Ammonothermal synthesis of binary and multinary nitrides, amides and imides of Ga, Al, Si and Ge

Ga、Al、Si 和 Ge 的二元和多元氮化物、酰胺和酰亚胺的氨热合成

• 批准号: 201503442
• 负责人: Professor Dr. Wolfgang Schnick
• 金额: --
• 依托单位: Lehrstuhl für Anorganische Festkörperchemie
• 依托单位国家: 德国
• 项目类别: Research Units
• 财政年份: 2011
• 资助国家: 德国
• 起止时间: 2010-12-31 至 2018-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/201503442?language=en
• 关键词: Ammonothermal; synthesis; binary; multinary; nitrides

During the last couple of years, main group nitrides got in the focus of numerous investigations . Especially compounds of group III (Al, Ga, In) and group IV (Si, Ge) elements show interesting material properties . Typical syntheses are hereby based on pyrolysis of molecular precursors, solid-state reactions at rather high temperatures or the use of salts or metals acting as fluxing agents. These routes usually enable access only to single crystals inµm scale of these ternary or multinary compounds . Here, ammonothermal reactions could be an attractive alternative. The huge potential of solvothermal syntheses for growing !arge single crystals, for example hydrothermal processing of quartz, is well known for a long time. A similar technique can be used for the synthesis of nitrides employing supercritical ammonia, which can act as solvent as well as nitrogen source. Beyond the Forschergruppe AmmonoFOR1600 ammonothermal processing finds only minor application, although the academic background has been generated in Germany decades ago . The scope of this subproject is to reestablish ammonothermal synthesis, focusing on synthesis and crystal growth of novel multinary nitrides including the elements Al, Ga, Mg, Li, Si or Ge. Hitherto, nitrides, also including alkaline and alkaline earth or rare earth metals as well as intermediates, obtained during synthesis will be structurally characterized. Understanding reaction mechanisms and characterization of intermediates should help to enable a targeted synthesis of novel nitride compounds . Furthermore, it is essential to elucidate the structures of these nitrides, investigate material properties and understand structure-property­ relationships. Within the first funding period it was possible to optimize synthesis conditions and to evaluate appropriate multinary model compounds. lnvestigations showed that nitrides crystallizing in wurtzite type of structure or related superstructures (e.g. LiSbN3 or CaAISiN3)seem to be very promising model candidates.

在过去的几年里，主族氮化物成为众多研究的焦点。特别是III族（Al、Ga、In）和IV族（Si、Ge）元素的化合物显示出令人感兴趣的材料性质。因此，典型的合成是基于分子前体的热解、在相当高的温度下的固态反应或使用盐或金属作为助熔剂。这些路线通常只能获得这些三元或多元化合物的微米级单晶。在这里，氨化反应可能是一个有吸引力的替代方案。溶剂热合成的巨大发展潜力！大单晶例如石英的水热处理长期以来是公知的。类似的技术可以用于使用超临界氨合成氮化物，超临界氨可以充当溶剂以及氮源。除了Forschergruppe AmmonoFOR 1600之外，氨处理只有很小的应用，尽管学术背景已经在德国产生了几十年。该子项目的范围是重建氨合成，重点是合成和晶体生长的新型多元氮化物，包括元素铝，镓，镁，锂，硅或锗。在合成过程中获得的氮化物，也包括碱金属和碱土金属或稀土金属以及中间体，将在结构上进行表征。了解反应机理和中间体的表征应有助于实现新型氮化物化合物的靶向合成。此外，阐明这些氮化物的结构，研究材料性能和理解结构-性能间的关系是至关重要的。在第一个供资期内，有可能优化合成条件并评估适当的多元模型化合物。研究表明，以纤锌矿型结构或相关超结构（例如LiSbN 3或CaAlSiN 3）结晶的氮化物似乎是非常有前途的模型候选者。