nanomaterials

Communication
Investigating Charge-Induced Transformations of Metal
Nanoparticles in a Radically-Inert Liquid: A Liquid-Cell
TEM Study
Kunmo Koo 1 , Jong Hyeok Seo 1,2 , Joohyun Lee 1 , Sooheyong Lee 1,2, * and Ji-Hwan Kwon 1,2, *

1 Korea Research Institute of Standards and Science, Daejeon 34113, Republic of Korea;
[email protected] (K.K.); [email protected] (J.H.S.); [email protected] (J.L.)
2 Department of Nano Convergence Measurement, Korea University of Science and Technology,
Daejeon 34113, Republic of Korea
* Correspondence: [email protected] (S.L.); [email protected] (J.-H.K.)

Abstract: We present a novel in situ liquid-cell transmission electron microscopy (TEM) approach
to study the behavior of metal nanoparticles under high-energy electron irradiation. By utilizing a
radically-inert liquid environment, we aim to minimize radiolysis effects and explore the influence of
charge-induced transformations. We observed complex dynamics in nanoparticle behavior, including
morphological changes and transitions between amorphous and crystalline states. These transforma-
tions are attributed to the delicate interplay between charge accumulation on the nanoparticles and
enhanced radiolysis, suggesting a significant role for charge-assisted processes in nanoparticle evolu-
tion. Our findings provide valuable insights into the fundamental mechanisms driving nanoparticle
behavior at the nanoscale and demonstrate the potential of liquid-cell TEM for studying complex
physicochemical processes in controlled environments.

Keywords: liquid-phase transmission electron microscopy; Au nanoparticle; phase transition

Citation: Koo, K.; Seo, J.H.; Lee, J.; 1. Introduction

Lee, S.; Kwon, J.-H. Investigating
Melting, a fundamental phase transition in condensed matter systems, is a complex
Charge-Induced Transformations of
process with far-reaching implications across various scientific disciplines and industrial
Metal Nanoparticles in a
applications. This transition involves the transformation of an ordered crystalline structure
Radically-Inert Liquid: A Liquid-Cell
TEM Study. Nanomaterials 2024, 14,
into a disordered liquid phase, characterized by significant changes in atomic mobility and
1709. https://doi.org/10.3390/
structural properties. While macroscopic properties of melting are well-understood, the
nano14211709 atomic-scale aspects of this phenomenon remain elusive. Traditionally, it was believed that
melting preferentially initiates at crystal surfaces, grain boundaries, and dislocations [1].
Academic Editor: Giancarlo Rizza
However, recent research has revealed that it often begins at defect sites within crystal
Received: 4 September 2024 structures, challenging the conventional view [2]. The essence of melting lies in the dra-
Revised: 18 October 2024 matic increase in atomic mobility as a material approaches and undergoes the structural
Accepted: 24 October 2024 transition from a solid to a liquid. Therefore, the ability to visualize real-time structural
Published: 26 October 2024 changes at the relevant length scale is crucial for both underlying scientific principles and
practical applications.
In recent years, advancements in experimental techniques, such as high-resolution
electron diffraction and in-situ transmission electron microscopy (TEM), have enabled
Copyright: © 2024 by the authors.
direct investigation of nanomaterial structures and dynamics under various conditions.
Licensee MDPI, Basel, Switzerland.
For instance, the development of closed environmental cells has broadened the scope
This article is an open access article
of electron microscopy, allowing for the study of materials that easily vaporize from
distributed under the terms and
solid specimens [3–5]. Modern encapsulation techniques, such as silicon nitride [6–8],
conditions of the Creative Commons
Attribution (CC BY) license (https://
graphene [9–12], and their hybrids [13–15], offer the necessary physical robustness and
creativecommons.org/licenses/by/
electron transparency. These features enable the safe and efficient handling of liquid-
4.0/). containing specimens within the extreme high vacuum conditions of electron optics. Liquid

Nanomaterials 2024, 14, 1709. https://doi.org/10.3390/nano14211709 https://www.mdpi.com/journal/nanomaterials

