Synthesis, stoichiometry and thermal stability of Zn{sub 3}N{sub 2} powders prepared by ammonolysis reactions

Journal Article · Tue Jan 15 04:00:00 UTC 2008 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/j.jssc.2007.11.005· OSTI ID:21043872

Paniconi, Giordano; Stoeva, Zlatka ^[1]; Smith, Ronald I ^[2]; Dippo, Patricia C ^[3]; Gallagher, Bryan L ^[4]

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1. School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD (United Kingdom)
2. ISIS Facility, Rutherford Appleton Laboratory, Chilton, Didcot OX11 0QX (United Kingdom)
3. Measurements and Characterization Division, National Renewable Energy Laboratory, 1617 Cole Boulevard, Golden, CO 80401 (United States)
4. School of Physics and Astronomy, University of Nottingham, University Park, Nottingham NG7 2RD (United Kingdom)

Zn{sub 3}N{sub 2} powders were prepared by ammonolysis reactions at 600 deg. C and examined by thermogravimetric analysis, powder X-ray and neutron diffraction. The powders obtained in this way are unstable in an oxygen atmosphere above 450 deg. C. In an argon atmosphere, the powders are stable up to their decomposition point at around 700 deg. C. Structural models obtained from Rietveld refinements against the powder neutron diffraction data indicate that the Zn{sub 3}N{sub 2} powders so-prepared have the anti-bixbyite structure and are almost certainly stoichiometric with no compelling evidence of nitrogen vacancies. Further, no evidence was found for aliovalent oxygen substitution at the nitrogen sites. The calculated bond valence sums imply that Zn{sub 3}N{sub 2} cannot be described as a 100% ionic compound. The structural findings are supported by photoluminescence measurements that reveal a band gap of approximately 0.9 eV. - Graphical abstract: Zn{sub 3}N{sub 2} powders prepared by careful ammonolysis reactions form with the anti-bixbyite structure and are almost certainly stoichiometric with no evidence for aliovalent oxygen substitution at the nitrogen sites. Zn{sub 3}N{sub 2} cannot be described as a 100% ionic compound and PL measurements reveal a narrow band gap of approximately 0.9 eV.

• OSTI ID: 21043872
• Journal Information: Journal of Solid State Chemistry, Journal Name: Journal of Solid State Chemistry Journal Issue: 1 Vol. 181; ISSN 0022-4596; ISSN JSSCBI
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
AMMONOLYSIS
ARGON
NEUTRON DIFFRACTION
NITROGEN
OXYGEN
PHOTOLUMINESCENCE
STRUCTURAL MODELS
SYNTHESIS
TEMPERATURE RANGE 0400-1000 K
THERMAL GRAVIMETRIC ANALYSIS
VACANCIES
X-RAY DIFFRACTION
ZINC NITRIDES