AUTHOR=Chiappim William , Fraga Mariana Amorim , Maciel Homero Santiago , Pessoa Rodrigo Sávio TITLE=An Experimental and Theoretical Study of the Impact of the Precursor Pulse Time on the Growth Per Cycle and Crystallinity Quality of TiO2 Thin Films Grown by ALD and PEALD Technique JOURNAL=Frontiers in Mechanical Engineering VOLUME=6 YEAR=2020 URL=https://www.frontiersin.org/journals/mechanical-engineering/articles/10.3389/fmech.2020.551085 DOI=10.3389/fmech.2020.551085 ISSN=2297-3079 ABSTRACT=

In this paper, theoretical and experimental approaches were used to evaluate the impact of the precursor's pulse time on the growth per cycle and the crystallinity quality of atomic layer deposited TiO2 thin films on Si(100) and FTO substrates. We employ a general model that can be applied to both metal and oxidant precursors, based on the Maxwell-Boltzmann velocity distribution from which the molecular flux of gases that collide with the substrate is deduced to adjust the experimental characteristics of growth per cycle vs. pulse time. This model allowed us to adjust the growth per cycle of TiO2 films produced by thermal atomic layer deposition and by plasma-enhanced atomic layer deposition under different deposition parameters and substrates. The influence of growth per cycle on the chemical and structural properties of TiO2 thin films was evaluated by Rutherford backscattering spectroscopy, grazing incidence x-ray diffraction, and ellipsometry techniques. In thermal mode, using H2O as an oxidant precursor, the stoichiometry of TiOx films has an x value of 1.98 from the growth per cycle saturated regardless of the metal precursor or substrate used. Using O2 plasma, a super-stoichiometric film with x values from 2.02 to 2.30 was obtained. In thermal mode, the growth per cycle saturated and film thickness are, on average, 40% higher for TiCl4 compared to TTIP precursor. Using O2 plasma, the growth per cycle saturated is approximately twice as high as the thermal mode using the TTIP precursor. For both atomic layer deposition modes, the degree of crystallinity showed values of 50–80% for TiCl4 in the temperature range of 250–350°C. For TTIP, it was below 40% in thermal mode and between 80 and 95% in plasma mode (250°C). It was observed that the reaction rate, the diffusion coefficient, and the molecular flux are inversely proportional to the temperature. These results provide evidence that the crystallinity and epitaxial quality of the TiO2 film are higher for TTIP using O2 plasma. However, we verified that there was better stability of the parameters analyzed for TiCl4 in the two atomic layer deposition modes.