DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Verification of stability and unraveling the electronic and physical properties of bulk and (001)-surfaces of newly synthesized Ti2ZnX (X = C, N) MAX phases

Abstract

MAX phase family has been extended by the addition of late transition metals at the A-site with the expectation of diverse functional properties. Here, we present our systematic density functional investigation on the thermodynamic and phonon stabilities, elastic properties, including elastic constants, elastic moduli and elastic anisotropy of newly synthesized Ti2ZnX (X = C, N) phases in comparison with conventional Ti2AlX (X = C, N). Due to the smaller size of N as compared to C, the unit cell dimension is reduced when C atoms are replaced by N atoms at the X-site. Furthermore, the Ti2ZnC and Ti2ZnN are stable at the equilibrium volume of 110.84 Å3 and 105.70 Å3. The thermodynamic, mechanical and dynamical stabilities are validated by estimating the formation energies, elastic constants and phonon dispersions, respectively. The elastic properties of Ti2ZnN are less anisotropic as compared to those of Ti2ZnC. To understand the thin-film characteristics in Ti2ZnX, the surface properties with (001)-terminated slabs are investigated. Both Ti2ZnX bulk and (001)-surfaces exhibit metal-like electronic structures. There is a strong covalent bonding between Ti-X and Ti-Zn atoms confirmed by the charge density map and Mulliken population analysis. Additional states are generated at the Fermi level (EF) due to themore » unusual d-p states hybridization between Ti and Zn atoms. The anisotropy in chemical bonding is confirmed by the cleavage energy difference between Ti-X and Ti-Zn. Here, Ti(X)-001 and Zn-001 terminations are stable surfaces; however, in terms of chemical potentials, Zn-001 termination is the most favourable in Ti2ZnX.« less

Authors:
ORCiD logo [1];  [2];  [3];  [3];  [4];  [5]
  1. Univ. of Wisconsin, Madison, WI (United States)
  2. Chittagong Univ. of Engineering and Technology (CUET), Chattogram (Bangladesh)
  3. Harbin Inst. of Technology (China)
  4. National Taiwan Univ., Taipei (Taiwan)
  5. Ames Lab., and Iowa State Univ., Ames, IA (United States)
Publication Date:
Research Org.:
Ames Lab., Ames, IA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1875266
Report Number(s):
IS-J 10,846
Journal ID: ISSN 2468-0230; 2017-VII-0003-0096; DE-AC02-07CH11358; 51971084; 52031003
Grant/Contract Number:  
AC02-07CH11358
Resource Type:
Accepted Manuscript
Journal Name:
Surfaces and Interfaces
Additional Journal Information:
Journal Volume: 31; Journal ID: ISSN 2468-0230
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; MAX phase; Phase stability; Surface energy; Surface stability; Electronic structure; Density functional investigation

