Cluster nucleation and growth from a highly supersaturated adatom phase: Silver on magnetite

Roland Bliem, Rukan Kosak, Lukas Perneczky, Zbynek Novotny, Oscar Gamba, David Fobes, Zhiqiang Mao, Michael Schmid, Peter Blaha, Ulrike Diebold, Gareth S. Parkinson

Research output: Contribution to journalArticle

29 Citations (Scopus)

Abstract

The atomic-scale mechanisms underlying the growth of Ag on the (√2×√2)R45°-Fe3O4(001) surface were studied using scanning tunneling microscopy and density functional theory based calculations. For coverages up to 0.5 ML, Ag adatoms populate the surface exclusively; agglomeration into nanoparticles occurs only with the lifting of the reconstruction at 720 K. Above 0.5 ML, Ag clusters nucleate spontaneously and grow at the expense of the surrounding material with mild annealing. This unusual behavior results from a kinetic barrier associated with the (√2×√2)R45° reconstruction, which prevents adatoms from transitioning to the thermodynamically favorable 3D phase. The barrier is identified as the large separation between stable adsorption sites, which prevents homogeneous cluster nucleation and the instability of the Ag dimer against decay to two adatoms. Since the system is dominated by kinetics as long as the (√2×√2)R45° reconstruction exists, the growth is not well described by the traditional growth modes. It can be understood, however, as the result of supersaturation within an adsorption template system.

Original languageEnglish (US)
Pages (from-to)7531-7537
Number of pages7
JournalACS nano
Volume8
Issue number7
DOIs
StatePublished - Jul 22 2014

Fingerprint

Ferrosoferric Oxide
Adatoms
Magnetite
Silver
magnetite
adatoms
Nucleation
silver
nucleation
Adsorption
Kinetics
adsorption
Supersaturation
kinetics
Scanning tunneling microscopy
supersaturation
agglomeration
Dimers
Density functional theory
scanning tunneling microscopy

All Science Journal Classification (ASJC) codes

  • Materials Science(all)
  • Engineering(all)
  • Physics and Astronomy(all)

Cite this

Bliem, R., Kosak, R., Perneczky, L., Novotny, Z., Gamba, O., Fobes, D., ... Parkinson, G. S. (2014). Cluster nucleation and growth from a highly supersaturated adatom phase: Silver on magnetite. ACS nano, 8(7), 7531-7537. https://doi.org/10.1021/nn502895s
Bliem, Roland ; Kosak, Rukan ; Perneczky, Lukas ; Novotny, Zbynek ; Gamba, Oscar ; Fobes, David ; Mao, Zhiqiang ; Schmid, Michael ; Blaha, Peter ; Diebold, Ulrike ; Parkinson, Gareth S. / Cluster nucleation and growth from a highly supersaturated adatom phase : Silver on magnetite. In: ACS nano. 2014 ; Vol. 8, No. 7. pp. 7531-7537.
@article{a7ac2e4ed6224435a463dc309c0670fe,
title = "Cluster nucleation and growth from a highly supersaturated adatom phase: Silver on magnetite",
abstract = "The atomic-scale mechanisms underlying the growth of Ag on the (√2×√2)R45°-Fe3O4(001) surface were studied using scanning tunneling microscopy and density functional theory based calculations. For coverages up to 0.5 ML, Ag adatoms populate the surface exclusively; agglomeration into nanoparticles occurs only with the lifting of the reconstruction at 720 K. Above 0.5 ML, Ag clusters nucleate spontaneously and grow at the expense of the surrounding material with mild annealing. This unusual behavior results from a kinetic barrier associated with the (√2×√2)R45° reconstruction, which prevents adatoms from transitioning to the thermodynamically favorable 3D phase. The barrier is identified as the large separation between stable adsorption sites, which prevents homogeneous cluster nucleation and the instability of the Ag dimer against decay to two adatoms. Since the system is dominated by kinetics as long as the (√2×√2)R45° reconstruction exists, the growth is not well described by the traditional growth modes. It can be understood, however, as the result of supersaturation within an adsorption template system.",
author = "Roland Bliem and Rukan Kosak and Lukas Perneczky and Zbynek Novotny and Oscar Gamba and David Fobes and Zhiqiang Mao and Michael Schmid and Peter Blaha and Ulrike Diebold and Parkinson, {Gareth S.}",
year = "2014",
month = "7",
day = "22",
doi = "10.1021/nn502895s",
language = "English (US)",
volume = "8",
pages = "7531--7537",
journal = "ACS Nano",
issn = "1936-0851",
publisher = "American Chemical Society",
number = "7",

