Self-Catalyzed, Low-Temperature Atomic Layer Deposition of Ruthenium Metal Using Zero-Valent Ru(DMBD)(CO)3 and Water

Gao, Zhengning; Le, Duy; Khaniya, Asim; Dezelah, Charles L.; Woodruff, Jacob; Kanjolia, Ravindra K.; Kaden, William E.; Rahman, Talat S.; Banerjee, Parag

doi:10.1021/acs.chemmater.8b04456

Title: Self-Catalyzed, Low-Temperature Atomic Layer Deposition of Ruthenium Metal Using Zero-Valent Ru(DMBD)(CO)₃ and Water

Journal Article · 29 January 2019 · Chemistry of Materials

DOI: https://doi.org/10.1021/acs.chemmater.8b04456 · OSTI ID:1542427

^[1];

^[2]; Khaniya, Asim ^[2]; Dezelah, Charles L. ^[3]; Woodruff, Jacob ^[3]; Kanjolia, Ravindra K. ^[3]; Kaden, William E. ^[2]; Rahman, Talat S. ^[2];

^[1]

Washington Univ., St. Louis, MS (United States); Univ. of Central Florida, Orlanda, FL (United States)
Univ. of Central Florida, Orlando, FL (United States)
EMD Performance Materials, Haverhill, MA (United States)

Ruthenium (Ru) films are deposited using atomic layer deposition (ALD), promoted by a self-catalytic reaction mechanism. Using zero-valent, η⁴-2,3-dimethylbutadiene Ruthenium tricarbonyl (Ru(DMBD)(CO)₃) and H₂O, Ru films are deposited at a rate of 0.1 nm/cycle. The temperature for steady deposition lies between 160 and 210 °C. Film structure and composition are confirmed via X-ray diffraction, high-resolution transmission electron microscopy, and X-ray photoelectron spectroscopy. The room-temperature electrical resistivity of 10 nm Ru films is found to be 39 μΩ·cm. In situ quadrupole mass spectrometry and density functional theory are used to understand ALD surface reactions. The ligand, dimethylbutadiene dissociatively desorbs on the surface. On the other hand, the carbonyl ligand is catalyzed by the Ru center. This leads to the water gas shift reaction, forming CO₂ and H₂. Modulating deposition temperature affects these two ligand dissociation reactions. This in turn affects nucleation, growth, and hence, Ru film properties. Self-catalyzed reactions provide a pathway for low-temperature ALD with milder co-reactants.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Organization:: USDOE

Grant/Contract Number:: FG02-07ER15842

OSTI ID:: 1542427

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 4 Vol. 31; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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