Nanomaterials 2024, 14, 1709 2 of 9

phase electron microscopy (LPEM) has been employed to explore a variety of chemicals,
ranging from aqueous solutions [16–18] to organic solvents [19–21], and from acidic [22]
to basic solutions [23]. This approach has proven effective in characterizing nanomaterial
formation dynamics [9,16,24,25], electrochemical reactions [26–28], and in capturing high-
resolution images of wet biomolecules [18,29] under specialized configurations. However,
many in-situ reactions occurring within an environmental cell TEM can trigger undesirable
side reactions, potentially altering the reaction mechanisms compared to ex-situ conditions.
To better understand the mechanisms behind these redox-related etching, nucleation, and
electrochemical reactions, radical chemistry is often considered [30–32], especially since
the direct energy transfer from highly accelerated incident electron beams involves very
small cross-sections. Consequently, minimizing the effects of reactive radicals should be a
primary consideration unless they are intentionally used to initiate the reaction during in
situ electron microscopy. Several methods are available to suppress or neutralize radical
generation during electron microscopy, ensuring more accurate observations. For instance,
cryogenic electron microscopy mitigates radiolytic decomposition by reducing the mobility
and reaction rate of generated radicals [33]. Also, graphene-based liquid cell techniques
exploit the radical-scavenging properties of graphene derivatives [11,34,35], and low-dose
electron microscopy [18] minimizes the production of radical molecules.
In this work, we circumvented the effects of radiolysis by using a radically inert liquid
and investigated the charge-induced melting of metal nanoparticles in TEM. In our finding,
even at a high electron dose rate of 105 e− /Å2 ·s, radiolysis-induced etching or precipitation
was absent, with only charge-induced disordering of colloidal nanoparticles being observed.
We examined the changes in morphology and crystallinity of nanoparticles dispersed in
the liquid under substantial electron irradiation. The experimental configuration ensured
that suspended nanoparticles did not contact the membrane during melting, allowing
nucleation to occur independently of membrane interaction. This approach enabled probing
the solid-liquid phase transition while preventing direct vaporization or sublimation into
the vacuum. In-situ and postmortem analyses revealed that the amorphous and crystalline
phases transition between each other during the melting process, closely mirroring the
dense-phase formation stage in nucleation.

2. Experimental Methods
The Au nanoparticles utilized in our experiments were approximately 30 nm in diam-
eter and sourced from certified reference materials (CRM) provided by the Korea Research
Institute of Standards and Science (KRISS). For the in situ liquid-cell TEM experiments, we
employed a Poseidon liquid holder from Protochips, Morrisville, NC, USA. The experi-
ments were conducted using a liquid microelectromechanical system (MEMS) chip with
a window size of 550 × 50 µm and a spacer thickness of 50 nm for electron irradiation.
Additionally, we used the Poseidon electrochemistry E-chip for potential measurements.
The Si3 N4 membrane in the liquid cell was also approximately 50 nm thick, facilitating
electron beam irradiation while preserving the liquid environment. The Au nanoparticles
were suspended in solvents, including acetonitrile and water, and the suspension was
carefully applied to the liquid MEMS chip. The static-type liquid phase TEM experiments
were then performed, during which electron beam irradiation was applied, and potential
measurements were recorded as part of the experimental procedure.
The real-time TEM images from the liquid cell were acquired using a FEI Tecnai F30
(Thermo Fisher, Waltham, MA, USA) equipped with a Gatan OneView camera at the Korea
Research Institute of Standards and Science (KRISS). The microprobe mode was used with
a fixed electron beam size of 50 nm and 190 nm, corresponding to 1.3 × 105 e− /Å2 ·s and
9.2 × 103 e− /Å2 ·s, respectively. The screen current for the electron beam was 4 nA. The
TEM operated at 300 kV with an energy spread of approximately 1 eV (∆E/E ~ 10−6 ), as
determined by the zero-loss peak in electron energy loss spectroscopy.
Nanomaterials 2024, 14, 1709 3 of 9

