Crystalline Nitridophosphates by Ammonothermal Synthesis.

Nitridophosphates are a well-studied class of compounds with high structural diversity. However, their synthesis is quite challenging, particularly due to the limited thermal stability of starting materials like P3 N5 . Typically, it requires even high-pressure techniques (e.g. multianvil) in most cases. Herein, we establish the ammonothermal method as a versatile synthetic tool to access nitridophosphates with different degrees of condensation. α-Li10 P4 N10 , ß-Li10 P4 N10 , Li18 P6 N16 , Ca2 PN3 , SrP8 N14 , and LiPN2 were synthesized in supercritical NH3 at temperatures and pressures up to 1070 K and 200 MPa employing ammonobasic conditions. The products were analyzed by powder X-ray diffraction, energy dispersive X-ray spectroscopy, and FTIR spectroscopy. Moreover, we established red phosphorus as a starting material for nitridophosphate synthesis instead of commonly used and not readily available precursors, such as P3 N5 . This opens a promising preparative access to the emerging compound class of nitridophosphates.

Sr3 P3 N7 : Complementary Approach by Ammonothermal and High-Pressure Syntheses.

Nitridophosphates exhibit an intriguing structural diversity with different structural motifs, for example, chains, layers or frameworks. In this contribution the novel nitridophosphate Sr3 P3 N7 with unprecedented dreier double chains is presented. Crystalline powders were synthesized using the ammonothermal method, while single crystals were obtained by a high-pressure multianvil technique. The crystal structure of Sr3 P3 N7 was solved and refined from single-crystal X-ray diffraction and confirmed by powder X-ray methods. Sr3 P3 N7 crystallizes in monoclinic space group P2/c. Energy-dispersive X-ray and Fourier-transformed infrared spectroscopy were conducted to confirm the chemical composition, as well as the absence of NHx functionality. The optical band gap was estimated to be 4.4 eV using diffuse reflectance UV/Vis spectroscopy. Upon doping with Eu2+ , Sr3 P3 N7 shows a broad deep-red to infrared emission (λem =681 nm, fwhm≈3402 cm-1 ) with an internal quantum efficiency of 42 %.

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

Grimm-Sommerfeld analogous II-IV-N2 nitrides such as ZnSiN2 , ZnGeN2 , and MgGeN2 are promising semiconductor materials for substitution of commonly used (Al,Ga,In)N. Herein, the ammonothermal synthesis of solid solutions of II-IV-N2 compounds (II=Mg, Mn, Zn; IV=Si, Ge) having the general formula (IIa 1-x IIb x )-IV-N2 with x≈0.5 and ab initio DFT calculations of their electronic and optical properties are presented. The ammonothermal reactions were conducted in custom-built, high-temperature, high-pressure autoclaves by using the corresponding elements as starting materials. NaNH2 and KNH2 act as ammonobasic mineralizers that increase the solubility of the reactants in supercritical ammonia. Temperatures between 870 and 1070 K and pressures up to 200 MPa were chosen as reaction conditions. All solid solutions crystallize in wurtzite-type superstructures with space group Pna21 (no. 33), confirmed by powder XRD. The chemical compositions were analyzed by energy-dispersive X-ray spectroscopy. Diffuse reflectance spectroscopy was used for estimation of optical bandgaps of all compounds, which ranged from 2.6 to 3.5 eV (Ge compounds) and from 3.6 to 4.4 eV (Si compounds), and thus demonstrated bandgap tunability between the respective boundary phases. Experimental findings were corroborated by DFT calculations of the electronic structure of pseudorelaxed mixed-occupancy structures by using the KKR+CPA approach.

Ammonothermal Synthesis, Optical Properties, and DFT Calculations of Mg2 PN3 and Zn2 PN3.

The phosphorus nitrides, Mg2 PN3 and Zn2 PN3 , are wide band gap semiconductor materials with potential for application in (opto)electronics or photovoltaics. For the first time, both compounds were synthesized ammonothermally in custom-built high-temperature, high-pressure autoclaves starting from P3 N5 and the corresponding metals (Mg or Zn). Alkali amides (NaNH2 , KNH2 ) were employed as ammonobasic mineralizers to increase solubility of the starting materials in supercritical ammonia through formation of reactive intermediates. Single crystals of Mg2 PN3 , with length up to 30 µm, were synthesized at 1070 K and 140 MPa. Zn2 PN3 already decomposes at these conditions and was obtained as submicron-sized crystallites at 800 K and 200 MPa. Both compounds crystallize in a wurtzite-type superstructure in orthorhombic space group Cmc21 , which was confirmed by powder X-ray diffraction. In addition, single-crystal X-ray diffraction measurements of Mg2 PN3 were carried out for the first time. To our knowledge, this is the first single-crystal X-ray study of ternary nitrides synthesized by the ammonothermal method. The band gaps of both nitrides were estimated to be 5.0 eV for Mg2 PN3 and 3.7 eV for Zn2 PN3 by diffuse reflectance spectroscopy. DFT calculations were carried out to verify the experimental values. Furthermore, a dissolution experiment was conducted to obtain insights into the crystallization behavior of Mg2 PN3 .

Ammonothermal Synthesis of Novel Nitrides: Case Study on CaGaSiN3.

The first gallium-containing nitridosilicate CaGaSiN3 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 NaN3 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., LiN3 , KN3 , and CsN3 ) on the product formation was investigated as well. The crystal structure of CaGaSiN3 was analyzed by powder X-ray diffraction and refined by the Rietveld method. The structural results were further corroborated by transmission electron microscopy, 29 Si MAS-NMR, and first-principle DFT calculations. CaGaSiN3 crystallizes in the orthorhombic space group Cmc21 (no. 36) with lattice parameters a=9.8855(11), b=5.6595(1), c=5.0810(1) Å, (Z=4, Rwp =0.0326), and is isostructural with CaAlSiN3 (CASN). Eu2+ doped samples exhibit red luminescence with an emission maximum of 620 nm and FWHM of 90 nm. Thus, CaGaSiN3 :Eu2+ 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)AlSiN3 :Eu2+ , inclusion of Ga is a further and promising perspective for luminescence tuning of widely used red-emitting CASN type materials.

Electronic structure investigation of wide band gap semiconductors-Mg2PN3 and Zn2PN3: experiment and theory.

The research on nitridophosphate materials has gained significant attention in recent years due to the abundance of elements like Mg, Zn, P, and N. We present a detailed study of band gap and electronic structure of M2PN3 (M = Mg, Zn), using synchrotron-based soft x-ray spectroscopy measurements as well as density functional theory (DFT) calculations. The experimental N K-edge x-ray emission spectroscopy (XES) and x-ray absorption spectroscopy (XAS) spectra are used to estimate the band gaps, which are compared with our calculations along with the values available in literature. The band gap, which is essential for electronic device applications, is experimentally determined for the first time to be 5.3 ± 0.2 eV and 4.2 ± 0.2 eV for Mg2PN3 and Zn2PN3, respectively. The experimental band gaps agree well with our calculated band gaps of 5.4 eV for Mg2PN3 and 3.9 eV for Zn2PN3, using the modified Becke-Johnson (mBJ) exchange potential. The states that contribute to the band gap are investigated with the calculated density of states especially with respect to two non-equivalent N sites in the structure. The calculations and the measurements predict that both materials have an indirect band gap. The wide band gap of M2PN3 (M = Mg, Zn) could make it promising for the application in photovoltaic cells, high power RF applications, as well as power electronic devices.