Hopping Diffusion of Gold Nanoparticles Observed with Liquid Cell TEM
See Wee Chee
1,2
, Duane Loh
1
, Zhaslan Baraissov
1,2
, Paul Matsudaira
1
and Utkur Mirsaidov
1,2,3
1.
Center for BioImaging Sciences, Department of Biological Sciences, National University of
Singapore, Singapore
2.
Centre for Advanced 2D Materials and Graphene Research Centre, Department of Physics, National
University of Singapore, Singapore
3.
Nanocore, Faculty of Engineering, National University of Singapore, Singapore
The diffusion of nanoparticles in the microfluidic cells used for liquid cell transmission electron
microscopy (TEM) have always been found to be much slower [1-6], often by several orders of
magnitude, when compared with bulk diffusion. While this highly suppressed motion is serendipitous
for the atomic resolution imaging of nanoparticle nucleation and coalescence events, we still lack a
compelling explanation for this anomalous phenomena. Here, we report results from our experiments
tracking the motion of Au nanoparticles in water, using a combination of energy filtered imaging and
image acquisition at frame rates of 100 Hz.
The Au nanoparticles (~20-70 nm in diameter) are dispersed in water and sandwiched between 30 nm
thick SiN
x
windows in a Hummingbird Scientific liquid flow holder. The holder is loaded into a JEOL
2200FS TEM with an Omega filter, where zero loss imaging (using a 20 eV energy slit) was used to
mitigate the resolution loss from imaging through the liquid layer. Movies are recorded on a Direct
Electron DE-12 camera system at 100 frames per second. The field of view is 819.2 nm by 819.2 nm
and electron dose rate used was between 30-100 electrons/Å
2
/s. The field of view and frame rate were
chosen so that it was possible, in principle, to capture nanoparticles moving at bulk velocities, while
minimizing the electron dose rate. The liquid layer thickness in each liquid cell was also measured using
electron energy loss spectroscopy.
In these experiments, we observed that nanoparticles moved via surface hops. This motion is illustrated
in Figure 1 as an image sequence where the nanoparticle made a series of such transient displacements
over 0.10 seconds; 1 between the second and third frame, and at least 8 between the fourth and tenth
frame, as inferred from the remnant contrast of the nanoparticle. We further deduce from the
discontinuous motion blur that these displacements are discrete. The nanoparticle also appear to re-visit
a few of the same locations. Figure 2 shows the entire recorded trajectory and the displacements
between frames as a function of time. In general, the nanoparticles move in a pattern where intermittent
hops that are tens of nanometers long are interspaced between lengthier segments of short displacements
that are only a few nanometers long. Our analysis indicates that the short, stuck motion is similar to the
reported suppressed diffusion, whereas during hops, the nanoparticles have mobility only two to three
orders of magnitude slower than bulk values calculated from the Stokes-Einstein equation. We propose
that the observed motion is due to surface potential wells, where a nanoparticle can make larger
displacements when it escapes a trapping well. This motion is, however, short-lived because the
nanoparticle is quickly trapped again. The implications of this study will be discussed. [7]
References:
[1] H.M. Zheng et al., Nano Lett. 9 (2009) p. 2460.
[2] E.A Ring and N. de Jonge, Micron 43 (2012) p. 1078.
[3] White et al. Langmuir 28 (2012) p. 3695.
[4] J.Y. Lu et al. Nano Lett. 14 (2014) p. 2111.
750
doi:10.1017/S1431927616004608
Microsc. Microanal. 22 (Suppl 3), 2016
© Microscopy Society of America 2016