Saturday, September 5, 2015

Role of Surface Termination in Atomic Layer Deposition of Silicon Nitride

Yet another fundamental publication from Eindhoven and Oxford Instruments on one of the most important (PE)ALD processes for scaled semiconductor devices - silicon nitride. This time Tyndall has helped them out to sort out the growth mechanism to better understand growth promotion and inhibition that has been reported previously - BTBAS Silicon nitride PEALD by TU Eindhoven, Oxford Instruments and ASM Microchemistry

Role of Surface Termination in Atomic Layer Deposition of Silicon Nitride

Chaitanya Krishna Ande†, Harm C. M. Knoops†‡, Koen de Peuter†, Maarten van Drunen†, Simon D. Elliott§, and Wilhelmus M. M. Kessels*†

† Department of Applied Physics, Eindhoven University of Technology, Den Dolech 2, 5600 MB Eindhoven, The Netherlands
‡ Oxford Instruments Plasma Technology, North End, Bristol BS49 4AP, United Kingdom
§ Tyndall National Institute, University College Cork, Dyke Parade, Lee Maltings, Cork, Ireland
J. Phys. Chem. Lett., 2015, 6, pp 3610–3614
DOI: 10.1021/acs.jpclett.5b01596

There is an urgent need to deposit uniform, high-quality, conformal SiNx thin films at a low-temperature. Conforming to these constraints, we recently developed a plasma enhanced atomic layer deposition (ALD) process with bis(tertiary-butyl-amino)silane (BTBAS) as the silicon precursor. However, deposition of high quality SiNx thin films at reasonable growth rates occurs only when N2 plasma is used as the coreactant; strongly reduced growth rates are observed when other coreactants like NH3 plasma, or N2–H2 plasma are used. Experiments reported in this Letter reveal that NHx- or H- containing plasmas suppress film deposition by terminating reactive surface sites with H and NHx groups and inhibiting precursor adsorption. To understand the role of these surface groups on precursor adsorption, we carried out first-principles calculations of precursor adsorption on the β-Si3N4(0001) surface with different surface terminations. They show that adsorption of the precursor is strong on surfaces with undercoordinated surface sites. In contrast, on surfaces with H, NH2 groups, or both, steric hindrance leads to weak precursor adsorption. Experimental and first-principles results together show that using an N2 plasma to generate reactive undercoordinated surface sites allows strong adsorption of the silicon precursor and, hence, is key to successful deposition of silicon nitride by ALD.

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