ChemPhysMater 3 (2024) 341–356

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ChemPhysMater
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Review Article

Anisotropic etching of 2D layered materials

Yuge Zhang a,b , Qian Liu a,c , Deliang Zhang a , Yue Hong a , Qiang Li a,∗
a
Key Laboratory of Colloid and Interface Chemistry of the Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100,
China
b
Interdisciplinary Nanoscience Center (iNANO), Aarhus University, Aarhus C DK-8000, Denmark
c
Department of Biomedicine, Aarhus University, Aarhus C DK-8000, Denmark

a r t i c l e i n f o a b s t r a c t

Keywords: Two-dimensional (2D) layered materials with unique physicochemical properties, such as graphene, transition
2D materials metal dichalcogenides, and hexagonal boron nitride, have shown considerable potential in the electrical and
Anisotropic etching electronics industries as well as society. To realize the practical applications of 2D materials, the size, shape,
Nanostructures
and edge structures must be refined. Etching is a critical processing step in the semiconducting industry and its
Graphene
potential as an efficient approach for fabricating diverse nanostructures of 2D materials has been demonstrated,
MoS2
broadening their applications in the field of nanoelectronics. In this paper, we present an overview of recent
advances in anisotropic etching of various 2D materials. Anisotropic etching and the associated mechanisms
are discussed in context of the synthesis, processing, and characterization of 2D materials. An overview of the
applications of anisotropic etched 2D materials is provided. Finally, the challenges and future opportunities for
anisotropic etching of 2D materials are discussed.

1. Introduction devices. Herein, we review the recent progress in anisotropic etching of

2D materials research. The various etching methods, including metal-
Since the successful preparation of graphene in 2004 [1-5], two- nanoparticle catalytic etching, post-growth etching, thermal annealing
dimensional (2D) layered materials such as graphene, molybdenum etching, and plasma etching along with their associated mechanisms are
disulfide (MoS2 ), and hexagonal boron nitride (h-BN) have attracted discussed. The potential applications of anisotropic etching of 2D mate-
enormous research interest. These materials’ unique 2D structure and rials are then demonstrated. Finally, the challenges and future prospects
electrical/optical properties make them ideal channel materials for fu- of anisotropic etching of 2D materials are discussed. We expect that this
ture electronic and optoelectronic applications [6,7]. Both experimental review will provide new insights into 2D material etching and promote
and theoretical studies have shown that the edge structure, shape, and the practical usage of 2D materials as channel materials for future elec-
size of 2D materials have a significant impact on their electrical prop- tronic and optoelectronic applications.
erties [8-25]. Therefore, precise definition of the nanostructures of 2D
materials is critical for progress in the field. To achieve this control, nu- 2. Anisotropic etching methods of 2D materials
merous strategies for fabricating 2D material nanostructures with well-
defined edges have been developed, such as direct synthesis (comprising 2.1. Transition-metal (TM) -nanoparticle-catalyzed etching
organic synthesis [26] and chemical vapor deposition (CVD) [27-29])
and indirect fabrication via anisotropic etching [30-36]. Among these 2D materials can be etched anisotropically along crystallographic
potential strategies, controllable anisotropic etching, in which the 2D axes by utilizing transition metal (TM) nanoparticles (such as Fe, Ni,
material is selectively removed by etching at different rates along dif- Co, Pt, and Ag) as catalysts in an H2 atmosphere and at a high temper-
ferent crystallographic axes, is an effective method for removing atoms ature [30,31,45-53]. TM nanoparticles can catalyze the hydrogenation
and precisely defining the edge termination of 2D materials to modulate reaction; specifically, they can promote the dissociation of H2 molecules
their electrical properties [37-44]. into H radicals, weaken the nearby C–C bonds in graphene, and pro-
Etching has been successfully employed in the past decade to fabri- mote the formation of C–H bonds on the TM nanoparticle surface. Fe,
cate various nanostructures of 2D materials, effectively broadening the Co, Ni nanoparticles often achieve good control over catalytic etching of
potential applications of these materials in electronic and optoelectronic graphene, occurring along the zigzag (ZZ) or armchair (AC) directions

∗
Corresponding author.
E-mail address: [email protected] (Q. Li).

https://doi.org/10.1016/j.chphma.2024.07.001
Received 14 April 2024; Received in revised form 13 June 2024; Accepted 1 July 2024
Available online 18 July 2024
2772-5715/© 2024 The Authors. Publishing Services by Elsevier B.V. on behalf of KeAi Communications Co. Ltd. This is an open access article under the CC
BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/)
Y. Zhang, Q. Liu, D. Zhang et al. ChemPhysMater 3 (2024) 341–356

