skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Thin Film Synthesis of Semiconductors in the Mg–Sb–N Materials System

Abstract

Nitrides feature many interesting properties, such as a wide range of bandgaps suitable for optoelectronic devices including light-emitting diodes (LEDs), and piezoelectric response used in microelectromechanical systems (MEMS). Nitrides are also significantly underexplored compared to oxides and other chemistries, with many being thermochemically metastable, sparking interest from a basic science point of view. This paper reports on experimental and computational exploration of the Mg-Sb-N material system, featuring both metastable materials and semiconducting properties. Using sputter deposition, we discovered a new Mg2SbN3 nitride with a wurtzite-derived crystal structure, and synthesized the antimonide-nitride Mg3SbN with an antiperovskite crystal structure for the first time in thin film form. Theoretical calculations indicate that Mg2SbN3 is metastable and has properties relevant to LEDs and MEMS, whereas Mg3SbN has a large dielectric constant (28εo) and low hole effective masses (0.9mo), of interest for photovoltaic solar cell absorbers. The experimental solar-matched 1.3 eV optical absorption onset of the Mg3SbN antiperovskite agrees with the theoretical prediction (1.3 eV direct, 1.1 eV indirect), and with the measurements of room-temperature near-bandgap photoluminescence. Furthermore, these results make an important contribution towards understanding semiconductor properties and chemical trends in the Mg-Sb-N materials system, paving the way to future practical applications of thesemore » novel materials.« less

Authors:
ORCiD logo [1];  [1];  [1]; ORCiD logo [2]; ORCiD logo [1]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  2. National Renewable Energy Lab. (NREL), Golden, CO (United States); Colorado School of Mines, Golden, CO (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Next Generation of Materials by Design: Incorporating Metastability (CNGMD); National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Renewable Power Office. Solar Energy Technologies Office
OSTI Identifier:
1570960
Report Number(s):
NREL/JA-5K00-74199
Journal ID: ISSN 0897-4756
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 31; Journal Issue: 21; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
14 SOLAR ENERGY; 36 MATERIALS SCIENCE; nitrides; antimonides; RF sputtering; combinatorial; antiperovskite

Citation Formats

Heinselman, Karen N., Lany, Stephan, Perkins, John D., Talley, Kevin R., and Zakutayev, Andriy. Thin Film Synthesis of Semiconductors in the Mg–Sb–N Materials System. United States: N. p., 2019. Web. doi:10.1021/acs.chemmater.9b02380.
Heinselman, Karen N., Lany, Stephan, Perkins, John D., Talley, Kevin R., & Zakutayev, Andriy. Thin Film Synthesis of Semiconductors in the Mg–Sb–N Materials System. United States. doi:https://doi.org/10.1021/acs.chemmater.9b02380
Heinselman, Karen N., Lany, Stephan, Perkins, John D., Talley, Kevin R., and Zakutayev, Andriy. Wed . "Thin Film Synthesis of Semiconductors in the Mg–Sb–N Materials System". United States. doi:https://doi.org/10.1021/acs.chemmater.9b02380. https://www.osti.gov/servlets/purl/1570960.
@article{osti_1570960,
title = {Thin Film Synthesis of Semiconductors in the Mg–Sb–N Materials System},
author = {Heinselman, Karen N. and Lany, Stephan and Perkins, John D. and Talley, Kevin R. and Zakutayev, Andriy},
abstractNote = {Nitrides feature many interesting properties, such as a wide range of bandgaps suitable for optoelectronic devices including light-emitting diodes (LEDs), and piezoelectric response used in microelectromechanical systems (MEMS). Nitrides are also significantly underexplored compared to oxides and other chemistries, with many being thermochemically metastable, sparking interest from a basic science point of view. This paper reports on experimental and computational exploration of the Mg-Sb-N material system, featuring both metastable materials and semiconducting properties. Using sputter deposition, we discovered a new Mg2SbN3 nitride with a wurtzite-derived crystal structure, and synthesized the antimonide-nitride Mg3SbN with an antiperovskite crystal structure for the first time in thin film form. Theoretical calculations indicate that Mg2SbN3 is metastable and has properties relevant to LEDs and MEMS, whereas Mg3SbN has a large dielectric constant (28εo) and low hole effective masses (0.9mo), of interest for photovoltaic solar cell absorbers. The experimental solar-matched 1.3 eV optical absorption onset of the Mg3SbN antiperovskite agrees with the theoretical prediction (1.3 eV direct, 1.1 eV indirect), and with the measurements of room-temperature near-bandgap photoluminescence. Furthermore, these results make an important contribution towards understanding semiconductor properties and chemical trends in the Mg-Sb-N materials system, paving the way to future practical applications of these novel materials.},
doi = {10.1021/acs.chemmater.9b02380},
journal = {Chemistry of Materials},
number = 21,
volume = 31,
place = {United States},
year = {2019},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 3 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Design of nitride semiconductors for solar energy conversion
journal, January 2016

