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Atomic/molecular layer deposition of Ti-organic thin films from different aromatic alcohol and amine precursors
Thin Solid Films ( IF 2.0 ) Pub Date : 2021-08-18 , DOI: 10.1016/j.tsf.2021.138896
Anne Tanskanen 1 , Pia Sundberg 1 , Michael Nolan 2 , Maarit Karppinen 1
Affiliation  

Atomic/molecular layer deposition (ALD/MLD) processes based on TiCl4 as the metal source, and hydroquinone (HQ), 4-aminophenol (AP), p-phenylenediamine (PDA) or 4,4′-oxydianiline (ODA) as the organic precursor are systematically investigated to shed light on the factors affecting the inorganic-organic thin film growth. All the four ALD/MLD processes yield amorphous Ti-organic thin films which are here characterized by ex-situ X-ray reflectivity and Fourier transform infrared measurements for the film thickness and bonding scheme. First principles modelling results are presented to explore differences in the interaction of organic precursors with surface-bound TiCl4. For the TiCl4+AP process the high growth rate achieved, i.e. ca. 10 Å per one ALD/MLD cycle, essentially corresponds to the ideal thickness of the [Ti-O-C6H4single bondN-Ti] building unit. For both the ODA- and PDA-based processes the growth rates are considerably lower, while the TiCl4+HQ process yields the hybrid film with an intermediate growth rate. We attribute these observations to (i) the higher reactivity of the OH groups in comparison to the NH2 groups towards TiCl4, and (ii) the higher tendency of a heterobifunctional organic precursor to orientate vertically and avoid unwanted double reactions on the surface.



中文翻译:

来自不同芳香醇和胺前体的钛有机薄膜的原子/分子层沉积

基于 TiCl 4作为金属源,以氢醌 (HQ)、4-氨基苯酚 (AP)、对苯二胺 (PDA) 或 4,4'-氧二苯胺 (ODA) 为基础的原子/分子层沉积 (ALD/MLD) 工艺系统地研究了有机前体,以阐明影响无机 - 有机薄膜生长的因素。所有四种 ALD/MLD 工艺都产生非晶钛有机薄膜,其特征在于非原位 X 射线反射率和傅里叶变换红外测量的薄膜厚度和键合方案。呈现第一性原理建模结果以探索有机前体与表面结合的 TiCl 4相互作用的差异。对于 TiCl 4+AP 过程实现了高增长率,即大约。每个 ALD/MLD 循环 10 Å,基本上对应于 [Ti-OC 6 H 4单键 N-Ti] 构建单元的理想厚度。对于基于 ODA 和基于 PDA 的工艺,生长速率相当低,而 TiCl 4 +HQ 工艺产生具有中等生长速率的混合膜。我们将这些观察结果归因于 (i) 与 NH 2基团相比,OH 基团对 TiCl 4具有更高的反应性,以及 (ii) 异双功能有机前体垂直取向并避免表面上不需要的双反应的更高趋势。

更新日期:2021-08-27
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