Fig. 1. Metal-nanoparticle catalytic etching of graphene. (a) Scanning electron microscopy (SEM) image (upper) and atomic force microscopy (AFM) image (lower)
showing etched nanotrenches along the ZZ and AC orientation of graphene catalyzed by a single Fe nanoparticle. [45] Copyright 2008, American Chemical Society.
(b) Schematic (left) and AFM images (right) showing Ni nanoparticle-etched trenches with turns of 60° or 120°, leading to the formation of crystallographically
oriented GNRs. [49] Copyright 2009, American Chemical Society. (c) SEM image showing a triangular graphene piece formed along the ZZ orientation of graphene.
[30] Copyright 2009, Wiley-VCH. (d) SEM image showing highly aligned GNRs parallel to the [11̄ 01̄ ] direction of the sapphire substrate. [31] Copyright 2013,
Wiley-VCH. (e) SEM image showing open channels (blue arrows), closed channels (red arrows), and subsurface catalyst particles (green arrow). [54] Copyright 2013,
Macmillan Publishers Limited. (f) Illustration showing TM nanoparticle catalytic etching along the ZZ (left) and AC (right) edge channels of graphene and the corre-
sponding metal-graphene interfaces. (g) Formation energy of different metal-graphene interfaces as a function of graphene edge orientation. (h) Illustration showing
nanoparticle-terminated ZZ/AC edge interfaces in various graphene channels and the formation energy of metal-graphene versus the etched channel orientation.
[50] Copyright 2014, American Chemical Society.

of the graphene lattice, with etching direction changes typically having terms of catalytic activity, stability, and cost, allowing researchers to
turns of 60° or 120° (Figs. 1(a)(b)) [45,49]. Through TM-nanoparticle- tailor the etching process to suit specific applications and requirements.
catalyzed etching, graphene nanostructures with specific well defined It is worth noting that the etching rate (defined as the number of
shapes were fabricated, including equilateral triangles (Fig. 1(c)) [30] etched atoms per unit time) can be influenced by the size of metal
and highly aligned graphene nanoribbons (GNRs) (Fig. 1(d)) [31]. Be- nanoparticles [46,47,49]. The overall cutting rate was experimentally
sides surface trenches, subsurface tunnels could be formed in multi- determined to be proportional to the square of the nanoparticle radius
layer graphene during etching (Fig. 1(e)) [54]. To understand why TM (R2 ) [58,59]. The underlying mechanism was accurately described us-
nanoparticles tend to cut graphene along the direction of either ZZ or AC ing a combination of kinetic Monte Carlo (KMC) simulations and DFT
edges, the Metal-Graphene interfaces were constructed via density func- calculations [56]. The etching rate was limited by the ZZ-site etching
tional theory (DFT) (Fig. 1(f)) [55]. In addition, calculations of the inter- and ZZ-site atoms were more accessible at the larger metal-graphene in-
facial formation energy of graphene edges attached to particle surfaces terface, resulting in a shorter delay before ZZ-site etching was triggered,
(Fig. 1(g)) revealed that the Metal-ZZ and Metal-AC interfaces were the increasing the etching rate. By simply selecting metal nanoparticles of
two local minima, suggesting that the surface of metal particles prefer- an appropriate size, the etching rate during graphene cutting can be
entially bind to the ZZ or AC edges. Furthermore, as shown in Fig. 1(h), controlled.
a comparison of the formation energies of the Metal-Graphene interface
in cutting channels with different orientations showed that the forma- 2.2. Post-growth etching
tion energies of Metal-ZZ and Metal-AC were the lowest, causing the
graphene to cut along the ZZ or AC direction. Moreover, the energy bar- Post-growth etching is a process used in materials science and semi-
rier of ZZ-edge bond breaking (1.45 eV) was much higher than that of conductor fabrication where a material, typically a thin film or nanos-
AC-edge bond breaking (0.50 eV) [56]. Therefore, it was significantly tructure, is selectively removed after the initial growth or deposition
easier to remove a carbon atom from AC edge sites, which explains why phase. A critical step in many fabrication processes, this technique is em-
trenches parallel to the ZZ orientation usually occurred in graphene after ployed to refine the structure, improve the quality, or modify the prop-
metal-nanoparticle catalytic etching. A similar theoretical analysis was erties of as-grown materials. By carefully selecting the etching method
applied to better understand the catalytic etching of h-BN [57]. Among and conditions, researchers and engineers can achieve the desired struc-
the mentioned metal particles, each type offers distinct advantages in tural and functional properties in their materials and devices.