  • Zakutayev, Andriy
  • Journal of Materials Chemistry A, Vol. 4, Issue 18
  • DOI: 10.1039/C5TA09446A

The thermodynamic scale of inorganic crystalline metastability
journal, November 2016

  • Sun, Wenhao; Dacek, Stephen T.; Ong, Shyue Ping
  • Science Advances, Vol. 2, Issue 11
  • DOI: 10.1126/sciadv.1600225

Thermodynamic Routes to Novel Metastable Nitrogen-Rich Nitrides
journal, August 2017


A map of the inorganic ternary metal nitrides
journal, June 2019


Discovery of earth-abundant nitride semiconductors by computational screening and high-pressure synthesis
journal, June 2016

  • Hinuma, Yoyo; Hatakeyama, Taisuke; Kumagai, Yu
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms11962

Redox-Mediated Stabilization in Zinc Molybdenum Nitrides
journal, February 2018

  • Arca, Elisabetta; Lany, Stephan; Perkins, John D.
  • Journal of the American Chemical Society, Vol. 140, Issue 12
  • DOI: 10.1021/jacs.7b12861

Photovoltaic performances of mono- and mixed-halide structures for perovskite solar cell: A review
journal, July 2018


Scalable fabrication of perovskite solar cells
journal, March 2018


High dielectric constant conjugated materials for organic photovoltaics
journal, January 2017

  • Brebels, Jeroen; Manca, Jean V.; Lutsen, Laurence
  • Journal of Materials Chemistry A, Vol. 5, Issue 46
  • DOI: 10.1039/C7TA06808E

Time-of-flight neutron diffraction study of the structure of the perovskite-type oxynitride LaWO0.6N2.4
journal, November 1988


Lattice dynamics and ferroelectric properties of the nitride perovskite LaWN 3
journal, January 2017


Synthesis of the First Thorium-Containing Nitride Perovskite, TaThN3
journal, December 1995

  • Brese, Nathaniel E.; DiSalvo, F. J.
  • Journal of Solid State Chemistry, Vol. 120, Issue 2
  • DOI: 10.1006/jssc.1995.1423

Protons in perovskite nitrides and oxide nitrides: A first principles study of ThTaN3 and SrTaO2N
journal, October 2012


Electronic structure of the perovskite-type nitride RuFe3N
journal, July 2004


Rare-earth magnetic nitride perovskites
journal, March 2019

  • Flores-Livas, José A.; Sarmiento-Pérez, R.; Botti, Silvana
  • Journal of Physics: Materials, Vol. 2, Issue 2
  • DOI: 10.1088/2515-7639/ab083e

Prediction of Stable Nitride Perovskites
journal, August 2015


Synthesis of Lanthanum Tungsten Oxynitride Perovskite Thin Films
journal, May 2019

  • Talley, Kevin R.; Mangum, John; Perkins, Craig L.
  • Advanced Electronic Materials, Vol. 5, Issue 7
  • DOI: 10.1002/aelm.201900214

Les deformations quadratiques T1 et T4 dans les carbures et nitrures perowskites du manganese
journal, January 1970


Giant Field-Induced Distortion in Mn 3 SbN at Room Temperature
journal, April 2012

  • Takenaka, Koshi; Shibayama, Takashi; Kasugai, Daiki
  • Japanese Journal of Applied Physics, Vol. 51, Issue 4R
  • DOI: 10.7567/JJAP.51.043001

Giant negative thermal expansion in Ge-doped anti-perovskite manganese nitrides
journal, December 2005

  • Takenaka, K.; Takagi, H.
  • Applied Physics Letters, Vol. 87, Issue 26
  • DOI: 10.1063/1.2147726

(Sr3N)E and (Ba3N)E (E = Sb, Bi): Synthesis, Crystal Structures, and Physical Properties
journal, November 2004

  • G�bler, Frank; Kirchner, Martin; Schnelle, Walter
  • Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 630, Issue 13-14
  • DOI: 10.1002/zaac.200400256

Zn 2 SbN 3 : growth and characterization of a metastable photoactive semiconductor
journal, January 2019

  • Arca, Elisabetta; Perkins, John D.; Lany, Stephan
  • Materials Horizons, Vol. 6, Issue 8
  • DOI: 10.1039/C9MH00369J

Implications of heterostructural alloying for enhanced piezoelectric performance of (Al,Sc)N
journal, June 2018


COMBIgor: Data-Analysis Package for Combinatorial Materials Science
journal, May 2019

  • Talley, Kevin R.; Bauers, Sage R.; Melamed, Celeste L.
  • ACS Combinatorial Science, Vol. 21, Issue 7
  • DOI: 10.1021/acscombsci.9b00077

