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Mechanism of Stoichiometrically Governed Titanium Oxide Brownian Tree Formation on Stepped Au(111)

Journal Article · · Journal of Physical Chemistry. C
 [1];  [2];  [3];  [4];  [4]
  1. Univ. of California, Los Angeles, CA (United States)
  2. Stony Brook Univ., NY (United States)
  3. Stony Brook Univ., NY (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States). Chemistry Division
  4. Univ. of California, Los Angeles, CA (United States); California NanoSystems Institute, Los Angeles, CA (United States)
+ Show Author Affiliations
Previously observed formation of substoichiometric titanium oxide dendritic structures across terraces of Au(111) is computationally studied and shown to follow the classical fractal formation mechanism of diffusion-limited aggregation (DLA). Globally optimized gas-phase oxide cluster structures are sampled in a variety of landing formations on gold surfaces and shown to favor isomers driving polymerization to Brownian tree fractal structures. Mobility of Ti3O5 monomers is shown to be extremely high, with diffusion barriers of 0.21 eV or less. Through bonding stabilization, polymerization of these monomers is energetically favorable and irreversible on the 111 terrace but geometrically impossible to propagate along the step edge. Simulated scanning tunneling microscopy (STM) images show strong similarity to experiment. By contrast, observation of Ti3O6 aggregating as wires along step edges is explained by the affinity of oxygen to step edges and statistical arguments for aggregation entropy at the step, in addition to low barriers for monomer diffusion and polymerization.
Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States); Univ. of California, Los Angeles, CA (United States); University of California, Los Angeles, CA (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)
Grant/Contract Number:
AC02-05CH11231; AC02-06CH11357; SC0012704; SC0019152
OSTI ID:
1983767
Alternate ID(s):
OSTI ID: 2337936
OSTI ID: 2001181
Report Number(s):
BNL--224457-2023-JAAM
Journal Information:
Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 17 Vol. 127; ISSN 1932-7447
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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