Understanding the growth mechanisms during the early stages of atomic layer deposition (ALD) is of interest for several applications including thin film deposition, catalysis, and area‐selective deposition. The surface dependence and growth mechanism of (ethylbenzyl)(1‐ethyl‐1,4‐cyclohexadienyl)ruthenium and O₂ ALD at 325 °C on HfO₂, Al₂O₃, OH, and SiOSi terminated SiO₂, and organosilicate glass (OSG) are investigated. The experimental results show that precursor adsorption is strongly affected by the surface termination of the dielectric, and proceeds most rapidly on OH terminated dielectrics, followed by SiOSi and finally SiCH₃ terminated dielectrics. The initial stages of growth are characterized by the formation and growth of Ru nanoparticles, which is mediated by the diffusion of Ru species. Mean‐field and kinetic Monte Carlo modeling show that ALD on OSG is best described when accounting for (1) cyclic generation of new nanoparticles at the surface, (2) surface diffusion of both atomic species and nanoparticles, and (3) size‐dependent nanoparticle reactivity. In particular, the models indicate that precursor adsorption initially occurs only on the dielectric substrate, and occurs on the Ru nanoparticles only when these reach a critical size of about 0.85 nm. This phenomenon is attributed to the catalytic decomposition of oxygen requiring a minimum Ru nanoparticle size.

中文翻译：

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介电基体上钌原子层沉积过程中扩散介导的生长和尺寸依赖性纳米颗粒反应性

了解原子层沉积（ALD）早期阶段的生长机制对于包括薄膜沉积，催化和区域选择性沉积在内的多种应用很重要。（乙基苄基）（1-乙基-1,4-环己二烯基）钌和O的表面依赖性和生长机制₂在上的HfO 325℃ALD ₂，AL ₂ ö ₃， OH和Si  ö 的Si的SiO终止参照图₂，对有机硅玻璃（OSG）进行了研究。实验结果表明，前驱体的吸附受到电介质表面终止的强烈影响，并且在时进行得最快。OH封端的电介质，随后的Si  Ó  Si和最后的Si  CH ₃端接的电介质。生长的初始阶段的特征是Ru纳米颗粒的形成和生长，这是通过Ru物种的扩散来介导的。平均场和动力学蒙特卡洛模型表明，当考虑（1）表面上新纳米颗粒的循环生成，（2）原子种类和纳米颗粒的表面扩散以及（3）尺寸依赖性时，OSG上的ALD可以得到最好的描述纳米颗粒反应性。特别地，模型表明，前体吸附最初仅在介电基材上发生，并且仅在Ru纳米颗粒达到约0.85 nm的临界尺寸时才发生。该现象归因于需要最小Ru纳米颗粒尺寸的氧的催化分解。