1270 Microsc. Microanal. 27 (Suppl 1), 2021
doi:10.1017/S1431927621004761 © Microscopy Society of America 2021
Graphene encapsulation enables vitreous ice sample for APT and near-atomic
reconstruction of nanoparticle-liquid interface
Shi Qiu
1
, Gediminas Gervinskas
2
, Hariprasad Venugopal
2
, Ross Marceau
3
and Jing Fu
1
1
Monash University, Clayton, Victoria, Australia,
2
Monash University, Victoria, Australia,
3
Deakin
University, Geelong, Victoria, Australia
We report an approach based on graphene encapsulation to investigate the structure and chemical
composition of liquid samples with APT. The specimens for probing are prepared by encapsulating the
solution with a single graphene membrane on top of a W or Si specimen needle tips, with the final diameter
maintained at less than 100 nm. The liquid specimens are then transferred to a laser-pulsed atom probe
instrument, and frozen by direct loading and contact onto the cryogenically cooled stage. Field evaporation
has been proven to be feasible, and the mass-to-charge-state ratio spectrum acquired from APT determines
the ion species. The reconstructed 3D chemical maps further reveal the original position of ions within
the frozen hydrated sample [1]. This approach allows exploring domains previously unreachable, such as
a single protein in solution [2].
To confirm the sample preparation process, additional graphene-encapsulated liquid specimens have been
directly loaded to the cryogenic stage in cryo-TEM without any pre-freezing technique, which is similar
to the cooling method performed in the APT experiment. The TEM image acquired, as well as the
diffraction pattern (Figure 1), reveal that no significant crystalline ice has been formed in the sub-100 nm
frozen hydrated domain. This suggests contact freezing of graphene-encapsulated liquid specimens is an
effective approach to ensure the near-native state of frozen samples. Using gold nanoparticles (AuNPs) in
suspension as an example, analysis of the mass spectrum and three-dimensional (3D) chemical maps
(Figure 2) from APT provides a detailed image of the water-gold interface at near-atomic resolution [3].
A locally dense region of Au
+
ions has been reconstructed, representing a portion of an individual AuNP.
A large number of water-related ions have also been identified, confirming the AuNP in the hydrated state.
At the water-gold interface, the trisodium-citrate layer has been observed based on Na
+
and C-containing
ions.
Acknowledgement.
The authors acknowledge funding from the Australian Research Council (DP180103955) and also the
contributions from coauthors in [1-3]. This work was performed in part at the Melbourne Centre for
Nanofabrication (MCN), Victorian Node of the Australian National Fabrication Facility (ANFF). Also,
the authors acknowledge the use of facilities within the Monash Centre for Electron Microscopy (MCEM),
Monash Ramaciotti Cryo-EM platform, Monash Campus Cluster (MCC), and Deakin University’s
Advanced Characterisation Facility.
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