Dipole-like electrostatic asymmetry of gold nanorods

Kim, Ji -Young; Han, Myung -Geun; Lien, Miao -Bin; Magonov, Sergei; Zhu, Yimei; George, Heather; Norris, Theodore B.; Kotov, Nicholas A.

doi:10.1126/sciadv.1700682

Dipole-like electrostatic asymmetry of gold nanorods

Journal Article · Fri Feb 09 00:00:00 EST 2018 · Science Advances

DOI:https://doi.org/10.1126/sciadv.1700682· OSTI ID:1434778

^[1]; Han, Myung -Geun ^[2]; Lien, Miao -Bin ^[1]; Magonov, Sergei ^[3]; ^[2]; ^[1]; ^[1]; ^[1]

Univ. of Michigan, Ann Arbor, MI (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)
SPM Labs LLC, Tempe, AZ (United States)

The symmetry of metallic nanocolloids, typically envisaged as simple geometrical shapes, is rarely questioned. However, the symmetry considerations are so essential for understanding their electronic structure, optical properties, and biological effects that it is important to reexamine these foundational assumptions for nanocolloids. Gold nanorods (AuNRs) are generally presumed to have nearly perfect geometry of a cylinder and therefore are centrosymmetric. We show that AuNRs, in fact, have a built-in electrostatic potential gradient on their surface and behave as noncentrosymmetric particles. The electrostatic potential gradient of 0.11 to 0.07 V/nm along the long axes of nanorods is observed by off-axis electron holography. Kelvin probe microscopy, secondary electron imaging, energy-filtered transmission electron microscopy, and plasmon mapping reveal that the axial asymmetry is associated with a consistently unequal number of cetyltrimethylammonium bromide moieties capping the two ends of the AuNRs. Electrostatic field maps simulated for the AuNR surface reproduce the holography images. The dipole-like surface potential gradient explains previously puzzling discrepancies in nonlinear optical effects originating from the noncentrosymmetric nature of AuNRs. Furthermore, similar considerations of symmetry breaking are applicable to other nanoscale structures for which the property-governing symmetry of the organic shell may differ from the apparent symmetry of inorganic core observed in standard electron microscopy images.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0012704

OSTI ID:: 1434778

Report Number(s):: BNL--203570-2018-JAAM

Journal Information:: Science Advances, Journal Name: Science Advances Journal Issue: 2 Vol. 4; ISSN 2375-2548

Publisher:: AAASCopyright Statement

Country of Publication:: United States

Language:: English

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