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Title: Synthesis, Hardness, and Electronic Properties of Stoichiometric VN and CrN

Abstract

Here, we report synthesis of single-crystal VN and CrN through high-pressure ionexchange reaction routes. The final products are stoichiometric and have crystallite sizes in the range of 50-120 μm. We also prepared VN and TiN crystals using high-pressure sintering of nitride powders. On the basis of single-crystal indentation testing, the determined asymptotic Vickers hardness for TiN, VN, and CrN is 18 (1), 10 (1), and 16 (1) GPa, respectively. The relatively low hardness in VN indicates that the metallic bonding prevails due to the overfilled metallic σ bonds, although the cation-anion covalent hybridization in this compound is much stronger than that in TiN and CrN. All three nitrides are intrinsically excellent metals at ambient pressure. In particular, VN exhibits superconducting transition at Tc ≈ 7.8 K, which is slightly lower than the reported values for nitrogen-deficient or crystallinedisordered samples due to unsuppressed “spin fluctuation” in the well-crystallized stoichiometric VN. The magnetostructural transition in CrN correlates with a metal-metal transition at TN = 240(5) K and is accompanied by a ~40% drop in electrical resistivity. In addition, more detailed electronic properties are presented with new insights into these nitrides.

Authors:
 [1];  [2];  [3];  [4];  [5];  [6];  [4]
  1. Univ. of Nevada, Las Vegas, NV (United States); Sichuan Univ., Chengdu (China)
  2. Chinese Academy of Sciences (CAS), Beijing (China)
  3. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  4. Univ. of Nevada, Las Vegas, NV (United States)
  5. Arizona State Univ., Tempe, AZ (United States)
  6. Sichuan Univ., Chengdu (China)
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Univ. of Nevada, Las Vegas, NV (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1261496
Alternate Identifier(s):
OSTI ID: 1332351
Grant/Contract Number:  
AC05-00OR22725; NA0001982
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Crystal Growth and Design
Additional Journal Information:
Journal Volume: 16; Journal Issue: 1; Journal ID: ISSN 1528-7483
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; transition-metal nitrides; vickers hardness; ion-exchange reaction; high-pressure synthesis; 36 MATERIALS SCIENCE

Citation Formats

Wang, Shanmin, Yu, Xiaohui, Zhang, Jianzhong, Wang, Liping, Leinenweber, Kurt, He, Duanwei, and Zhao, Yusheng. Synthesis, Hardness, and Electronic Properties of Stoichiometric VN and CrN. United States: N. p., 2015. Web. doi:10.1021/acs.cgd.5b01312.
Wang, Shanmin, Yu, Xiaohui, Zhang, Jianzhong, Wang, Liping, Leinenweber, Kurt, He, Duanwei, & Zhao, Yusheng. Synthesis, Hardness, and Electronic Properties of Stoichiometric VN and CrN. United States. https://doi.org/10.1021/acs.cgd.5b01312
Wang, Shanmin, Yu, Xiaohui, Zhang, Jianzhong, Wang, Liping, Leinenweber, Kurt, He, Duanwei, and Zhao, Yusheng. 2015. "Synthesis, Hardness, and Electronic Properties of Stoichiometric VN and CrN". United States. https://doi.org/10.1021/acs.cgd.5b01312. https://www.osti.gov/servlets/purl/1261496.
@article{osti_1261496,
title = {Synthesis, Hardness, and Electronic Properties of Stoichiometric VN and CrN},
author = {Wang, Shanmin and Yu, Xiaohui and Zhang, Jianzhong and Wang, Liping and Leinenweber, Kurt and He, Duanwei and Zhao, Yusheng},
abstractNote = {Here, we report synthesis of single-crystal VN and CrN through high-pressure ionexchange reaction routes. The final products are stoichiometric and have crystallite sizes in the range of 50-120 μm. We also prepared VN and TiN crystals using high-pressure sintering of nitride powders. On the basis of single-crystal indentation testing, the determined asymptotic Vickers hardness for TiN, VN, and CrN is 18 (1), 10 (1), and 16 (1) GPa, respectively. The relatively low hardness in VN indicates that the metallic bonding prevails due to the overfilled metallic σ bonds, although the cation-anion covalent hybridization in this compound is much stronger than that in TiN and CrN. All three nitrides are intrinsically excellent metals at ambient pressure. In particular, VN exhibits superconducting transition at Tc ≈ 7.8 K, which is slightly lower than the reported values for nitrogen-deficient or crystallinedisordered samples due to unsuppressed “spin fluctuation” in the well-crystallized stoichiometric VN. The magnetostructural transition in CrN correlates with a metal-metal transition at TN = 240(5) K and is accompanied by a ~40% drop in electrical resistivity. In addition, more detailed electronic properties are presented with new insights into these nitrides.},
doi = {10.1021/acs.cgd.5b01312},
url = {https://www.osti.gov/biblio/1261496}, journal = {Crystal Growth and Design},
issn = {1528-7483},
number = 1,
volume = 16,
place = {United States},
year = {Mon Nov 09 00:00:00 EST 2015},
month = {Mon Nov 09 00:00:00 EST 2015}
}

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Cited by: 43 works
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Works referenced in this record:

Nitrogen-rich transition metal nitrides
journal, July 2013


High-pressure chemistry of nitride-based materials
journal, January 2006


Role of N defects in paramagnetic CrN at finite temperatures from first principles
journal, March 2015


Temperature dependence of TiN elastic constants from ab initio molecular dynamics simulations
journal, March 2013