3. Results and Discussion

3.1. Charge-Induced Breakdown of Nanoparticles in a Liquid Cell Electron Microscopy
Compared to water-filled liquid environmental cells, Au nanoparticle dispersions in
acetonitrile exhibit greater tolerance to high electron beam doses due to reduced radical
generation. In aqueous LPEM systems, primary decomposition and subsequent chain
reactions produce reactive oxygen species (ROS) such as OH,·O2 − ,·O2 2− , HO2 , HO3 ,·O3 ,
and other unstable radicals [30]. These radicals contribute to radiolytic decomposition by
breaking material bonds during the propagation stage. While acetonitrile also undergoes
bond dissociation under high energy intake, its primary decomposition products, ·H and
CH2 CN, are more stable than those from water. The bond dissociation energy (BDE), a
measure of radical stabilization enthalpy (RSE), of the·CH2 CN radical (401.71 kJ mol−1 )
is lower than that of the hydroxyl radical (497.1 kJ mol−1 ), indicating its greater stability.
At steady state, stable methyl radicals (CH3 , BDE = 439.3 kJ mol−1 ) and reactive cyanide
radicals (CN, BDE = 527.6 kJ mol−1 ) are generated, but their saturation concentrations are
approximately 105 times lower than the primary species [36–38].
While the use of radiolytic intervention-suppressed liquid cells allow for electron
microscopy without undesirable side reactions at lower electron doses, higher irradiation
levels introduce new challenges. The insulating properties of the liquid cell’s constituent
elements, such as acetonitrile and silicon nitride [39], can lead to significant charge buildup
during electron illumination. This charge accumulation, caused by the ejection of secondary
and Auger electrons, can negatively impact imaging quality and even lead to sample
decomposition at extreme levels [40–43]. Unlike conventional conducting carbon-coated
grid specimens or graphene liquid cells, the insulating nature of acetonitrile and silicon
nitride hinders charge dissipation, exacerbating the issue. The internal potential, induced
by electron illumination, could potentially be measured using off-axis holography [44,45].
However, this technique is challenging to implement in liquid cell microscopy due to
the lack of a suitable vacuum phase reference. As an alternative, the relative electrical
potential of the liquid holder system was measured directly using an electrically isolated
environmental cell setup (Figure 1a). To ensure accurate potential measurement, the
Nanomaterials 2024, 14, x FOR PEER REVIEW 4 of 10
dielectric materials and electron-transparent window were replaced with a 300 nm thick
membrane, deviating from the conventionally used 50 nm-thick liquid MEMS chip.

Figure 1. (a) Schematics of an electrically insulated liquid cell configuration with electrodes. (b) The
Figure 1. (a) Schematics of an electrically insulated liquid cell configuration with electrodes. (b) The
potential between the working electrode and reference electrode was measured during electron il-
potential ofbetween
lumination the working
the environmental cell. electrode and reference electrode was measured during electron
illumination of the environmental cell.
3.2. Morphology Change of Nanoparticle During Charge-Induced Melt
Focused electron beam irradiation can induce ballistic damage in only 16% of atoms
with a single positive charge, resulting from broken bonds [46]. In gold nanoparticles, this
damage can manifest as surface fluctuations, atomic relocation, loss of crystal ordering, or
field evaporation [47]. However, in an acetonitrile liquid cell, evaporation is prevented by
the surrounding liquid, leading to local mass effusion. To investigate the effects of charge
on particle deformation in a liquid, a gold nanoparticle suspended in an acetonitrile solu-
Nanomaterials 2024, 14, 1709 4 of 9

When the liquid cell was filled with acetonitrile, the magnitude of potential change
decreased compared to the vacuum case (Figure 1b). This reduction is expected, as the
effective escape surface for low-energy secondary electrons remains constant while the
illuminated volume increases due to the liquid. Although the potential change in the
liquid cell system (20 ± 0.3 mV) was smaller than that observed for gold in vacuum
(70.4 ± 1.7 mV), it was comparable to the potential measured during the illumination of
an insulator in vacuum (17.4 ± 1.3 mV). While the overall potential measurement of the
liquid cell does not provide an accurate estimate of the gold nanoparticle’s charge state, it
suggests that the illuminated area is positively charged relative to the surrounding system.
Given that the cumulative charge in the illuminated liquid column is similar to that of the
irradiated nitride membrane in vacuum, the material within the liquid cell is also likely to
experience charge-induced structural changes under focused electron beam irradiation.

