Zinc nitride

Zinc nitride
Identifiers
CAS Number	1313-49-1 ;
3D model (JSmol)	Interactive image;
ECHA InfoCard	100.013.826
EC Number	215-207-3;
PubChem CID	12130759;
UNII	7OOJ6UE14L ;
CompTox Dashboard (EPA)	DTXSID001014317 ;
	InChI InChI=1S/2N.3Zn/q2*-1;;;+2 Key: AKJVMGQSGCSQBU-UHFFFAOYSA-N;
	SMILES [N-]=[Zn].[N-]=[Zn].[Zn+2];
Properties
Chemical formula	Zn3N2
Molar mass	224.154 g/mol
Appearance	blue-gray cubic crystals
Density	6.22 g/cm3, solid
Melting point	decomposes 700°C
Solubility in water	insoluble, reacts
Structure
Crystal structure	Cubic, cI80
Space group	Ia-3, No. 206
Hazards
	GHS labelling:
Pictograms
Signal word	Warning
Hazard statements	H315, H319
Precautionary statements	P264, P280, P302+P352, P305+P351+P338, P321, P332+P313, P337+P313, P362
NFPA 704 (fire diamond)	1 0 2 W
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). verify (what is ?) Infobox references

Zinc nitride (Zn₃ N₂) is an inorganic compound of zinc and nitrogen, usually obtained as (blue)grey crystals. It is a semiconductor. In pure form, it has the anti-bixbyite structure.

Chemical properties

Zinc nitride can be obtained by thermally decomposing zincamide (zinc diamine)^[3] in an anaerobic environment, at temperatures in excess of 200 °C. The by-product of the reaction is ammonia.^[4]

3 Zn(NH₂)₂ → Zn₃N₂ + 4 NH₃

It can also be formed by heating zinc to 600 °C in a current of ammonia; the by-product is hydrogen gas.^[3]^[5]

3 Zn + 2 NH₃ → Zn₃N₂ + 3 H₂

The decomposition of Zinc Nitride into the elements at the same temperature is a competing reaction.^[6] At 700 °C Zinc Nitride decomposes.^[1] It has also been made by producing an electric discharge between zinc electrodes in a nitrogen atmosphere.^[6]^[7] Thin films have been produced by chemical vapour deposition of Bis(bis(trimethylsilyl)amido]zinc with ammonia gas onto silica or ZnO coated alumina at 275 to 410 °C.^[8]

The crystal structure is anti-isomorphous with Manganese(III) oxide. (bixbyite).^[2]^[7] The heat of formation is c. 24 kilocalories (100 kJ) per mol.^[7] It is a semiconductor with a reported bandgap of c. 3.2eV,^[9] however, a thin zinc nitride film prepared by electrolysis of molten salt mixture containing Li₃N with a zinc electrode showed a band-gap of 1.01 eV.^[10]

Zinc nitride reacts violently with water to form ammonia and zinc oxide.^[3]^[4]

Zn₃N₂ + 3 H₂O → 3 ZnO + 2 NH₃

Zinc nitride reacts with lithium (produced in an electrochemical cell) by insertion. The initial reaction is the irreversible conversion into LiZn in a matrix of beta-Li₃N. These products then can be converted reversibly and electrochemically into LiZnN and metallic Zn.^[11]^[12]

References

^ ^a ^b ^c ^d CRC Handbook of Chemistry and Physics (96 ed.), §4-100 Physical Constants of Inorganic Compounds
^ ^a ^b Partin, D. E.; Williams, D. J.; O'Keeffe, M. (1997). "The Crystal Structures of Mg₃N₂ and Zn₃N₂". Journal of Solid State Chemistry. 132 (1): 56–59. Bibcode:1997JSSCh.132...56P. doi:10.1006/jssc.1997.7407.
^ ^a ^b ^c Roscoe, H. E.; Schorlemmer, C. (1907) [1878]. A Treatise on Chemistry: Volume II, The Metals (4th ed.). London: Macmillan. pp. 650–651. Retrieved 2007-11-01.
^ ^a ^b Bloxam, C. L. (1903). Chemistry, Inorganic and Organic (9th ed.). Philadelphia: P. Blakiston's Son & Co. p. 380. Retrieved 2007-10-31.
^ Lowry, M. T. (1922). Inorganic Chemistry. Macmillan. p. 872. Retrieved 2007-11-01.
^ ^a ^b Maxtead, E.B. (1921), Ammonia and the Nitrides, pp. 69–20
^ ^a ^b ^c Mellor, J.W. (1964), A Comprehensive Treatise on Inorganic and Theoretical Chemistry, vol. 8, Part 1, pp. 160–161
^ Maile, E.; Fischer, R. A. (Oct 2005), "MOCVD of the Cubic Zinc Nitride Phase, Zn3N2, Using Zn[N(SiMe3)2]2 and Ammonia as Precursors", Chemical Vapor Deposition, 11 (10): 409–414, doi:10.1002/cvde.200506383
^ Ebru, S.T.; Ramazan, E.; Hamide, K. (2007), "Structural and Optical Properties of Zinc Nitride Films Prepared by Pulsed Filtered Cathodic Vacuum Arc Deposition" (PDF), Chin. Phys. Lett., 24 (12): 3477, Bibcode:2007ChPhL..24.3477S, doi:10.1088/0256-307x/24/12/051, S2CID 123496085
^ Toyoura, Kazuaki; Tsujimura, Hiroyuki; Goto, Takuya; Hachiya, Kan; Hagiwara, Rika; Ito, Yasuhiko (2005), "Optical properties of zinc nitride formed by molten salt electrochemical process", Thin Solid Films, 492 (1–2): 88–92, Bibcode:2005TSF...492...88T, doi:10.1016/j.tsf.2005.06.057
^ Amatucci, G. G.; Pereira, N. (2004). "Nitride and Silicide Negative Electrodes". In Nazri, G.-A.; Pistoia, G. (eds.). Lithium Batteries: Science and Technology. Kluwer Academic Publishers. p. 256. ISBN 978-1-4020-7628-2. Retrieved 2007-11-01.
^ Pereiraa, N.; Klein, L.C.; Amatuccia, G.G. (2002), "The Electrochemistry of Zn3 N 2 and LiZnN - A Lithium Reaction Mechanism for Metal Nitride Electrodes", Journal of the Electrochemical Society, 149 (3): A262, Bibcode:2002JElS..149A.262P, doi:10.1149/1.1446079