Ammonothermal Synthesis of Novel Nitrides: Case Study on CaGaSiN3

Haeusler J, Neudert L, Mallmann M, Niklaus R, Kimmel AC, Alt N, Schlücker E, Oeckler O, Schnick W (2017)

Publication Status: Published

Publication Type: Journal article, Original article

Publication year: 2017


Publisher: Wiley-VCH Verlag

Book Volume: 23

Pages Range: 2583-2590

Journal Issue: 11

DOI: 10.1002/chem.201605344


The first gallium-containing nitridosilicate CaGaSiN was synthesized in newly developed high-pressure autoclaves using supercritical ammonia as solvent and nitriding agent. The reaction was conducted in an ammonobasic environment starting from intermetallic CaGaSi with NaN as a mineralizer. At 770 K, intermediate compounds were obtained, which were subsequently converted to the crystalline nitride at temperatures up to 1070 K (70–150 MPa). The impact of other mineralizers (e.g., LiN, KN, and CsN) on the product formation was investigated as well. The crystal structure of CaGaSiN was analyzed by powder X-ray diffraction and refined by the Rietveld method. The structural results were further corroborated by transmission electron microscopy, Si MAS-NMR, and first-principle DFT calculations. CaGaSiN crystallizes in the orthorhombic space group Cmc2 (no. 36) with lattice parameters a=9.8855(11), b=5.6595(1), c=5.0810(1) Å, (Z=4, R=0.0326), and is isostructural with CaAlSiN (CASN). Eu doped samples exhibit red luminescence with an emission maximum of 620 nm and FWHM of 90 nm. Thus, CaGaSiN:Eu also represents an interesting candidate as a red-emitting material in phosphor-converted light-emitting diodes (pc-LEDs). In addition to the already known substitution of alkaline-earth metals in (Ca,Sr)AlSiN:Eu, inclusion of Ga is a further and promising perspective for luminescence tuning of widely used red-emitting CASN type materials.

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Haeusler, J., Neudert, L., Mallmann, M., Niklaus, R., Kimmel, A.-C., Alt, N.,... Schnick, W. (2017). Ammonothermal Synthesis of Novel Nitrides: Case Study on CaGaSiN3. Chemistry - A European Journal, 23(11), 2583-2590.


Haeusler, Jonas, et al. "Ammonothermal Synthesis of Novel Nitrides: Case Study on CaGaSiN3." Chemistry - A European Journal 23.11 (2017): 2583-2590.

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