Zou Yiming, Cheng Chunyu, Guo Yuanyuan, Ong Amanda Jiamin, Goei Ronn, Li Shuzhou, Yoong Tok Alfred Iing
School of Materials Science and Engineering, Nanyang Technological University Singapore 639798 Singapore
RSC Adv. 2021 Jun 28;11(37):22773-22779. doi: 10.1039/d1ra03942c. eCollection 2021 Jun 25.
Rhodium (Rh) and palladium (Pd) thin films have been fabricated using an atomic layer deposition (ALD) process using Rh(acac) and Pd(hfac) as the respective precursors and using short-pulse low-concentration ozone as the co-reactant. This method of fabrication does away with the need for combustible reactants such as hydrogen or oxygen, either as a precursor or as an annealing agent. All previous studies using only ozone could not yield metallic films, and required post treatment using hydrogen or oxygen. In this work, it was discovered that the concentration level of ozone used in the ALD process was critical in determining whether the pure metal film was formed, and whether the metal film was oxidized. By controlling the ozone concentration under a critical limit, the fabrication of these noble metal films was successful. Rhodium thin films were deposited between 200 and 220 °C, whereas palladium thin films were deposited between 180 and 220 °C. A precisely controlled low ozone concentration of 1.22 g m was applied to prevent the oxidation of the noble metallic film, and to ensure fast growth rates of 0.42 Å per cycle for Rh, and 0.22 Å per cycle for Pd. When low-concentration ozone was applied to react with ligand, no excess ozone was available to oxidize the metal products. The surfaces of deposited films obtained the RMS roughness values of 0.30 nm for Rh and 0.13 nm for Pd films. The resistivities of 18 nm Rh and 22 nm Pd thin films were 17 μΩ cm and 63 μΩ cm.
已经使用原子层沉积(ALD)工艺制备了铑(Rh)和钯(Pd)薄膜,分别使用Rh(acac)和Pd(hfac)作为前驱体,并使用短脉冲低浓度臭氧作为共反应物。这种制备方法无需使用氢气或氧气等可燃反应物作为前驱体或退火剂。以前所有仅使用臭氧的研究都无法得到金属薄膜,并且需要使用氢气或氧气进行后处理。在这项工作中,发现ALD工艺中使用的臭氧浓度水平对于确定是否形成纯金属薄膜以及金属薄膜是否被氧化至关重要。通过将臭氧浓度控制在临界值以下,成功制备了这些贵金属薄膜。铑薄膜在200至220°C之间沉积,而钯薄膜在180至220°C之间沉积。应用精确控制的1.22 g/m的低臭氧浓度以防止贵金属薄膜氧化,并确保铑的生长速率为每循环0.42 Å,钯的生长速率为每循环0.22 Å。当使用低浓度臭氧与配体反应时,没有多余的臭氧可用于氧化金属产物。沉积薄膜的表面,铑薄膜的均方根粗糙度值为0.30 nm,钯薄膜的为0.13 nm。18 nm铑薄膜和22 nm钯薄膜的电阻率分别为17 μΩ·cm和63 μΩ·cm。