铝和钽氧化物表面原子层沉积钌的表面化学反应

IF 2.1 4区 化学 Q3 CHEMISTRY, PHYSICAL Surface Science Pub Date : 2024-08-10 DOI:10.1016/j.susc.2024.122572
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引用次数: 0

摘要

通过结合使用表面敏感技术,对基于三(2,2,6,6-四甲基-3,5-庚二酮酸)钌(III) (Ru(tmhd)3)和分子氧或原子氢在氧化铝薄膜上的 Ru 原子层沉积 (ALD) 过程的表面化学性质进行了表征。通过结合使用反射吸收红外光谱(RAIRS)、温度编程解吸(TPD)和 X 射线光电子能谱(XPS),确定 Ru 金属有机前体的热分解始于 400 K 以下,并在广泛的温度范围内逐步进行。这种化学反应产生的气相产物包括 2,2,6,6-四甲基-3,5-庚二酮(质子化配体 Htmhd;在 520 K 时出现 TPD 峰)、异丁烯(540 K;表明有机配体发生了破碎)以及异构化和/或醛醇缩合(650 和 730 K)产生的其他产物。伴随着这种化学反应,Ru3+ 离子的还原过程分为两个阶段,首先是失去部分配位体并与基底直接结合(500 至 600 K 之间),然后完全还原为金属态(600 至 700 K)。使用分子氧或原子氢的 ALD 循环可使 Ru 在表面上缓慢沉积,但碳的共沉积无法避免,至少在最初的循环中,氧化铝表面仍然暴露在外。使用 O2 时,Ru 原子在部分氧化(O2 暴露后)和零价(Ru(tmhd)3 剂量后)状态之间交替,在 ALD 循环的后半段后,可以看到一些 Ru 以挥发性 RuO4 氧化物的形式流失;使用 H- 时,既没有观察到 Ru 氧化状态的交替,也没有观察到一些 Ru 从表面消失。结合角度分辨 XPS(ARXPS)和低能离子散射(LEIS)实验的结果,可以确定沉积的 Ru 是以三维纳米颗粒的形式生长,而不是以逐层二维薄膜的形式生长,这可能是因为 Ru 前驱体优先吸附在金属表面(并且分解得更干净)。本文讨论了这些结果对 ALD 工艺设计的影响。
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The surface chemistry of the atomic layer deposition of ruthenium on aluminum and tantalum oxide surfaces

The surface chemistry of Ru atomic layer deposition (ALD) processes based on the use of tris(2,2,6,6-tetramethyl-3,5-heptanedionato)ruthenium(III) (Ru(tmhd)3) and either molecular oxygen or atomic hydrogen on aluminum oxide films was characterized by a combination of surface-sensitive techniques. The thermal decomposition of the Ru metalorganic precursor was determined, by using a combination of reflection-absorption infrared spectroscopy (RAIRS), temperature programmed desorption (TPD), and X-ray photoelectron spectroscopy (XPS), to start below 400 K and to take place in a stepwise fashion over a wide range of temperatures. Gas-phase products from this chemistry include 2,2,6,6-tetramethyl-3,5-heptanedione (the protonated ligand, Htmhd; in a TPD peak at 520 K), isobutene (540 K; indicating the fragmentation of the organic ligands), and other products from isomerization and/or aldol condensation (650 and 730 K). This chemistry is accompanied by the reduction of the Ru3+ ions in two stages, involving the loss of some of their ligands and their direct bonding to the substrate first (between 500 and 600 K) and a full reduction to a metallic state later on (600–700 K). ALD cycles using either molecular oxygen or atomic hydrogen resulted in the slow build-up of Ru on the surface, but the co-deposition of carbon could not be avoided, at least in the initial cycles, while the alumina surface was still exposed. With O2, the Ru atoms alternate between partially-oxidized (after the O2 exposures) and zero-valent (after the Ru(tmhd)3 doses) states, and some Ru loss in the form of the volatile RuO4 oxide was seen after the second half of the ALD cycles; neither the Ru oxidation state alternation nor the elimination of some Ru from the surface were observed when using H·. The deposited Ru was determined, by combining results from angle-resolved XPS (ARXPS) and low-energy ion scattering (LEIS) experiments, to grow as 3D nanoparticles rather than as a layer-by-layer 2D film, presumably because the Ru precursor preferentially adsorbs (and decomposes more cleanly) on the metal surface. A discussion is provided of the implications of these results for the design of ALD processes.

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来源期刊
Surface Science
Surface Science 化学-物理:凝聚态物理
CiteScore
3.30
自引率
5.30%
发文量
137
审稿时长
25 days
期刊介绍: Surface Science is devoted to elucidating the fundamental aspects of chemistry and physics occurring at a wide range of surfaces and interfaces and to disseminating this knowledge fast. The journal welcomes a broad spectrum of topics, including but not limited to: • model systems (e.g. in Ultra High Vacuum) under well-controlled reactive conditions • nanoscale science and engineering, including manipulation of matter at the atomic/molecular scale and assembly phenomena • reactivity of surfaces as related to various applied areas including heterogeneous catalysis, chemistry at electrified interfaces, and semiconductors functionalization • phenomena at interfaces relevant to energy storage and conversion, and fuels production and utilization • surface reactivity for environmental protection and pollution remediation • interactions at surfaces of soft matter, including polymers and biomaterials. Both experimental and theoretical work, including modeling, is within the scope of the journal. Work published in Surface Science reaches a wide readership, from chemistry and physics to biology and materials science and engineering, providing an excellent forum for cross-fertilization of ideas and broad dissemination of scientific discoveries.
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