE-NNSAAHA

OSTI ID:: 1418047

Journal Information:: Physical Review Materials, Journal Name: Physical Review Materials Journal Issue: 1 Vol. 2; ISSN PRMHAR; ISSN 2475-9953

Publisher:: American Physical Society (APS)

Country of Publication:: United States

Language:: ENGLISH

References (44)

Synthesis, Crystal Structure, and High Temperature Behavior of Zr3N4 Lerch, M.; F�glein, E.; Wrba, J. Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 622, Issue 2 https://doi.org/10.1002/zaac.19966220227	journal	February 1996
Indexing of powder diffraction patterns for low-symmetry lattices by the successive dichotomy method Boultif, A.; Louër, D. Journal of Applied Crystallography, Vol. 24, Issue 6 https://doi.org/10.1107/S0021889891006441	journal	December 1991
Synthesis of cubic zirconium and hafnium nitride having Th3P4 structure Zerr, Andreas; Miehe, Gerhard; Riedel, Ralf Nature Materials, Vol. 2, Issue 3 https://doi.org/10.1038/nmat836	journal	February 2003
�ber Nitridhalogenide des Titans und Zirkons Juza, Robert; Heners, J�rgen Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 332, Issue 3-4 https://doi.org/10.1002/zaac.19643320307	journal	October 1964
Nitrogen-rich transition metal nitrides Salamat, Ashkan; Hector, Andrew L.; Kroll, Peter Coordination Chemistry Reviews, Vol. 257, Issue 13-14 https://doi.org/10.1016/j.ccr.2013.01.010	journal	July 2013
Design of Metastable Tin Titanium Nitride Semiconductor Alloys Bikowski, Andre; Siol, Sebastian; Gu, Jing Chemistry of Materials, Vol. 29, Issue 15 https://doi.org/10.1021/acs.chemmater.7b02122	journal	July 2017
Modeling amorphous thin films: Kinetically limited minimization Zawadzki, Paweł P.; Perkins, John; Lany, Stephan Physical Review B, Vol. 90, Issue 9 https://doi.org/10.1103/PhysRevB.90.094203	journal	September 2014
Structure Prediction of Binary Pernitride MN ₂ Compounds (M=Ca, Sr, Ba, La, and Ti) Kulkarni, A.; Schön, J. C.; Doll, K. Chemistry - An Asian Journal, Vol. 8, Issue 4 https://doi.org/10.1002/asia.201200794	journal	January 2013
Assessment of the Hf–N, Zr–N and Ti–N phase diagrams at high pressures and temperatures: balancing between MN and M ₃ N ₄ (M = Hf, Zr, Ti) Kroll, Peter Journal of Physics: Condensed Matter, Vol. 16, Issue 14 https://doi.org/10.1088/0953-8984/16/14/035	journal	March 2004
Advanced flat top laser heating system for high pressure research at GSECARS: application to the melting behavior of germanium Prakapenka, V. B.; Kubo, A.; Kuznetsov, A. High Pressure Research, Vol. 28, Issue 3 https://doi.org/10.1080/08957950802050718	journal	September 2008
The thermodynamic scale of inorganic crystalline metastability Sun, Wenhao; Dacek, Stephen T.; Ong, Shyue Ping Science Advances, Vol. 2, Issue 11 https://doi.org/10.1126/sciadv.1600225	journal	November 2016
Optical properties of cubic Ti3N4, Zr3N4, and Hf3N4 Xu, Ming; Wang, Songyou; Yin, Gang Applied Physics Letters, Vol. 89, Issue 15 https://doi.org/10.1063/1.2360937	journal	October 2006
CALYPSO: A method for crystal structure prediction Wang, Yanchao; Lv, Jian; Zhu, Li Computer Physics Communications, Vol. 183, Issue 10 https://doi.org/10.1016/j.cpc.2012.05.008	journal	October 2012
Vibrational spectra of ternary sulfides with the Th3P4 structure Provenzano, Paul L.; Boldish, Steven I.; White, William B. Materials Research Bulletin, Vol. 12, Issue 9 https://doi.org/10.1016/0025-5408(77)90106-4	journal	September 1977
An ultrasensitive molybdenum-based double-heterojunction phototransistor No authors listed Zenodo https://doi.org/10.5281/zenodo.4835973	text	January 2021
CALYPSO: a method for crystal structure prediction Wang, Yanchao; Lv, Jian; Zhu, Li arXiv https://doi.org/10.48550/arxiv.1205.2264	text	January 2012
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
High-Pressure Multianvil Synthesis and Structure Refinement of Oxygen-Bearing Cubic Zirconium(IV) Nitride. Dzivenko, Dmytro A.; Zerr, Andreas; Bulatov, Vadim K. ChemInform, Vol. 38, Issue 40 https://doi.org/10.1002/chin.200740026	journal	October 2007
Raman spectrum of rutile: Polarisation studies Narayanan, P. S. Proceedings of the Indian Academy of Sciences - Section A, Vol. 37, Issue 3 https://doi.org/10.1007/BF03052659	journal	March 1953
High-Pressure Synthesis and Characterization of Incompressible Titanium Pernitride Bhadram, Venkata S.; Kim, Duck Young; Strobel, Timothy A. Chemistry of Materials, Vol. 28, Issue 6 https://doi.org/10.1021/acs.chemmater.6b00042	journal	February 2016
Thin film synthesis and properties of copper nitride, a metastable semiconductor Caskey, Christopher M.; Richards, Ryan M.; Ginley, David S. Mater. Horiz., Vol. 1, Issue 4 https://doi.org/10.1039/C4MH00049H	journal	January 2014
