Journal
ACS APPLIED MATERIALS & INTERFACES
Volume 12, Issue 8, Pages 9989-9999Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acsami.9b22065
Keywords
area-selective deposition (ASD); chemical vapor deposition (CVD); competitive adsorption; coadsorbate; 4-octyne; dielectric-on-dielectric (DoD); density functional theory (DFT); binding free energies
Funding
- Cornell University
- Cornell Center for Materials Research (CCMR)
- National Science Foundation MRSEC program [DMR-1719875]
- Office of Science of the U.S. Department of Energy [DE-AC02-06CH11357, DE-AC02-05CH11231]
- Semiconductor Research Corporation (SRC) [2644.001, 2889.001]
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In this work, we have explored the use of a third species during chemical vapor deposition (CVD) to direct thin-film growth to occur exclusively on one surface in the presence of another. Using a combination of density functional theory (DFT) calculations and experiments, including in situ surface analysis, we have examined the use of 4-octyne as a coadsorbate in the CVD of ZrO2 thin films on SiO2 and Cu surfaces. At sufficiently high partial pressures of the coadsorbate and sufficiently low substrate temperatures, we find that 4-octyne can effectively compete for adsorption sites, blocking chemisorption of the thin-film precursor, Zr[N(CH3C2H5)](4), and preventing growth on Cu, while leaving growth unimpeded on SiO2. The selective dielectric-on-dielectric (DoD) process developed herein is fast, totally vapor phase, and does not negatively alter the composition or morphology of the deposited thin film. We argue that this approach to area-selective deposition (ASD) should be widely applicable, provided that suitable candidates for preferential binding can be identified.
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