van Limpt Renée T M, van Helvoirt Cristian A A, Creatore Mariadriana, Verheijen Marcel A
Eindhoven University of Technology, 5600 MB, Eindhoven, The Netherlands.
Eindhoven Institute of Renewable Energy Systems (EIRES), 5600 MB Eindhoven, The Netherlands.
Nanoscale. 2025 May 2;17(17):11037-11048. doi: 10.1039/d5nr01212k.
NiO and CoO are versatile materials studied for a plethora of applications, yet their performance for a specific application relies on the control of their crystallographic texture and corresponding surface facets. Achieving such control can be challenging, often requiring hetero-epitaxial growth on single-crystalline substrates, which are frequently incompatible with the requirements of the application. The combination of NiO and CoO in heterostructures provides potential to control texture due to their similar crystal structures, whilst retaining the possibility to work with more versatile substrates. In this study, atomic layer deposited (ALD) thin films based on cyclopentadienyl precursors and an oxygen plasma are adopted to tailor the crystallographic texture of NiO from 〈100〉 to 〈111〉 using an ALD CoO template layer, and similarly, to modify the CoO texture from 〈111〉 to 〈100〉 on a NiO template. The films are shown to conform to the crystal orientation of the template material, whilst crystallizing directly in their own stable crystal structure with corresponding metal atom coordination. Further investigation includes ALD process parameters for NiO growth: the film texture is found to depend on the choice of co-reactant and the above-highlighted hetero-epitaxial relationship is stronger for plasma-based processes. In conclusion, these results demonstrate an original approach for application-oriented crystallographic engineering in thin films.
氧化镍(NiO)和氧化钴(CoO)是用于众多应用研究的多功能材料,然而它们在特定应用中的性能取决于对其晶体织构和相应表面晶面的控制。实现这种控制可能具有挑战性,通常需要在单晶衬底上进行异质外延生长,而这种衬底往往与应用要求不兼容。由于氧化镍和氧化钴具有相似的晶体结构,在异质结构中结合它们可提供控制织构的潜力,同时保留使用更通用衬底的可能性。在本研究中,采用基于环戊二烯基前驱体和氧等离子体的原子层沉积(ALD)薄膜,利用ALD氧化钴模板层将氧化镍的晶体织构从〈100〉调整为〈111〉,同样地,在氧化镍模板上将氧化钴的织构从〈111〉修改为〈100〉。结果表明,这些薄膜符合模板材料的晶体取向,同时以相应金属原子配位直接在其自身稳定的晶体结构中结晶。进一步的研究包括氧化镍生长的ALD工艺参数:发现薄膜织构取决于共反应物的选择,并且上述突出的异质外延关系在基于等离子体的工艺中更强。总之,这些结果展示了一种用于薄膜中面向应用的晶体工程的原创方法。