Prediction of the new spinel phase of Ti 3 N 4 and SiTi 2 N 4 and the metal-insulator transition Ching, W. Y.; Mo, Shang-Di; Ouyang, Lizhi Physical Review B, Vol. 61, Issue 16 https://doi.org/10.1103/PhysRevB.61.10609	journal	April 2000
Rare‐Earth Compounds with the Th ₃ P ₄ ‐Type Structure Holtzberg, F.; Methfessel, S. Journal of Applied Physics, Vol. 37, Issue 3 https://doi.org/10.1063/1.1708500	journal	March 1966
High-Pressure Multianvil Synthesis and Structure Refinement of Oxygen-Bearing Cubic Zirconium(IV) Nitride Dzivenko, D. A.; Zerr, A.; Bulatov, V. K. Advanced Materials, Vol. 19, Issue 14 https://doi.org/10.1002/adma.200602610	journal	July 2007
Crystal structure prediction via particle-swarm optimization Wang, Yanchao; Lv, Jian; Zhu, Li Physical Review B, Vol. 82, Issue 9 https://doi.org/10.1103/PhysRevB.82.094116	journal	September 2010
Thin films of hard cubic Zr3N4 stabilized by stress Chhowalla, Manish; Unalan, H. Emrah Nature Materials, Vol. 4, Issue 4 https://doi.org/10.1038/nmat1338	journal	March 2005
Hafnium Nitride with Thorium Phosphide Structure: Physical Properties and an Assessment of the Hf-N, Zr-N, and Ti-N Phase Diagrams at High Pressures and Temperatures Kroll, Peter Physical Review Letters, Vol. 90, Issue 12 https://doi.org/10.1103/PhysRevLett.90.125501	journal	March 2003
High-pressure chemistry of nitride-based materials Horvath-Bordon, Elisabeta; Riedel, Ralf; Zerr, Andreas Chemical Society Reviews, Vol. 35, Issue 10 https://doi.org/10.1039/b517778m	journal	January 2006
Synthesis of cubic silicon nitride Zerr, Andreas; Miehe, Gerhard; Serghiou, George Nature, Vol. 400, Issue 6742 https://doi.org/10.1038/22493	journal	July 1999
Influence of the exchange screening parameter on the performance of screened hybrid functionals Krukau, Aliaksandr V.; Vydrov, Oleg A.; Izmaylov, Artur F. The Journal of Chemical Physics, Vol. 125, Issue 22 https://doi.org/10.1063/1.2404663	journal	December 2006
Electronic Structure of Spinel-Type Nitride Compounds Si 3 N 4 , Ge 3 N 4 , and Sn 3 N 4 with Tunable Band Gaps: Application to Light Emitting Diodes Boyko, T. D.; Hunt, A.; Zerr, A. Physical Review Letters, Vol. 111, Issue 9 https://doi.org/10.1103/PhysRevLett.111.097402	journal	August 2013
Raman spectrum of anatase, TiO2 Ohsaka, Toshiaki; Izumi, Fujio; Fujiki, Yoshinori Journal of Raman Spectroscopy, Vol. 7, Issue 6 https://doi.org/10.1002/jrs.1250070606	journal	December 1978
Monte Carlo simulations of disorder in ZnSn N 2 and the effects on the electronic structure Lany, Stephan; Fioretti, Angela N.; Zawadzki, Paweł P. Physical Review Materials, Vol. 1, Issue 3 https://doi.org/10.1103/PhysRevMaterials.1.035401	journal	August 2017
Thermodynamic Routes to Novel Metastable Nitrogen-Rich Nitrides Sun, Wenhao; Holder, Aaron; Orvañanos, Bernardo Chemistry of Materials, Vol. 29, Issue 16 https://doi.org/10.1021/acs.chemmater.7b02399	journal	August 2017
Recent Advances in New Hard High-Pressure Nitrides Zerr, A.; Riedel, R.; Sekine, T. Advanced Materials, Vol. 18, Issue 22 https://doi.org/10.1002/adma.200501872	journal	November 2006
Raman scattering, superconductivity, and phonon density of states of stoichiometric and nonstoichiometric TiN Spengler, W.; Kaiser, R.; Christensen, A. N. Physical Review B, Vol. 17, Issue 3 https://doi.org/10.1103/PhysRevB.17.1095	journal	February 1978
2D metal carbides and nitrides (MXenes) for energy storage Anasori, Babak; Lukatskaya, Maria R.; Gogotsi, Yury Nature Reviews Materials, Vol. 2, Issue 2 https://doi.org/10.1038/natrevmats.2016.98	journal	January 2017
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Synthesis of Tetragonal and Orthorhombic Polymorphs of Hf ₃ N ₄ by High-Pressure Annealing of a Prestructured Nanocrystalline Precursor Salamat, Ashkan; Hector, Andrew L.; Gray, Benjamin M. Journal of the American Chemical Society, Vol. 135, Issue 25 https://doi.org/10.1021/ja403368b	journal	June 2013
Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets Chen, Ruyi; Cui, Qirui; Liao, Liyang Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-23414-3	journal	May 2021
Recent Advances in New Hard High-Pressure Nitrides Zerr, Andreas; Riedel, Ralf; Sekine, Toshimori ChemInform, Vol. 38, Issue 3 https://doi.org/10.1002/chin.200703212	journal	January 2007
Phase stability, chemical bonding and mechanical properties of titanium nitrides: a first-principles study Yu, Shuyin; Zeng, Qingfeng; Oganov, Artem R. Physical Chemistry Chemical Physics, Vol. 17, Issue 17 https://doi.org/10.1039/C5CP00156K	journal	January 2015
High-Pressure Chemistry of Nitride-Based Materials Horvath-Bordon, Elisabeta; Riedel, Ralf; Zerr, Andreas ChemInform, Vol. 37, Issue 51 https://doi.org/10.1002/chin.200651227	journal	December 2006

