Bulk Synthesis, Structure, and Electronic Properties of Magnesium Zirconium Nitride Solid Solutions
Bulk Synthesis, Structure, and Electronic Properties of Magnesium Zirconium Nitride Solid Solutions
复制标题
氮化锆镁固溶体的本体合成、结构和电子性能
DOI：
10.1021/acs.chemmater.1c01450
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发表时间：
2021
影响因子：
8.6
通讯作者：
Neilson, James R.
中科院分区：
文献类型：
--
作者：
Rom, Christopher L.;Fallon, M. Jewels;Wustrow, Allison;Prieto, Amy L.;Neilson, James R.
三元氮化物相空间具有很大的潜力，新的功能材料，建议计算预测尚未被发现的稳定相。本文报道了MgZrN 2块体粉末和固溶体MgxZr 2-xN 2（0 <x< 1）的复分解反应路线。这些三元相仅在使用较低温度反应时产生，与使用导致仅形成ZrN的类似Mg基复分解反应的先前工作相反。热化学计算说明了为什么较低温度的复分解反应产生Mg的掺入，而较高温度的陶瓷反应只产生ZrN。在加热过程中的复分解反应的原位X射线衍射实验揭示了反应途径中的两个阶段：最初消耗前体以制备无定形产物（Trxn> 350 °C），然后在较高温度下结晶（Trxn> 500 °C）。改变复分解前体（Mg 2NCl和ZrCl 4）的比例可控地改变MgxZr 2-xN 2的组成，其结晶为阳离子无序的岩盐，如高分辨率同步辐射X射线衍射，电子显微镜，和散装组成分析所证明的。组合物中的变化导致逐渐的金属到绝缘体的过渡与increasingx，类似于其他报告的类似的薄膜样品组合溅射。同时，这些粉末的光学行为表明纳米级组成的不均匀性，因为即使在富含Mg的样品中也可以检测到ZrN样吸收的特征。这种复分解方法似乎可以推广到块状三元氮化物材料的合成。
Ternary nitride phase space holds great potential for new functional materials, as suggested by computational predictions of yet-to-be discovered stable phases. Here, we report a metathesis route to bulk powders of MgZrN2and the solid solutions MgxZr2–xN2(0 <x< 1). These ternary phases only result when lower temperature reactions are used, in contrast to previous work using the similar Mg-based metathesis reactions that resulted in the formation of exclusively ZrN. Thermochemical calculations illustrate why lower temperature metathesis reactions yield the incorporation of Mg, while higher temperature ceramic reactions yield exclusively ZrN. Experimentalin situX-ray diffraction of metathesis reactions during heating reveals two stages in the reaction pathway: initial consumption of the precursors to make an amorphous product (Trxn> 350 °C) followed by crystallization at higher temperatures (Trxn> 500 °C). Changing the ratio of the metathesis precursors (Mg2NCl and ZrCl4) controllably varies the composition of MgxZr2–xN2, which crystallizes as a cation-disordered rock salt, as evidenced by high-resolution synchrotron X-ray diffraction, electron microscopy, and bulk compositional analysis. Variation in composition leads to a gradual metal-to-insulator transition with increasingx, similar to other reports of analogous thin film specimens produced by combinatorial sputtering. Meanwhile, the optical behavior of these powders suggests nanoscale compositional inhomogeneity, as signatures of ZrN-like absorption are detectable even in Mg-rich samples. This metathesis approach appears to be generalizable to the synthesis of bulk ternary nitride materials.
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