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Mechanistic Study of Nucleation Enhancement in Atomic Layer Deposition by Pretreatment with Small Organometallic Molecules
Chemistry of Materials ( IF 7.2 ) Pub Date : 2019-12-26 , DOI: 10.1021/acs.chemmater.9b03826 Camila de Paula 1 , Nathaniel E. Richey 1 , Li Zeng 1 , Stacey F. Bent 1
Chemistry of Materials ( IF 7.2 ) Pub Date : 2019-12-26 , DOI: 10.1021/acs.chemmater.9b03826 Camila de Paula 1 , Nathaniel E. Richey 1 , Li Zeng 1 , Stacey F. Bent 1
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Thermal atomic layer deposition (ALD) of metals on metal oxide surfaces typically suffers from nucleation delays that result in poor-quality films. The poor nucleation may be caused by a lack of suitable chemisorption sites on the oxide surface, which are needed for metal nucleation to occur. In this work, we demonstrate that prefunctionalizing the surface with a single monolayer of small organometallic molecules from the vapor phase can lead to a significant increase in surface coverage of the metal deposited by ALD. This process is demonstrated for Pt ALD from (methylcyclopentadienyl)trimethylplatinum (MeCpPtMe3) and O2, with nucleation enhanced almost 3-fold at 100 ALD cycles after the pretreatment. We hypothesize that the high coverage of the organometallic molecule provides an alternative chemisorption mechanism for the platinum precursor and thus leads to an increase in its uptake. The proposed chemisorption mechanism is robust across several organometallic molecule pretreatments and could potentially be exploited for other organometallic-based metal ALD processes. This chemisorption mechanism was probed using in situ quadrupole mass spectrometry (QMS). The growth of the platinum deposits was investigated in depth through scanning electron microscopy (SEM) and grazing incidence small-angle X-ray scattering (GISAXS). These studies show that the pretreatment also results in the improved wettability of Pt nanoparticles (NPs). The improved wettability is likely to affect the Pt diffusion properties, further contributing to the enhancement observed on the treated substrates. In addition, GISAXS and SEM studies indicate the growth of larger, denser, and more highly ordered Pt NPs at early cycle numbers, which subsequently coalesce into continuous and pinhole-free films. Surface pretreatment by organometallic molecules therefore introduces a potential route to achieve improved nucleation and growth of ultrathin films.
中文翻译：
小有机金属分子预处理促进原子层沉积成核的机理研究
金属在金属氧化物表面上的热原子层沉积（ALD）通常会遭受成核延迟，导致成膜质量差。不良的成核作用可能是由于氧化物表面缺乏合适的化学吸附位点所必需的，而金属的成核作用是这些位置所必需的。在这项工作中，我们证明了用来自气相的有机金属小分子的单层预功能化表面可以导致ALD沉积的金属表面覆盖率显着增加。对于来自（甲基环戊二烯基）三甲基铂（MeCpPtMe 3）和O 2的Pt ALD证明了该过程在预处理后的100个ALD循环中，成核作用增强了几乎3倍。我们假设有机金属分子的高覆盖率为铂前体提供了另一种化学吸附机制，从而导致其吸收增加。所提出的化学吸附机制在几种有机金属分子预处理中均很稳定，并且可能会被其他有机金属基金属ALD工艺开发利用。使用原位四极杆质谱（QMS）探测了这种化学吸附机理。通过扫描电子显微镜（SEM）和掠入射小角X射线散射（GISAXS）深度研究了铂沉积物的生长。这些研究表明，预处理还可以改善Pt纳米颗粒（NPs）的润湿性。改善的润湿性可能会影响Pt扩散性能，进一步有助于在处理后的基材上观察到的增强。此外，GISAXS和SEM研究表明，更大，更密实和更有序的Pt NP在早期循环数时会增长，随后会聚集成连续且无针孔的薄膜。因此，通过有机金属分子进行的表面预处理引入了一种潜在的途径，可以改善超薄膜的形核和生长。
更新日期：2019-12-27
中文翻译：
小有机金属分子预处理促进原子层沉积成核的机理研究
金属在金属氧化物表面上的热原子层沉积（ALD）通常会遭受成核延迟，导致成膜质量差。不良的成核作用可能是由于氧化物表面缺乏合适的化学吸附位点所必需的，而金属的成核作用是这些位置所必需的。在这项工作中，我们证明了用来自气相的有机金属小分子的单层预功能化表面可以导致ALD沉积的金属表面覆盖率显着增加。对于来自（甲基环戊二烯基）三甲基铂（MeCpPtMe 3）和O 2的Pt ALD证明了该过程在预处理后的100个ALD循环中，成核作用增强了几乎3倍。我们假设有机金属分子的高覆盖率为铂前体提供了另一种化学吸附机制，从而导致其吸收增加。所提出的化学吸附机制在几种有机金属分子预处理中均很稳定，并且可能会被其他有机金属基金属ALD工艺开发利用。使用原位四极杆质谱（QMS）探测了这种化学吸附机理。通过扫描电子显微镜（SEM）和掠入射小角X射线散射（GISAXS）深度研究了铂沉积物的生长。这些研究表明，预处理还可以改善Pt纳米颗粒（NPs）的润湿性。改善的润湿性可能会影响Pt扩散性能，进一步有助于在处理后的基材上观察到的增强。此外，GISAXS和SEM研究表明，更大，更密实和更有序的Pt NP在早期循环数时会增长，随后会聚集成连续且无针孔的薄膜。因此，通过有机金属分子进行的表面预处理引入了一种潜在的途径，可以改善超薄膜的形核和生长。
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