Summary of “IAEA intercomparison of IBA software”
journal, April 2008

  • Barradas, N. P.; Arstila, K.; Battistig, G.
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 266, Issue 8
  • DOI: 10.1016/j.nimb.2007.10.043

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Implementation and performance of the frequency-dependent G W method within the PAW framework
journal, July 2006


Correcting density functional theory for accurate predictions of compound enthalpies of formation: Fitted elemental-phase reference energies
journal, March 2012


Band-structure calculations for the 3 d transition metal oxides in G W
journal, February 2013


Linear optical properties in the projector-augmented wave methodology
journal, January 2006


Systematic treatment of displacements, strains, and electric fields in density-functional perturbation theory
journal, July 2005


Semiconducting transition metal oxides
journal, June 2015


New Mg-based antiperovskites PnNMg3 (Pn=As, Sb)
journal, February 2002


Monte Carlo simulations of disorder in ZnSn N 2 and the effects on the electronic structure
journal, August 2017


Exciton photoluminescence and benign defect complex formation in zinc tin nitride
journal, January 2018

  • Fioretti, Angela N.; Pan, Jie; Ortiz, Brenden R.
  • Materials Horizons, Vol. 5, Issue 5
  • DOI: 10.1039/C8MH00415C

Magnetism without Magnetic Ions: Percolation, Exchange, and Formation Energies of Magnetism-Promoting Intrinsic Defects in CaO
journal, March 2006


Thin film synthesis and properties of copper nitride, a metastable semiconductor
journal, January 2014

  • Caskey, Christopher M.; Richards, Ryan M.; Ginley, David S.
  • Mater. Horiz., Vol. 1, Issue 4
  • DOI: 10.1039/C4MH00049H

Composition, structure, and semiconducting properties of Mg x Zr 2− x N 2 thin films
journal, May 2019

  • Bauers, Sage R.; Hamann, Danielle M.; Patterson, Ashlea
  • Japanese Journal of Applied Physics, Vol. 58, Issue SC
  • DOI: 10.7567/1347-4065/ab0f0f

Ternary nitride semiconductors in the rocksalt crystal structure
journal, July 2019

  • Bauers, Sage R.; Holder, Aaron; Sun, Wenhao
  • Proceedings of the National Academy of Sciences, Vol. 116, Issue 30
  • DOI: 10.1073/pnas.1904926116

High-throughput synchrotron X-ray diffraction for combinatorial phase mapping
journal, October 2014

  • Gregoire, J. M.; Van Campen, D. G.; Miller, C. E.
  • Journal of Synchrotron Radiation, Vol. 21, Issue 6
  • DOI: 10.1107/S1600577514016488

Dielectric and ferroic properties of metal halide perovskites
journal, January 2019

  • Wilson, Jacob N.; Frost, Jarvist M.; Wallace, Suzanne K.
  • APL Materials, Vol. 7, Issue 1
  • DOI: 10.1063/1.5079633

Synthesis, structure, and optoelectronic properties of II–IV–V 2 materials
journal, January 2017

  • Martinez, Aaron D.; Fioretti, Angela N.; Toberer, Eric S.
  • Journal of Materials Chemistry A, Vol. 5, Issue 23
  • DOI: 10.1039/C7TA00406K

Growth, disorder, and physical properties of ZnSnN 2
journal, July 2013

  • Feldberg, N.; Aldous, J. D.; Linhart, W. M.
  • Applied Physics Letters, Vol. 103, Issue 4
  • DOI: 10.1063/1.4816438

Nitride-based semiconductors for blue and green light-emitting devices
journal, March 1997


Origin of the “green gap”: Increasing nonradiative recombination in indium-rich GaInN/GaN quantum well structures
journal, May 2011

  • Langer, Torsten; Kruse, Andreas; Ketzer, Fedor Alexej
  • physica status solidi (c), Vol. 8, Issue 7-8
  • DOI: 10.1002/pssc.201001051

Enhancement of Piezoelectric Response in Scandium Aluminum Nitride Alloy Thin Films Prepared by Dual Reactive Cosputtering
journal, December 2008

  • Akiyama, Morito; Kamohara, Toshihiro; Kano, Kazuhiko
  • Advanced Materials, Vol. 21, Issue 5
  • DOI: 10.1002/adma.200802611

Spinel compounds as multivalent battery cathodes: a systematic evaluation based on ab initio calculations
journal, January 2015

  • Liu, Miao; Rong, Ziqin; Malik, Rahul
  • Energy & Environmental Science, Vol. 8, Issue 3
  • DOI: 10.1039/C4EE03389B

Materials Design Rules for Multivalent Ion Mobility in Intercalation Structures
journal, August 2015


    Works referencing / citing this record:

    Wurtzite materials in alloys of rock salt compounds
    journal, January 2020

    • Han, Yanbing; Millican, Samantha L.; Liu, Jun
    • Journal of Materials Research, Vol. 35, Issue 8
    • DOI: 10.1557/jmr.2019.402