Citation Formats

Qureshi, Muhammad Waqas, Ali, M. A., Ma, Xinxin, Tang, Guangze, Javed, M. Usman, and Paudyal, Durga. Verification of stability and unraveling the electronic and physical properties of bulk and (001)-surfaces of newly synthesized Ti2ZnX (X = C, N) MAX phases. United States: N. p., 2022. Web. doi:10.1016/j.surfin.2022.102032.
Qureshi, Muhammad Waqas, Ali, M. A., Ma, Xinxin, Tang, Guangze, Javed, M. Usman, & Paudyal, Durga. Verification of stability and unraveling the electronic and physical properties of bulk and (001)-surfaces of newly synthesized Ti2ZnX (X = C, N) MAX phases. United States. https://doi.org/10.1016/j.surfin.2022.102032
Qureshi, Muhammad Waqas, Ali, M. A., Ma, Xinxin, Tang, Guangze, Javed, M. Usman, and Paudyal, Durga. Fri . "Verification of stability and unraveling the electronic and physical properties of bulk and (001)-surfaces of newly synthesized Ti2ZnX (X = C, N) MAX phases". United States. https://doi.org/10.1016/j.surfin.2022.102032. https://www.osti.gov/servlets/purl/1875266.
@article{osti_1875266,
title = {Verification of stability and unraveling the electronic and physical properties of bulk and (001)-surfaces of newly synthesized Ti2ZnX (X = C, N) MAX phases},
author = {Qureshi, Muhammad Waqas and Ali, M. A. and Ma, Xinxin and Tang, Guangze and Javed, M. Usman and Paudyal, Durga},
abstractNote = {MAX phase family has been extended by the addition of late transition metals at the A-site with the expectation of diverse functional properties. Here, we present our systematic density functional investigation on the thermodynamic and phonon stabilities, elastic properties, including elastic constants, elastic moduli and elastic anisotropy of newly synthesized Ti2ZnX (X = C, N) phases in comparison with conventional Ti2AlX (X = C, N). Due to the smaller size of N as compared to C, the unit cell dimension is reduced when C atoms are replaced by N atoms at the X-site. Furthermore, the Ti2ZnC and Ti2ZnN are stable at the equilibrium volume of 110.84 Å3 and 105.70 Å3. The thermodynamic, mechanical and dynamical stabilities are validated by estimating the formation energies, elastic constants and phonon dispersions, respectively. The elastic properties of Ti2ZnN are less anisotropic as compared to those of Ti2ZnC. To understand the thin-film characteristics in Ti2ZnX, the surface properties with (001)-terminated slabs are investigated. Both Ti2ZnX bulk and (001)-surfaces exhibit metal-like electronic structures. There is a strong covalent bonding between Ti-X and Ti-Zn atoms confirmed by the charge density map and Mulliken population analysis. Additional states are generated at the Fermi level (EF) due to the unusual d-p states hybridization between Ti and Zn atoms. The anisotropy in chemical bonding is confirmed by the cleavage energy difference between Ti-X and Ti-Zn. Here, Ti(X)-001 and Zn-001 terminations are stable surfaces; however, in terms of chemical potentials, Zn-001 termination is the most favourable in Ti2ZnX.},
doi = {10.1016/j.surfin.2022.102032},
journal = {Surfaces and Interfaces},
number = ,
volume = 31,
place = {United States},
year = {2022},
month = {5}
}

Works referenced in this record:

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Magnetron sputtered epitaxial single-phase Ti3SiC2 thin films
journal, July 2002

  • Palmquist, J. -P.; Jansson, U.; Seppänen, T.
  • Applied Physics Letters, Vol. 81, Issue 5
  • DOI: 10.1063/1.1494865

Growth and characterization of MAX-phase thin films
journal, April 2005


Processing of MAX phases: From synthesis to applications
journal, November 2020

  • Gonzalez‐Julian, Jesus
  • Journal of the American Ceramic Society, Vol. 104, Issue 2
  • DOI: 10.1111/jace.17544

High-throughput computational discovery of ternary-layered MAX phases and prediction of their exfoliation for formation of 2D MXenes
journal, January 2021

  • Khaledialidusti, Rasoul; Khazaei, Mohammad; Khazaei, Somayeh
  • Nanoscale, Vol. 13, Issue 15
  • DOI: 10.1039/D0NR08791B

First-principles study of Ti3AC2 (A=Si, Al) (001) surfaces
journal, August 2007


The Rise of MXenes
journal, July 2019


A genomic approach to the stability, elastic, and electronic properties of the MAX phases: A genomic approach to stability and properties of the MAX phases
journal, June 2014

  • Aryal, Sitaram; Sakidja, Ridwan; Barsoum, Michel W.
  • physica status solidi (b), Vol. 251, Issue 8
  • DOI: 10.1002/pssb.201451226

Tendencies in ABO3 Perovskite and SrF2, BaF2 and CaF2 Bulk and Surface F-Center Ab Initio Computations at High Symmetry Cubic Structure
journal, October 2021

  • Eglitis, Roberts I.; Purans, Juris; Popov, Anatoli I.
  • Symmetry, Vol. 13, Issue 10
  • DOI: 10.3390/sym13101920

Chemical bonding and electronic-structure in MAX phases as viewed by X-ray spectroscopy and density functional theory
journal, January 2017


Work of adhesion of interfaces between M2AlC (M = Ti, V, Cr) MAX phases and α-Al2O3
journal, December 2018


Formation of Ti 2 AuN from Au-Covered Ti 2 AlN Thin Films: A General Strategy to Thermally Induce Intercalation of Noble Metals into MAX Phases
journal, April 2020

  • Kashiwaya, Shun; Lai, Chung-Chuan; Lu, Jun
  • Crystal Growth & Design, Vol. 20, Issue 6
  • DOI: 10.1021/acs.cgd.0c00355

