Ammonothermal Synthesis and Crystal Structure of the Nitridoalumogermanate Ca_1–xLi_xAl_1–xGe_1+xN₃ (x ≈ 0.2)

Abstract

The new nitridoalumogermanate Ca 1-x Li x Al 1-x -Ge 1+x N 3 (x ≈ 0.2) was synthesized from supercritical ammonia at 925 K and 185 MPa starting from the intermetallic precursor Ca 3 Al 2 Ge 2 and Li as mineralizer. The crystal structure was refined by the Rietveld method; Ca 1-x Li x Al 1-x Ge 1+x N 3 with x ≈ 0.2 [a = 9.9822(5), b = 5.7763(2), c = 5.1484(1) Å, Z = 4, R wp = 0.0492] crystallizes in orthorhombic space group Cmc2 1 (no. 36). Needle-shaped crystals with up to 15 μm in length were detected by scanning electron microscopy. Possible cation ordering was analyzed by transmission electron microscopy. No su- [a]

Solid Solutions of Grimm–Sommerfeld Analogous Nitride Semiconductors II‐IV‐N2 (II=Mg, Mn, Zn; IV=Si, Ge): Ammonothermal Synthesis and DFT Calculations

“…Although the ammonothermal synthesis of ternary and higher (oxide) nitrides is still challenging and only a small number of synthesized compounds are known in the literature, these studies once again demonstrate the great potential of this method . Furthermore, it could be shown within the scope of this work that bandgap tunability is possible in this system, paving the way for possible future applications of bandgap engineering.…”

“…However, the bulk synthesis of these materials is still challenging. Recently, we employed the ammonothermal method as a suitable synthetic approach to Zn‐IV‐N 2 compounds (IV=Si, Ge), as well as other Grimm–Sommerfeld analogous nitrides such as II‐IV‐N 2 (II=Mg, Mn; IV=Si, Ge), II 2 ‐P‐N 3 (II=Mg, Zn), CaGaSiN 3 , and Ca 1− x Li x Al 1− x Ge 1+ x N 3 ( x ≈0.2) . By employing this method, we were able to synthesize crystalline ZnSiN 2 and ZnGeN 2 with crystal sizes of several micrometers and, for the first time, single crystals of Mg 2 PN 3 with lengths of up to 30 μm.…”

“…Recently,w ee mployed the ammonothermalm ethod as a suitable synthetica pproacht oZ n-IV-N 2 compounds (IV = Si, Ge), as well as other Grimm-Sommerfeld analogous nitrides such as II-IV-N 2 (II = Mg, Mn;I V = Si, Ge), II 2 -P-N 3 (II = Mg, Zn), CaGaSiN 3 ,a nd Ca 1Àx Li x Al 1Àx Ge 1 + x N 3 (x % 0.2). [11][12][13][14][15] By employing this method, we were ablet os ynthesize crystalline ZnSiN 2 and ZnGeN 2 with crystal sizes of several micrometers and, for the first time, single crystals of Mg 2 PN 3 with lengths of up to 30 mm. Furthermore,w ell-defined crystallites of InN were obtained ammonothermally quite recently,i ndicating the ammonothermal process as an auspicious methodf or synthesis and crystal growth of semiconducting nitrides.…”

Ammonothermal Synthesis of the Mixed‐Valence Nitrogen‐Rich Europium Tantalum Ruddlesden‐Popper Phase EuIIEuIII2Ta2N4O3

“…Subsequently, the autoclave was heated to the respective reaction temperature within 6 h and kept at this temperature for 110 h. The pressure slowly decreased over time because of hydrogen loss of the autoclave. Further details of the used autoclaves can be found in literature , , , …”

Ammonothermal Synthesis of Ba2PO3N – An Oxonitridophosphate with Non‐Condensed PO3N Tetrahedra

“…InN, II‐IV‐N 2 (II = Mg, Mn, Zn; IV = Si, Ge), CaGaSiN 3 or Ca 1– x Li x Al 1– x Ge 1+ x N 3 ( x ≈ 0.2)] and oxide nitride perovskites [e.g. EAM O 2 N ( EA = Sr, Ba; M = Nb, Ta)] as well . Most recently, the syntheses of numerous nitridophosphates with different degrees of condensations κ (i.e.…”