3.2. Morphology Change of Nanoparticle During Charge-Induced Melt

Focused electron beam irradiation can induce ballistic damage in only 16% of atoms
with a single positive charge, resulting from broken bonds [46]. In gold nanoparticles, this
damage can manifest as surface fluctuations, atomic relocation, loss of crystal ordering,
or field evaporation [47]. However, in an acetonitrile liquid cell, evaporation is prevented
by the surrounding liquid, leading to local mass effusion. To investigate the effects of
charge on particle deformation in a liquid, a gold nanoparticle suspended in an acetonitrile
solution was irradiated with an electron probe current of 4 nA and a diameter of 185 nm
(9.2 × 103 e− /Å2 ·s). A single floating Au nanoparticle, initially icosahedral, underwent a
shape transformation, initially becoming spherical and then elongating in one direction.
The elongated cuboid exhibited a minimal roundness factor and a maximum aspect ratio.
A twin boundary formed along the major axis, confirming the particle’s single-crystal
structure. Upon further irradiation to 1.7 × 106 e− /Å2 (180 s), the particle surface became
viscous and behaved like a dense liquid, with a minimum circularity factor indicating
an elongated perimeter and complex surface morphology. While additional irradiation
did not alter the particle’s overall shape, the perimeter remained larger than its original
state (Figure 2a). We note that, at this electron dose, aqueous liquid cells would typically
Nanomaterials 2024, 14, x FOR PEER REVIEW 5 of 10
undergo radiolytic decomposition and particle explosion, but the nanoparticle in this case
maintained its original projection area and did not experience radiolytic reactions.

Figure 2.
Figure Morphologicalevolution
2.Morphological evolutionof of
AuAu nanoparticles
nanoparticles dispersed
dispersed in acetonitrile
in acetonitrile underunder varying
varying elec-
tron doses.
electron (a) At
doses. (a)aAt
moderate electron
a moderate dosedose
electron raterate
of 9.2 10×
of×9.2 1032e·s,− typically
3 e−/Å
/Å2 ·s, typically
used during liquid phase
used during liquid
electron microscopy (LPEM), the nanoparticle exhibits slight surface deformation and viscous be-
havior. (b) At a high electron dose rate of 1.3 × 105 e−/Å2·s, comparable to high-resolution TEM con-
ditions for solid phases, the nanoparticle undergoes significant deformation, displaying behavior
characteristic of solid-liquid phase transformation. Scale bar is 10 nm.

At a significantly higher dose of 1.3 × 105 e−/Å2·s, dramatic deformation of the particle
Nanomaterials 2024, 14, 1709 5 of 9

phase electron microscopy (LPEM), the nanoparticle exhibits slight surface deformation and viscous
behavior. (b) At a high electron dose rate of 1.3 × 105 e− /Å2 ·s, comparable to high-resolution TEM
conditions for solid phases, the nanoparticle undergoes significant deformation, displaying behavior
characteristic of solid-liquid phase transformation. Scale bar is 10 nm.

At a significantly higher dose of 1.3 × 105 e− /Å2 ·s, dramatic deformation of the
particle is observed (Figure 2b). Liquefaction of the gold particle initiates at 2.3 × 106 e− /Å2
(18 s) when small protrusions appear on the surface. Up to this point, the particle maintains
its original crystallinity, as evidenced by the observable diffraction contrast throughout
its structure. The particle retains its solid state until 100 s of irradiation, beyond which it
loses convexity and structural integrity. When an equivalent electron dose is applied to a
multi-particle system, similar structural disordering occurs following particle coalescence.
Particle fusion also occurs slowly in vacuum under similarly focused irradiation. On rigid
supports, particles must overcome the anchoring force towards the membrane to form
oriented attachments. In contrast, free-floating nanoparticles encounter lower resistance to
movement. This reduced resistance facilitates easier steric relocation, promoting attachment
and mass transport throughout the joined region.