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Fig. 2. Post-growth etching of monolayer single-crystal graphene. (a)–(f) SEM images showing the morphology and edge evolution of graphene domains on a Pt
substrate during the etching process. (g) Illustration showing the graphene etching process obtained by 2D KWC analyses, corresponding to (a)–(f). (h) Schematic
showing the 2D KWC during graphene growth and etching. (i) Schematic showing the slanted edges that can be viewed as AC (top) and ZZ (middle) edges with
kinks, and 19.1° slanted edges (bottom) from the ZZ direction with the highest concentration of kinks. [33] Copyright 2013, National Academy of Sciences. (j)–(m)
SEM images showing the morphology and edge evolution of etched graphene domains on a Cu substrate at different time points. [39] Copyright 2017, American
Chemical Society.

2.2.1. Etching of monolayer 2D materials Te), have richer edge structures and sophisticated growth processes. As
Etching of 2D materials is a reversible growth process that can oc- a result, they have attracted more attention with respect to the edge
cur when the precursor is insufficient during CVD growth or by intro- evolution and mechanisms of the growth-etching process [39,68-73].
ducing an etchant (e.g., H2 or O2 ) after CVD growth [33,37-40,60-62]. The symmetry and crystal lattice of the above 2D crystals differ from
For example, when CVD monolayer graphene as-grown on Cu foil was graphene, which lead to differential morphological evolution and edge
exposed to hydrogen flow at high temperatures, continuous graphene termination of the crystals or inner holes during the etching process.
could be etched into hexagonal openings [60]. Monolayer graphene Triangular h-BN crystals grown on Cu foil could be etched using
domains grown on a Pt substrate with controlled edges ranging from H2 /Ar mixed gas, resulting in the formation of triangular holes in the
zigzag to armchair orientations were achieved through growth-etching- center of the crystal due to the highly anisotropic etching [39,69]. As
regrowth in a CVD process (Figs. 2(a)–(g)) [33]. The rates of growth shown in Fig. 3(a), the etched triangular hole was parallel to the triangu-
and etching of a monolayer graphene domain increased linearly with lar h-BN crystals. The edges of the triangular holes were parallel to the
the slanted angle of its edges ranging from 0° to 19°. In addition, the boron-terminated ZZ (B-ZZ) edges, opposite to the nitrogen-terminated
growth/etching rates for armchair edges were much faster than those for zigzag (N-ZZ) edges of the h-BN crystals (Fig. 3(d)) [39]. When the
zigzag edges. Based on the concentrations of kinks on different edges, buffer gas was N2 instead of Ar, the etched holes first changed from
the edge-structure-dependent graphene growth/etching kinetics were triangular with B-ZZ edges to truncated triangular/hexagonal with both
explained, enabling the evolution and control of the edge and mor- B-ZZ and N-ZZ edges (Figs. 3(b)(e)), and then to fully inversed triangu-
phology in monolayer graphene in accordance with the classical kinetic lar with N-ZZ edges (Figs. 3(c)(f)). This phenomenon could be explained
Wulff construction (KWC) theory (Figs. 2(h)–(i)) [63,64]. Besides the by the KWC model (Fig. 3(g)), where the slowest etching edges defined
outer edge structure, hexagonal holes with ZZ edges could be formed in the enlargement of a triangular hole in the center of the crystal, while
the center of the graphene domain, and the ZZ edge structure remained the fastest etching edge defined the circumference.
unaltered during the etching process (Figs. 2(d)–(f)). The formation of The triangular GaSe island, like h-BN, also possesses two types of ZZ
the inner hole was most likely caused by the structural defects produced edges: Se-terminated edges (Se-ZZ) and Ga-terminated edges (Ga-ZZ),
during the graphene nucleation [65,66]. The evolution of the hole was forming under Se-rich or Ga-rich growth conditions, respectively. As
identical to the growth process, as explained by the KWC theory, with ZZ shown in Fig. 3(h), most etched triangular holes anti-parallel to the is-
edges forming at the slowest propagation rates. Similarly, the shape evo- land edges were formed at the center of the triangular GaSe island due to
lution of both the outer edge structure and inner hole during the etch- the cutting off of the Ar carrier gas flow during the GaSe growth process
ing of monolayer graphene on a Cu substrate was observed (Figs. 2(j)– [72]. The morphological evolution of the etched holes on monolayer
(m)) [39]. The etching features discussed above were also verified by a GaSe during the etching process was likewise dependent on the edge
KMC simulation [67]. Obviously, the unique edge structure-dependent structure and also followed the KWC theory. The edges that were tilted
growth/etching behavior provided critical guidance for controlling the and had a tilt angle 𝜃 of approximately 19.1° relative to ZZ edges, de-
morphology of single-crystal graphene domains with specific edges, fined as the 19° Se-ZZ and 19° Ga-ZZ edges (Fig. 3(i)), had the largest
through simply changing the experiment parameters such as reactant kink density and the maximum local etching rate. Ideally, 19° Se-ZZ or
flow rate or reaction time. Ga-ZZ edges should initially originate at the vertices of the as-grown
Other 2D crystals with binary compositions, such as h-BN, transition triangular GaSe flakes during the etching from the outside edges; this
metal dichalcogenides (i.e., TMX2 , TM = Mo, W; X = S, Se, and Te), was followed by a rapid shortening that changed the triangular exterior
and metal monochalcogenides (i.e., MX, M = Ga, In; X = S, Se, and contour into a dodecagon with only 19° edges (Fig. 3(j)). However, most

