Zirconium disulfide (ZrS) is a two-dimensional (2D) layered transition metal dichalcogenide (TMDC) and has important implications in optoelectronics and energy storage. Despite some research efforts reported to date for synthesizing 2D ZrS, there still lacks a method to grow large-scale continuous ZrS thin films. In this study, we developed a low temperature vapor-phase process for controllably growing zirconium sulfide (ZrS) films via atomic layer deposition (ALD), using tetrakis (dimethylamido)zirconium (TDMA-Zr) and HS as the precursors in the range of 75–300 °C. We verified the self-limiting growth behavior of the ZrS ALD using an quartz crystal microbalance (QCM). Furthermore, we characterized the resultant ZrS films using a suite of instruments, including scanning electron microscopy (SEM), synchrotron X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and high-resolution transmission electron microscopy (HR-TEM). The results showed that the growth per cycle (GPC) of the ZrS films varies with temperature and decreases from ∼1.2 Å/cycle at 75 °C to ∼0.3 Å/cycle at 300 °C. The as-deposited films are mainly amorphous in all the temperatures and have an S/Zr ratio varying from ∼2 to 1. Very interestingly, our annealing HR-TEM analyses revealed that the resultant films could transform from an amorphous layer into a layer of crystalline nanoparticles of 2D ZrS with increasing temperatures up to 1000 °C. We also confirmed that the as-deposited ZrS films are electrochemically active and show promising capability as an anode material for lithium-ion batteries (LIBs). Thus, this study represents a new ALD process for ZrS, which may have important applications in multiple areas.

中文翻译：

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二维层状硫化锆的原子层沉积

二硫化锆（ZrS）是一种二维（2D）层状过渡金属二硫属化物（TMDC），在光电子和能源存储方面具有重要意义。尽管迄今为止报道了一些合成二维 ZrS 的研究工作，但仍然缺乏生长大规模连续 ZrS 薄膜的方法。在这项研究中，我们开发了一种低温气相工艺，通过原子层沉积 (ALD) 可控生长硫化锆 (ZrS) 薄膜，使用四(二甲基氨基)锆 (TDMA-Zr) 和 H2S 作为前体，范围为75–300°C。我们使用石英晶体微天平 (QCM) 验证了 ZrS ALD 的自限生长行为。此外，我们使用一套仪器对所得的 ZrS 薄膜进行了表征，包括扫描电子显微镜 (SEM)、同步加速器 X 射线衍射 (XRD)、X 射线光电子能谱 (XPS) 和高分辨率透射电子显微镜 (HR-透射电镜）。结果表明，ZrS 薄膜的每循环生长 (GPC) 随温度变化，从 75 °C 的~1.2 Å/循环减少到 300 °C 的~0.3 Å/循环。沉积态薄膜在所有温度下都主要是非晶态，并且 S/Zr 比从 ∼2 到 1 不等。非常有趣的是，我们的退火 HR-TEM 分析表明，所得薄膜可以从非晶层转变为非晶层。二维 ZrS 晶体纳米粒子的温度升高至 1000 °C。我们还证实，沉积的 ZrS 薄膜具有电化学活性，并且显示出作为锂离子电池（LIB）负极材料的前景。因此，这项研究代表了一种新的 ZrS ALD 工艺，可能在多个领域具有重要的应用。