Kim Hyo-Suk, Jung Eun Ae, Han Seong Ho, Han Jeong Hwan, Park Bo Keun, Kim Chang Gyoun, Chung Taek-Mo
Thin Film Materials Research Center, Korea Research Institute of Chemical Technology , 141 Gajeong-ro, Yuseong-gu, Daejeon 34114, Republic of Korea.
Inorg Chem. 2017 Apr 3;56(7):4084-4092. doi: 10.1021/acs.inorgchem.6b02697. Epub 2017 Mar 22.
New germanium chalcogenide precursors, S═Ge(dmamp) (3), S═Ge(dmampS) (4), Se═Ge(dmamp) (5), Se═Ge(dmampS) (6), Te═Ge(dmamp) (7), and Te═Ge(dmampS) (8), were synthesized from Ge(dmamp) (1) and Ge(dmampS) (2) using sulfur, selenium, and tellurium powders (dmamp = 1-dimethylamino-2-methyl-2-propanolate, dmampS = 1-dimethylamino-2-methylpropane-2-thiolate). Complexes 1 and 2 were synthesized from metathesis reactions of GeCl·dioxane with 2 equiv of aminoalkoxide or aminothiolate ligands. Thermogravimetric analysis of complex 1 displayed good thermal stability and volatility. The molecular structures of complexes 2-8 from X-ray single crystallography showed distorted trigonal bipyramidal geometry at the germanium centers. Germanium chalcogenide materials (GeSe and GeTe) were obtained from the thermal decomposition of complexes 5, 6, and 8 in hexadecane. X-ray diffraction patterns exhibited that GeSe and GeTe had orthorhombic and rhombohedral phases, respectively. This study affords a facile method to easily prepare germanium chalcogenide materials using well-designed and stable complexes by thermal decomposition of single-source precursors in solution.
新型锗硫属化物前驱体S═Ge(dmamp) (3)、S═Ge(dmampS) (4)、Se═Ge(dmamp) (5)、Se═Ge(dmampS) (6)、Te═Ge(dmamp) (7)和Te═Ge(dmampS) (8)，由Ge(dmamp) (1)和Ge(dmampS) (2)与硫粉、硒粉和碲粉反应合成（dmamp = 1 - 二甲基氨基 - 2 - 甲基 - 2 - 丙醇盐，dmampS = 1 - 二甲基氨基 - 2 - 甲基丙烷 - 2 - 硫醇盐）。配合物1和2由GeCl·二氧六环与2当量的氨基醇盐或氨基硫醇盐配体发生复分解反应合成。配合物1的热重分析显示出良好的热稳定性和挥发性。通过X射线单晶衍射确定的配合物2 - 8的分子结构表明，锗中心具有扭曲的三角双锥几何构型。锗硫属化物材料（GeSe和GeTe）由配合物5、6和8在十六烷中热分解得到。X射线衍射图谱表明，GeSe和GeTe分别具有正交相和菱面体相。本研究提供了一种简便的方法，通过在溶液中热分解单源前驱体，利用精心设计的稳定配合物轻松制备锗硫属化物材料。
