Vosseler Kathrin, Koldemir Aylin, Pöttgen Rainer, Doert Thomas, Nilges Tom
Synthesis and Characterization of Innovative Materials, TUM School of Natural Sciences, Department of Chemistry, Technical University of Munich, Lichtenbergstraße 4, Garching b. München 85748, Germany.
Institut für Anorganische und Analytische Chemie, Universität Münster, Corrensstraße 30, Münster 48149, Germany.
Inorg Chem. 2025 Sep 22;64(37):19055-19067. doi: 10.1021/acs.inorgchem.5c03307. Epub 2025 Sep 10.
Semiconductors with one-dimensional (1D) substructures are promising for next-generation optical and electronic devices due to their directional transport and flexibility. Representatives of this class include HgPbP-type materials. This study investigates the related semiconductors AgGeP and AgSnP. Single-crystal X-ray diffraction indicates that their structure is unconventional due to its incommensurate modulation. Both compounds crystallize orthorhombically in the (3 + 1)D superspace group (00)00 (No. 62.1.9.4). AgGeP (refined composition AgGeP) with the cell parameters = 12.986(1) Å, = 3.2648(4) Å, = 10.841(1) Å, and a modulation wave vector = (0, 0.39(1), 0), and AgSnP (refined as AgSnP) with = 13.014(1) Å, = 3.2602(4) Å, = 10.905(1) Å, and = (0, 0.42(1), 0) were investigated. Three structural models were generated, differing in modulation functions, site occupancies, and the split of one atomic position. Depending on the occupancy, the structure can be derived from CuP, AgP, or HgPbP -type materials. Sn Mössbauer spectroscopy confirms the +II oxidation state of tin in AgSnP. Additional characterization was performed by scanning electron microscopy with energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, angle-dependent Raman spectroscopy, and photoluminescence measurements. Single-crystal conductivity measurements revealed semiconducting behavior of AgGeP (0.2 S/cm).
具有一维（1D）子结构的半导体因其定向传输和灵活性而在下一代光学和电子器件方面具有广阔前景。这类材料的代表包括HgPbP型材料。本研究对相关半导体AgGeP和AgSnP进行了研究。单晶X射线衍射表明，由于其非公度调制，它们的结构是非传统的。两种化合物均在（3 + 1）D超空间群（00）00（编号62.1.9.4）中呈正交晶系结晶。研究了晶胞参数为 = 12.986(1) Å、 = 3.2648(4) Å、 = 10.841(1) Å且调制波矢 = (0, 0.39(1), 0)的AgGeP（精制组成为AgGeP）以及 = 13.014(1) Å、 = 3.2602(4) Å、 = 10.905(1) Å且 = (0, 0.42(1), 0)的AgSnP（精制为AgSnP）。生成了三种结构模型，它们在调制函数、位点占有率以及一个原子位置的分裂方面存在差异。根据占有率，该结构可源自CuP、AgP或HgPbP型材料。Sn穆斯堡尔光谱证实了AgSnP中锡的+II氧化态。通过能量色散X射线光谱扫描电子显微镜、X射线光电子能谱、角度相关拉曼光谱和光致发光测量进行了额外表征。单晶电导率测量揭示了AgGeP的半导体行为（0.2 S/cm）。