Questionable collapse of the bulk modulus in CrN
journal, April 2010


Reduction of the bulk modulus at high pressure in CrN
journal, October 2009


Superinsulator and quantum synchronization
journal, April 2008


Role of N Defects on Thermally Induced Atomic-Scale Structural Changes in Transition-Metal Nitrides
journal, September 2007


Vacancy Hardening and Softening in Transition Metal Carbides and Nitrides
journal, April 2001


Magnetic Stress as a Driving Force of Structural Distortions: The Case of CrN
journal, December 2000


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


Electronic structure of CrN: A borderline Mott insulator
journal, January 2009


Material selection for hard coatings
journal, November 1986


Antiferromagnetic Structure of CrN
journal, February 1960


Electronic properties of transition-metal nitrides: The group-V and group-VI nitrides VN, NbN, TaN, CrN, MoN, and WN
journal, January 1985


Microstructure and electronic properties of the refractory semiconductor ScN grown on MgO(001) by ultra-high-vacuum reactive magnetron sputter deposition
journal, July 1998


Superconductivity of VN under pressure
journal, February 1984


Neutron Diffraction Studies of the Compounds MnN and FeN
journal, April 2001


Crystal structure and magnetic properties of the compound CoN
journal, July 1995


Characterization of low temperature CrN and TiN (PVD) hard coatings
journal, September 1995


Epitaxial suppression of the metal-insulator transition in CrN
journal, August 2011


Synthesis of TiN, VN, and CrN from Ammonolysis of TiS2, VS2, and Cr2S3
journal, November 1997


Chemical vapor deposition of titanium nitride at low temperatures
journal, July 1986


Synthesis of Stoichiometric and Bulk CrN through a Solid-State Ion-Exchange Reaction
journal, October 2012


An investigation of the antiferromagnetic transition of CrN
journal, April 1970


Physical and mechanical properties of cubic δ-VN1−x
journal, July 1985


The N-Ti (Nitrogen-Titanium) system
journal, August 1987


CrN single-crystal growth using Cr–Ga–Na ternary melt
journal, December 2002


Experimental invalidation of phase-transition-induced elastic softening in CrN
journal, August 2012


Non-stoichiometry and Antiferromagnetic Phase Transition of NaCl-type CrN Thin Films Prepared by Reactive Sputtering
journal, January 1996


Synthesis of cubic zirconium and hafnium nitride having Th3P4 structure
journal, February 2003


Synthesis of Tetragonal and Orthorhombic Polymorphs of Hf 3 N 4 by High-Pressure Annealing of a Prestructured Nanocrystalline Precursor
journal, June 2013


High-Pressure Synthesis of Tantalum Nitride Having Orthorhombic U 2 S 3 Structure
journal, July 2009


Novel Rhenium Nitrides
journal, August 2010


Synthesis of Novel Transition Metal Nitrides IrN 2 and OsN 2
journal, April 2006


Synthesis and characterization of a binary noble metal nitride
journal, April 2004


Super hard cubic phases of period VI transition metal nitrides: First principles investigation
journal, November 2008


Elastic stability and electronic structure of pyrite type PtN2: A hard semiconductor
journal, January 2006


Electronic and bonding analysis of hardness in pyrite-type transition-metal pernitrides
journal, October 2014


Congruent melting of gallium nitride at 6 GPa and its application to single-crystal growth
journal, October 2003


Synthesis, Crystal Structure, and Elastic Properties of Novel Tungsten Nitrides
journal, August 2012


A New Molybdenum Nitride Catalyst with Rhombohedral MoS 2 Structure for Hydrogenation Applications
journal, April 2015


The Hardest Superconducting Metal Nitride
journal, September 2015


Pressure calibration for the cubic press by differential thermal analysis and the high-pressure fusion curve of aluminum
journal, December 2009


Cell assemblies for reproducible multi-anvil experiments (the COMPRES assemblies)
journal, January 2012


A study on the preparation and physical property determination of NaVO2
journal, April 1988


Hardness and fracture toughness of moissanite
journal, October 2005


Superhard B–C–N materials synthesized in nanostructured bulks
journal, December 2002


Harder than diamond: Dreams and reality
journal, January 2002


Hard superconducting nitrides
journal, February 2005


High-temperature hardness of bulk single-crystal gallium nitride - in comparison with other wide-gap materials
journal, November 2000


Growth of single‐crystal TiN/VN strained‐layer superlattices with extremely high mechanical hardness
journal, July 1987


On the intrinsic hardness of a metallic film/substrate system: Indentation size and substrate effects
journal, July 2012


Superconducting and normal-state properties of vanadium nitride
journal, June 1984


Evidence for a Correlated Insulator to Antiferromagnetic Metal Transition in CrN
journal, June 2010


X‐ray photoemission spectra of reactively sputtered TiN
journal, June 1992


Stoichiometric ScN and nitrogen deficient scandium nitride layers studied by photoelectron spectroscopy
journal, December 1985


Semiempirical Auger-electron energies for elements 10 ≤ Z ≤ 100
journal, October 1977


Charge transfer satellites and multiplet splitting in X-ray photoemission spectra of late transition metal halides
journal, June 1992


Works referencing / citing this record:

Magnetic origin of phase stability in cubic γ-MoN
journal, November 2018


Oxidation behaviour of composite CrN/(Cr,V)N coatings with different contents of vanadium induced by UV nanosecond laser pulses
journal, April 2018


X-ray absorption spectroscopy study of cobalt mononitride thin films
journal, December 2019


Revealing the Unusual Rigid Boron Chain Substructure in Hard and Superconductive Tantalum Monoboride
journal, March 2019


In-plane anisotropy and twin boundary effects in vanadium nitride under nanoindentation
journal, July 2017