Calculated elastic properties of M2AlC (M=Ti, V, Cr, Nb and Ta)
journal, March 2004


Origin of Chemically Ordered Atomic Laminates ( i -MAX): Expanding the Elemental Space by a Theoretical/Experimental Approach
journal, July 2018


Experimental and theoretical characterization of ordered MAX phases Mo 2 TiAlC 2 and Mo 2 Ti 2 AlC 3
journal, September 2015

  • Anasori, Babak; Dahlqvist, Martin; Halim, Joseph
  • Journal of Applied Physics, Vol. 118, Issue 9
  • DOI: 10.1063/1.4929640

Intrinsic defect processes and elastic properties of Ti 3 AC 2 (A = Al, Si, Ga, Ge, In, Sn) MAX phases
journal, January 2018

  • Christopoulos, S. -R. G.; Filippatos, P. P.; Hadi, M. A.
  • Journal of Applied Physics, Vol. 123, Issue 2
  • DOI: 10.1063/1.5011374

Corrosion mechanism of Ti2AlC MAX phase coatings under the synergistic effects of water vapor and solid NaCl at 600 °C
journal, November 2021


Interface properties of Ti3SiC2/Al2O3 ceramics: Combined experiments and first-principles calculations
journal, March 2021


Electronic, elastic, and thermal properties, fracture toughness, and damage tolerance of TM5Si3B (TM = V and Nb) MAB phases
journal, February 2022

  • Sun, Yuan; Yang, Ancang; Duan, Yonghua
  • International Journal of Refractory Metals and Hard Materials, Vol. 103
  • DOI: 10.1016/j.ijrmhm.2022.105781

Ab initio study of the Cr2AlC(0001) surface
journal, April 2006

  • Sun, Zhimei; Ahuja, Rajeev
  • Applied Physics Letters, Vol. 88, Issue 16
  • DOI: 10.1063/1.2197938

The Compressibility of Media under Extreme Pressures
journal, September 1944

  • Murnaghan, F. D.
  • Proceedings of the National Academy of Sciences, Vol. 30, Issue 9
  • DOI: 10.1073/pnas.30.9.244

Synthesis of Ti3AuC2, Ti3Au2C2 and Ti3IrC2 by noble metal substitution reaction in Ti3SiC2 for high-temperature-stable Ohmic contacts to SiC
journal, May 2017

  • Fashandi, Hossein; Dahlqvist, Martin; Lu, Jun
  • Nature Materials, Vol. 16, Issue 8
  • DOI: 10.1038/nmat4896

Carbides of formula T2MC
journal, August 1964


Oxidation of Cr2AlC coatings in the temperature range of 1230 to 1410°C
journal, November 2011


Conductive two-dimensional titanium carbide ‘clay’ with high volumetric capacitance
journal, November 2014

  • Ghidiu, Michael; Lukatskaya, Maria R.; Zhao, Meng-Qiang
  • Nature, Vol. 516, Issue 7529
  • DOI: 10.1038/nature13970

Structural and elastic properties under pressure effect of Hf 2 AlN and Hf 2 AlC
journal, March 2008


Anisotropy of the resistivity and charge-carrier sign in nanolaminated Ti 2 AlC: Experiment and ab initio calculations
journal, June 2013


Experimental and DFT investigation of (Cr,Ti) 3 AlC 2 MAX phases stability
journal, September 2016


Necessary and sufficient elastic stability conditions in various crystal systems
journal, December 2014


Structural, mechanical, dynamical and electronic properties and high-pressure behavior of Mo2GeC: A first-principles study
journal, September 2017


Electromagnetic interference shielding with 2D transition metal carbides (MXenes)
journal, September 2016


Stability trends of M A X phases from first principles
journal, June 2010


Magnetic nanoscale laminates with tunable exchange coupling from first principles
journal, December 2011


Pressure effect on the structural, elastic and electronic properties of Nb2AC (A=S and In) phases; ab initio study
journal, January 2014


Ab initio predictions of structure and physical properties of the Zr2GaC and Hf2GaC MAX phases under pressure
journal, February 2021


Fabrication and Mechanical Properties of Cr2AlC MAX Phase Coatings on TiBw/Ti6Al4V Composite Prepared by HiPIMS
journal, February 2021

  • Qureshi, Muhammad Waqas; Ma, Xinxin; Tang, Guangze
  • Materials, Vol. 14, Issue 4
  • DOI: 10.3390/ma14040826

Prediction of the stability of the M n + 1 A X n phases from first principles
journal, December 2009


Tribological behavior of select MAX phases against Al2O3 at elevated temperatures
journal, July 2008


Ab initio study on the adsorption mechanism of oxygen on Cr2AlC (0 0 0 1) surface
journal, October 2014


MXene-based gas sensors
journal, January 2021

  • Bhardwaj, Radha; Hazra, Arnab
  • Journal of Materials Chemistry C, Vol. 9, Issue 44
  • DOI: 10.1039/D1TC04085E

The origin of anisotropy and high density of states in the electronic structure of Cr 2 GeC by means of polarized soft x-ray spectroscopy and ab initio calculations
journal, September 2015


Radiation tolerance of Mn+1AXn phases, Ti3AlC2 and Ti3SiC2
journal, August 2010


Surface energy of M2AC(0001) determined by density functional theory (M=Ti,V,Cr; A=Al,Ga,Ge)
journal, February 2007


Computational Prediction of Boron-Based MAX Phases and MXene Derivatives
journal, July 2020


Application of MXenes for water treatment and energy-efficient desalination: A review
journal, February 2022


Physical properties of predicted Ti2CdN versus existing Ti2CdC MAX phase: An ab initio study
journal, February 2016


Synthesis and Design of Superhard Materials
journal, August 2001


Two-Dimensional Nanocrystals Produced by Exfoliation of Ti3AlC2
journal, August 2011

  • Naguib, Michael; Kurtoglu, Murat; Presser, Volker
  • Advanced Materials, Vol. 23, Issue 37, p. 4248-4253
  • DOI: 10.1002/adma.201102306

Screen the thermomechanical and optical properties of the new ductile 314 MAX phase boride Zr3CdB4: A DFT insight
journal, October 2021


Synthesis of MAX phases Nb 2 CuC and Ti 2 (Al 0.1 Cu 0.9 )N by A-site replacement reaction in molten salts
journal, October 2019


Layered machinable ceramics for high temperature applications
journal, March 1997


Structural investigation of substoichiometry and solid solution effects in Ti2Al(Cx,N1−x)y compounds
journal, July 2012


General methods for geometry and wave function optimization
journal, November 1992

  • Fischer, Thomas H.; Almlof, Jan
  • The Journal of Physical Chemistry, Vol. 96, Issue 24
  • DOI: 10.1021/j100203a036

V 2 CT x and Ti 3 C 2 T x MXenes Nanosheets for Gas Sensing
journal, June 2021


Ternary boride Hf3PB4: Insights into the physical properties of the hardest possible boride MAX phase
journal, March 2021


Theoretical predictive screening of noble-metal-containing M3AuC2 (M = Ti, V, and Cr) MAX phases
journal, February 2022


Synthesis and Characterization of Double Solid Solution (Zr,Ti) 2 (Al,Sn)C MAX Phase Ceramics
journal, May 2019


Iterative minimization techniques for ab initio total-energy calculations: molecular dynamics and conjugate gradients
journal, October 1992


Electronic mechanism of hardness enhancement in transition-metal carbonitrides
journal, May 1999

  • Jhi, Seung-Hoon; Ihm, Jisoon; Louie, Steven G.
  • Nature, Vol. 399, Issue 6732
  • DOI: 10.1038/20148

Ab initio study of ductility in M 2 Al C ( M = Ti , V, Cr)
journal, May 2007


Element Replacement Approach by Reaction with Lewis Acidic Molten Salts to Synthesize Nanolaminated MAX Phases and MXenes
journal, March 2019

  • Li, Mian; Lu, Jun; Luo, Kan
  • Journal of the American Chemical Society, Vol. 141, Issue 11
  • DOI: 10.1021/jacs.9b00574

2D metal carbides and nitrides (MXenes) for energy storage
journal, January 2017


A progress report on the MAB phases: atomically laminated, ternary transition metal borides
journal, July 2019


Insights into the physical properties of a new 211 MAX phase Nb2CuC
journal, February 2021


The MAX Phases: Unique New Carbide and Nitride Materials
journal, January 2001

  • Barsoum, Michel; El-Raghy, Tamer
  • American Scientist, Vol. 89, Issue 4
  • DOI: 10.1511/2001.28.334