3.3. Crystallographic Evolution of Nanoparticle During Charge-Induced Melt

Unlike radiolytic decomposition reactions, we found no chemical changes during
this structural deformation process. The particle’s redox state remains unaltered, and no
metastable reactants form. Consequently, studying the crystallographic evolution through
atomic movement during this charge-induced melting provides valuable insights into
structural changes during the solid-liquid phase transition. Several crystallinity changes,
including diffraction fringes and twin boundaries, were observed during the in situ melting
of Au nanoparticles. However, detailed atomic movements could not be rendered in
real-time due to the spatial resolution limitations of liquid-phase electron microscopy
Nanomaterials 2024, 14, x FOR PEER REVIEW 6 of 10
(LPEM). To overcome this constraint and acquire high-quality crystallographic information,
postmortem analysis of dissociated particles was conducted (See Figure 3).

Figure 3. The
Figure 3. The postmortem
postmortem crystallinity
crystallinity mapping
mapping of of the
the particle
particle revealed
revealed aa combination
combination of
of crystalline
crystalline
FCC
FCC Au andand amorphous
amorphousAu Auwithin
withina asingle
single particle.
particle. Regions
Regions 1, 2,1,and
2, and 5 show
5 show a well-ordered
a well-ordered face-
centered cubiccubic
face-centered (FCC) structure,
(FCC) while
structure, regions
while 3 and
regions 4 exhibit
3 and amorphous
4 exhibit amorphous phases.
phases.

Typical
Typical Au nanoparticlesconsist
Au nanoparticles consistofofmultiple
multiple crystallographic
crystallographic grains
grains with
with a face-
a face-cen-
centered cubic
tered cubic (FCC)
(FCC) structure.
structure. Initially,
Initially, these
these grains
grains appear
appear randomlyoriented,
randomly oriented,forming
forminga
quasi-spherical shape as shown in Figure 2. However, after electron beam irradiation, the
particle morphology begins to deform. The elongated particle develops internal voids and
locally amorphous regions during the liquid state. Selective inverse Fourier transform im-
aging (Figure 3) reveals a mixture of crystalline and amorphous regions throughout the
particle, with non-identifiable metastable lattice planes (d = 1.75 Å) distributed within the
Nanomaterials 2024, 14, 1709 6 of 9

a quasi-spherical shape as shown in Figure 2. However, after electron beam irradiation,