Cited By (5)

New nitrides: from high pressure–high temperature synthesis to layered nanomaterials and energy applications McMillan, Paul F. Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 377, Issue 2147 https://doi.org/10.1098/rsta.2018.0244	journal	April 2019
Ternary nitride semiconductors in the rocksalt crystal structure Bauers, Sage R.; Holder, Aaron; Sun, Wenhao Proceedings of the National Academy of Sciences, Vol. 116, Issue 30 https://doi.org/10.1073/pnas.1904926116	journal	July 2019
Eighteen functional monolayer metal oxides: wide bandgap semiconductors with superior oxidation resistance and ultrahigh carrier mobility Guo, Yu; Ma, Liang; Mao, Keke Nanoscale Horizons, Vol. 4, Issue 3 https://doi.org/10.1039/c8nh00273h	journal	January 2019
Discovery of Ternary Silicon Titanium Nitride with Spinel-Type Structure Bhat, Shrikant; Lale, Abhijeet; Bernard, Samuel Deutsches Elektronen-Synchrotron, DESY, Hamburg https://doi.org/10.3204/pubdb-2020-01228	text	January 2020
Discovery of Ternary Silicon Titanium Nitride with Spinel-Type Structure Bhat, Shrikant; Lale, Abhijeet; Bernard, Samuel Scientific Reports, Vol. 10, Issue 1 https://doi.org/10.1038/s41598-020-64101-5	journal	April 2020

Similar Records

Characterization of magnetic properties of

{Sr}_{2}

{CuWO}_{6}

and

{Sr}_{2}

{CuMoO}_{6}

Journal Article · Tue Apr 01 04:00:00 UTC 2014 · Physical Review. B, Condensed Matter and Materials Physics · OSTI ID:1392128

Pressure-induced cation-cation bonding in

V_{2} O_{3}

Journal Article · Fri Oct 09 00:00:00 UTC 2015 · Physical Review. B, Condensed Matter and Materials Physics · OSTI ID:1332787

Highly anisotropic exchange interactions of

j_{eff} = \frac{1}{2}

iridium moments on the fcc lattice in

{La}_{2} B {IrO}_{6} (B = Mg, Zn)

Journal Article · Mon Jun 20 00:00:00 UTC 2016 · Physical Review B · OSTI ID:1260071

Related Subjects

75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY