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of 2D layered materials are listed. From the chronical ten-
dency, it can be seen that 2D layered materials are a fasci-
nating field with novel and unusual properties in forms of
tremendous structural information. Number of publication
on TEM studies of 2D layered materials beyond graphene
is much less than that of the 2D materials. However, TEM
is indispensable in the development of 2D material science.
The physical properties of 2D layered materials are closely
related to their structures and chemical components. For
example, the thickness, structural distortions and doping may
lead to dramatic changes in the band gap.
[58–61]
In addition,
defects can significantly modulate the electrical, optical, mag-
netic, and chemical properties of 2D layered materials and
their devices.
[62–66]
As it stands, nearly all types of 2D layered
materials can be caricatured by TEM down to atomic levels,
such as MoS
2
and BN. Based on the idea of “setting up a lab
inside TEM”, it is indispensable that the dynamic structure
evolution of 2D layered materials can also be characterized
and manipulated at real-time under multifunctional fields.
2. Ex Situ TEM Characterization of 2D
Layered Materials
This section describes the static characterization of 2D lay-
ered materials, such as dopants, vacancies, grain boundaries
and heterostructures that affect the physical and chemical
properties of the materials. To take advantage of certain
properties of defects and minimize their detrimental effects
on targeted applications, characterizing defects on the atomic
scale by TEM is an effective way to study their formation and
evolution mechanisms.
2.1. Dopants
The Z-contrast annular dark-field (ADF) mode of STEM
can give the structure and chemical compositions of a sample
with atomic resolution, providing a clear observation of the
dopants and adatoms and their interactions with the host 2D
crystal lattices. The species, position and number of foreign
atoms after doping can be characterized clearly by STEM–
ADF, this information can be used to differentiate substitu-
tional dopants and adatoms. The substitutional dopants do
not change position during the experiment, while adatoms
change over time. Lin et al. study the atomic structures and
evolution of monolayer MoS
2
doped with Re and Au, as
shown in Figure 4.
[75]
The experiment is performed in an aber-
ration-corrected TEM at 60 kV to minimize the damage to
MoS
2
sample, while still provides the whole defects transition
process of the alien atoms’ migration at atomic resolution,
which cannot be achieved by other testing characterization
methods. It is found that Re atom prefers to be substitutional
dopant while Au atom prefers to be adatoms type. Gong et al.
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small 2017, 13, 1604259
Figure 2. The chronicle of TEM: the first TEM was built by Ernst Ruska and Max Knoll in 1931; the spherical aberration corrector was developed
with sub-angstrom resolution in 2000; the evolution trends of dynamic observation of nanomaterials by in situ TEM, including thermal, electrical,
mechanical, liquid/gas environmental, optical excitation, and magnetic fields. The tendency of spatial resolution is shown on the left side, time
and energy resolutions are shown on the right side, respectively. Reproduced with permission.
[48]
Copyright 2017, Royal Society of Chemistry.
Reproduced with permission.
[49]
Copyright 2016, Cambridge University Press. The TEM machine is Titan G2 60-300.