the particle morphology begins to deform. The elongated particle develops internal voids
and locally amorphous regions during the liquid state. Selective inverse Fourier transform
imaging (Figure 3) reveals a mixture of crystalline and amorphous regions throughout the
particle, with non-identifiable metastable lattice planes (d = 1.75 Å) distributed within the
amorphous region. As shown in Figure 3, two-dimensional FFT analysis on the selected
regions of interest in the TEM image reveals that the crystalline phase within a single melted
region tends to adopt a preferred orientation, even when separated by amorphous and void
regions. Here, we note that the permanent damage to the sample due to heating within the
irradiated volume is negligible, as the expected temperature of the gold nanoparticles is
far below their melting point. Furthermore, radiolysis is likely suppressed at the electron
beam dose rate employed in this experiment due to the nature of the solvent used and
the absence of significant reactive species. Therefore, we attribute the rich morphological
changes and phase transitions observed in this work primarily to the charging effect.
To further scrutinize our observations, we examined the changes in particle shape
as it is continuously exposed to electron beam irradiation. As shown in Figure 2a, Au
nanoparticles initially consist of polycrystalline FCC structures. Upon electron beam
irradiation, the particle perimeter becomes smoother and eventually exhibits signs of
deformation. The particle edges also show a loss of crystalline structure in localized areas.
We attribute this effect to the formation of highly defective gold layers near the surface.
The highly energized Au atoms near the surface with increased atomic mobility lead to
surface deformation until a new crystal equilibrium is found (See Figure 2a). This may
suggest partial surface melting of the particle, where surface atoms are considerably more
mobile than those in the interior. In contrast, in the higher fluence case (Figure 2b), surface
deformation continues to develop to likely an amorphous phase, which is accompanied by
a significant loss of material. Notably, the particle did not recover its original FCC structure
but retained a highly distorted shape. This observation implies that the particle has melted.
In some particles, a perfectly ordered single crystalline FCC structure is observed, even
in remote discrete areas within the same particle (regions 2 and 5 in Figure 3). This may
suggests that the formation of voids and locally amorphous regions occurs after at least one
crystalline arrangement during the liquefaction of the solid particle. In the melting process,
amorphization and crystallization could both be present, with each phase competing due to
local fluctuations and instabilities that are observed during the nucleation process [24,48].
To accurately capture and understand these intricate transient processes, high-speed, highly
sensitive detectors operating at sub-millisecond timescales are essential [49]. However, the
development and implementation of such advanced technology fall outside the scope of
this study.
Regarding the effect of nanoparticle size on charge-induced melting, it is established
that size plays a crucial role in determining the melting behavior of nanoparticles [50].
Smaller nanoparticles generally exhibit lower melting points than larger ones due to their
higher surface-to-volume ratios. This size effect results in more pronounced transformations
under the same conditions, with smaller particles melting or deforming at lower electron
doses or temperatures. In the case of charge-induced melting, the size of the nanoparticle
directly influences the extent of charge accumulation and the resulting morphological
changes. Due to their larger relative surface area, smaller particles tend to accumulate more
charge per unit volume, which can intensify the melting effect. As a result, smaller particles
may experience greater structural instability under comparable electron beam irradiation,
leading to faster deformation and melting.
Although we did not specifically investigate size-dependent melting in the current
study, it is reasonable to expect that nanoparticle size would significantly influence melting
behavior. Based on theoretical models and prior research, smaller nanoparticles are likely
to melt at lower thresholds compared to larger particles under similar charge conditions.
Conversely, larger nanoparticles may require higher electron doses or prolonged exposure
times to exhibit comparable melting dynamics. In our study, where we examined a 30-nm
Nanomaterials 2024, 14, 1709 7 of 9

diameter particle, we observed a distinct charge-induced melting phenomenon at a specific

threshold dose. We anticipate that future experiments exploring a range of particle sizes will
further clarify and validate the relationship between nanoparticle size and charge-induced
melting behavior.

4. Conclusions
We investigate the nanoscale dynamics of melting in metal nanoparticles by circum-
venting radiolysis challenges in liquid-phase electron microscopy. Using a radically in-
ert liquid (acetonitrile) and high-dose electron irradiation, we observed charge-induced
melting of gold nanoparticles without radiolytic interference. Our findings imply an
elaborate melting process characterized by electron beam fluence dependent transitions
between amorphous and crystalline phases, involving multiple stages. The observation
of preferred crystalline orientations within melted regions suggests that void and locally
amorphous area formation occurs after at least one crystalline arrangement during lique-
faction. These observations challenge conventional understanding of melting and provide
new perspectives on the structural evolution of materials during phase transitions. The
methodology demonstrated in this work opens new avenues for investigating other critical
phase transitions and may have implications for various fields, including materials science,
nanotechnology, and crystal growth studies.

Author Contributions: Conceptualization, J.-H.K. and S.L.; methodology, all authors; analysis, K.K.,
J.-H.K. and S.L.; writing—original draft preparation, K.K., J.-H.K. and S.L.; writing—review and
editing, K.K., J.H.S., J.L., S.L. and J.-H.K. All authors have read and agreed to the published version
of the manuscript.
Funding: This research was supported by characterization platform for advanced materials funded
by Korea Research Institute of Standards and Science (KRISS-2024-GP2024-0014).
Data Availability Statement: The data presented in this study are available on request from the
corresponding author.
Acknowledgments: The authors would like to express their gratitude to Joon Ha Chang from
Research Institute of Industrial Science and Technology (RIST), and Jinwoo Park from University of
Seoul for their valuable discussions on the charge measurement setup in liquid environments and for
contributing to the preliminary work on charge dissociation simulations.
Conflicts of Interest: The authors declare no conflict of interest.

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