首页> 外文期刊>Chemistry of Materials: A Publication of the American Chemistry Society >Evaluation of Homoleptic Guanidinate and Amidinate Complexes of Gadolinium and Dysprosium for MOCVD of Rare-Earth Nitride Thin Films
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Evaluation of Homoleptic Guanidinate and Amidinate Complexes of Gadolinium and Dysprosium for MOCVD of Rare-Earth Nitride Thin Films

机译:钆和镝的同源胍酸盐和脒酸盐配合物对稀土氮化物薄膜MOCVD的评价

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摘要

Metal-organic chemical vapor deposition (MOCVD) of thin films of two representative rare-earth nitrides is reported here for the first time. Four homoleptic, all-nitrogen-coordinated, rare-earth (RE) complexes were evaluated as precursors for the respective nitride thin film materials. Two guanidinato complexes RE{(~iPrN)_2C(NMe2)}_3 RE = Gd (1), Dy (2) and two amidinato complexes RE{(~iPrN)_2CMe}_3 RE = Gd (3), Dy (4) were compared and used either as single source precursors or together with ammonia for MOCVD of gadolinium nitride (GdN) and dysprosium nitride (DyN), respectively. The thermal properties of the precursors were studied and the fragmentation patterns were characterized by high-resolution electron impact-mass spectrometry (HR EI-MS). The obtained nitride films were investigated using a series of techniques, including X^ray diffraction (XRD), scanning electron microscopy (SEM), nuclear reaction analysis (NRA), Rutherford backscattering (RBS), and X-ray photoelectron spectroscopy (XPS). The films contain preferentially oriented grains of fcc-GdN and DyN and are contaminated with small amounts of carbon and oxygen (significantly below 10 at. in the best cases). The temperature-dependent magnetic properties of the films, as measured using a superconducting quantum interference device (SQUID), suggest the existence of small ferromagnetic grains of the rare-earth nitrides mat exhibit superparamagnetism. Despite the chemical and structural similarity of the guanidinato and amidinato complexes (1-4), a distinctly different behavior as MOCVD precursors was found for 1 and 2, compared with that for 3 and 4. While the guanidinates operate well as single-source precursors (SSPs), the amidinates are not suited at all as SSPs, but give very good nitride films when used in the presence of ammonia. This characteristic behavior was correlated with the different fragmentation mechanisms, as revealed by EI-MS.
机译:本文首次报道了两种代表性稀土氮化物薄膜的金属有机化学气相沉积(MOCVD)。评估了四种均质、全氮配位的稀土 (RE) 配合物作为各自氮化物薄膜材料的前体。比较了两种胍配合物[RE{(~iPrN)_2C(NMe2)}_3] [RE = Gd (1), Dy (2)] 和两种脒配合物 [RE{(~iPrN)_2CMe}_3] [RE = Gd (3), Dy (4)],分别用作单源前驱体或与氨一起用于氮化钆 (GdN) 和氮化镝 (DyN) 的 MOCVD。研究了前驱体的热性能,并通过高分辨电子冲击质谱(HR EI-MS)对碎裂模式进行了表征。采用X^射线衍射(XRD)、扫描电子显微镜(SEM)、核反应分析(NRA)、卢瑟福背散射(RBS)和X射线光电子能谱(XPS)等技术研究了所获得的氮化物薄膜。这些薄膜含有优先取向的fcc-GdN和DyN颗粒,并被少量的碳和氧污染(在最好的情况下明显低于10%。使用超导量子干涉装置(SQUID)测量的薄膜的温度依赖性磁性表明,稀土氮化物垫上存在小的铁磁颗粒,表现出超顺磁性。尽管胍地那托和脒地那托复合物具有化学和结构相似性 (1-4),但与 3 和 4 相比,1 和 2 的 MOCVD 前体行为明显不同。虽然胍酸盐作为单一来源前体 (SSP) 运行良好,但脒酸盐根本不适合作为 SSP,但在氨存在下使用时会产生非常好的氮化物膜。正如EI-MS所揭示的那样,这种特征行为与不同的碎裂机制相关。

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