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While reactor wall preconditioning was previously shown to influence the growth of carbon nanotubes (CNTs) by chemical vapor deposition (CVD), it was previously only limited to studying the accumulating carbon deposits over the history of a large number of growth runs. However, the effect of leaving the reactor walls for an extended period of time between growth runs was not previously systematically studied. Here, we combine experimental measurements with a mathematical model to investigate the effect of thermochemical history of reactor walls on growth yield of vertically aligned CNT forests. Importantly, we demonstrate unexpectedly high CNT yield, exceeding one-order-of-magnitude taller forests, by increasing the interim period between runs (IPBR). We explain the results based on previously unexplored process sensitivity to trace amounts of oxygen-containing species in the reactor. In particular, uncontrolled amounts of water vapor desorbing from reactor walls during growth are modelled in this work. Our modeling results show the effect of IPBR on the outgassing dynamics revealing the underlying mechanism of generating growth promoting molecules during growth. By installing a new humidity sensor in our multizone rapid thermal CVD reactor, we are able to uniquely correlate the amount of moisture within the reactor to real-time measurements of growth kinetics, as well as ex situ characterization of CNT alignment and atomic defects. Our findings enable a scientifically grounded approach toward both boosting growth yield and improving its consistency by reducing run-to-run variations. Accordingly, engineered growth recipes can be envisioned to leverage this effect for improving manufacturing process scalability and robustness. 

Abstract The synthesis of vertically aligned carbon nanotubes (CNTs), also referred to as CNT forest, by chemical vapor deposition (CVD) is an intricate process that is sensitive to multiple factors other than control of temperature, pressure, and gas flows. In particular, growth is highly sensitive to factors like ambient humidity, as well as small quantities of oxygen-containing species and carbon deposits inside the reactor. These typically uncontrolled factors significantly affect growth reproducibility and hinders the fundamental study of process–structure–property relationship for these emerging materials. Accordingly, universally applicable design modifications and process steps toward improving growth consistency are sought after. In this study, we introduce two new modifications to our custom-designed multizone rapid thermal CVD reactor and demonstrate their impact on growth: (1) reconfiguring the inlet gas plumbing to add a gas purifier to the helium (He) line, and (2) designing a new support wafer for consistent loading of substrates. We use statistical analysis to test the effectiveness of these modifications in improving growth and reducing variability of both CNT forest height and density. Analysis of our experimental results and hypothesis testing show that combining the implementation of He purifier with the redesigned support wafer increases forest height and reduces the variability in height (17-folds), both at statistically significant and practically significant levels. 

The synthesis of vertically aligned carbon nanotubes (CNTs), also referred to as CNT forest, by chemical vapor deposition (CVD) is an intricate process that is sensitive to multiple factors other than control of temperature, pressure, and gas flows. In particular, growth is highly sensitive to factors like ambient humidity, as well as small quantities of oxygen-containing species and carbon deposits inside the reactor. These typically uncontrolled factors significantly affect growth reproducibility and hinders the fundamental study of process-structure-property relationship for these emerging materials. Accordingly, universally applicable design modifications and process steps toward improve growth consistency are sought after. In this study, we introduce two new modifications to our custom-designed multizone rapid thermal CVD reactor and demonstrate their impact on growth: (1) reconfiguring the inlet gas plumbing to add a gas purifier to the helium (He) line, and (2) designing a new support wafer for consistent loading of substrates. We use statistical analysis to test the effectiveness of these modifications in improving growth and reducing variability of both CNT forest height and density. Analysis of our experimental results and hypothesis testing show that combining the implementation of He purifier with the redesigned support wafer increases forest height and reduces the variability in height (17-folds), both at statistically significant and practically significant levels.