}

Bliem, R, Kosak, R, Perneczky, L, Novotny, Z, Gamba, O, Fobes, D, Mao, Z, Schmid, M, Blaha, P, Diebold, U & Parkinson, GS 2014, 'Cluster nucleation and growth from a highly supersaturated adatom phase: Silver on magnetite', ACS nano, vol. 8, no. 7, pp. 7531-7537. https://doi.org/10.1021/nn502895s

Cluster nucleation and growth from a highly supersaturated adatom phase : Silver on magnetite. / Bliem, Roland; Kosak, Rukan; Perneczky, Lukas; Novotny, Zbynek; Gamba, Oscar; Fobes, David; Mao, Zhiqiang; Schmid, Michael; Blaha, Peter; Diebold, Ulrike; Parkinson, Gareth S.

In: ACS nano, Vol. 8, No. 7, 22.07.2014, p. 7531-7537.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Cluster nucleation and growth from a highly supersaturated adatom phase

T2 - Silver on magnetite

AU - Bliem, Roland

AU - Kosak, Rukan

AU - Perneczky, Lukas

AU - Novotny, Zbynek

AU - Gamba, Oscar

AU - Fobes, David

AU - Mao, Zhiqiang

AU - Schmid, Michael

AU - Blaha, Peter

AU - Diebold, Ulrike

AU - Parkinson, Gareth S.

PY - 2014/7/22

Y1 - 2014/7/22

N2 - The atomic-scale mechanisms underlying the growth of Ag on the (√2×√2)R45°-Fe3O4(001) surface were studied using scanning tunneling microscopy and density functional theory based calculations. For coverages up to 0.5 ML, Ag adatoms populate the surface exclusively; agglomeration into nanoparticles occurs only with the lifting of the reconstruction at 720 K. Above 0.5 ML, Ag clusters nucleate spontaneously and grow at the expense of the surrounding material with mild annealing. This unusual behavior results from a kinetic barrier associated with the (√2×√2)R45° reconstruction, which prevents adatoms from transitioning to the thermodynamically favorable 3D phase. The barrier is identified as the large separation between stable adsorption sites, which prevents homogeneous cluster nucleation and the instability of the Ag dimer against decay to two adatoms. Since the system is dominated by kinetics as long as the (√2×√2)R45° reconstruction exists, the growth is not well described by the traditional growth modes. It can be understood, however, as the result of supersaturation within an adsorption template system.

AB - The atomic-scale mechanisms underlying the growth of Ag on the (√2×√2)R45°-Fe3O4(001) surface were studied using scanning tunneling microscopy and density functional theory based calculations. For coverages up to 0.5 ML, Ag adatoms populate the surface exclusively; agglomeration into nanoparticles occurs only with the lifting of the reconstruction at 720 K. Above 0.5 ML, Ag clusters nucleate spontaneously and grow at the expense of the surrounding material with mild annealing. This unusual behavior results from a kinetic barrier associated with the (√2×√2)R45° reconstruction, which prevents adatoms from transitioning to the thermodynamically favorable 3D phase. The barrier is identified as the large separation between stable adsorption sites, which prevents homogeneous cluster nucleation and the instability of the Ag dimer against decay to two adatoms. Since the system is dominated by kinetics as long as the (√2×√2)R45° reconstruction exists, the growth is not well described by the traditional growth modes. It can be understood, however, as the result of supersaturation within an adsorption template system.

UR - http://www.scopus.com/inward/record.url?scp=84904768101&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84904768101&partnerID=8YFLogxK

U2 - 10.1021/nn502895s

DO - 10.1021/nn502895s

M3 - Article

AN - SCOPUS:84904768101

VL - 8

SP - 7531

EP - 7537

JO - ACS Nano

JF - ACS Nano

SN - 1936-0851

IS - 7

ER -

Bliem R, Kosak R, Perneczky L, Novotny Z, Gamba O, Fobes D et al. Cluster nucleation and growth from a highly supersaturated adatom phase: Silver on magnetite. ACS nano. 2014 Jul 22;8(7):7531-7537. https://doi.org/10.1021/nn502895s