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Fig. 3. Post-growth etching of (a)–(g) h-BN and (h)–(k) GaSe. (a)–(c) SEM images and (d)–(f) corresponding schematics showing the edge structure of crystal and
holes. (g) Schematic of evolution for etching process, showing the different termination of the circumference and the hole due to the difference in etching rate of
edges. [39] Copyright 2017, American Chemical Society. (h) SEM image showing the etched hole of GaSe monolayers and outside ∼9° tilted edges with respect to
the ZZ edges. (i) Schematic showing ∼19° tilted edges with respect to ZZ edges. (j) Theoretical etching process showing the shape evolution of the outer edges and
etched holes. (k) SEM images showing a GaSe bilayer in the initial etching stage, the zoomed-in area of the region marked by a red dashed square. [72] Copyright
2017, American Chemical Society.

of the GaSe flakes retained the similar pre-etched contour, while some ual graphene flakes exhibiting a hexagonal shape. Fractal patterns were
were etched into a polygon with approximately 9° tilted edges in rela- formed during h-BN etching at low and ambient pressure (Fig. 4(g)),
tion to the ZZ edges (Fig. 3(h)). The interaction between GaSe and the demonstrating that the diffusion-controlled mode may be applied to h-
substrate was proposed to be the source of the inconsistency between BN as well [70]. The effect of 𝑃H2 on graphene growth and etching was
the simulation and experiment. As shown in Fig. 3(k), during the ini- further explored by modulating the CH4 /H2 flow ratio during graphene
tial stages of etching the second triangular GaSe layer, approximately growth on a Cu surface via low-pressure CVD [38]. The CVD process
18° tilted edges, with respect to ZZ edges, were formed. This aligned was divided into two parts because hydrogen acted as both a growth ac-
well with the theoretical analysis and further confirmed the substrate’s tivator and an etchant. As 𝑃H2 gradually increased to the critical point,
significant influence on the etching process. the growth contribution to graphene morphology rose and then leveled
The partial pressure of the etchants during the etching process is off, while etching had the opposite impact on growth (Fig. 4(h)). When
crucial to the morphological evolution of etched patterns. In addition the amount of H2 was below the critical point, etching regulated the
to the regular geometric shapes, fractal patterns can be generated by growth of graphene. To verify that 𝑃H2 dominated the competitive ki-
varying this parameter. As shown in Figs. 4(a)–(d), fractal etching on netics between graphene growth and etching, a phase-field model was
a graphene monolayer grown on a liquid Cu surface was achieved by developed. Figs. 4(i)(j) illustrate this process, which led to the variations
varying the ratio of Ar/H2 flow rate after interrupting the methane flow in etched patterns depending on growth-etching balance [38].
[37]. The resulting pattern changed from a simple hexagon to a sixfold
symmetric fractal shape as the partial pressure of H2 (𝑃H2 ) decreased. 2.2.2. Etching of multilayer 2D materials
The evolution of etched graphene patterns followed the same diffusion- Stacking of layers significant effects the etching process of 2D mate-
controlled mechanism as the growth of dendritic graphene flakes. The rials with multiple layers, differing from the etching behaviors of single
etching pathway was determined by the competition between the rate layer 2D materials. This section will discuss etching behaviors on mul-
of etching and the rate of etchant diffusion to the etched area to identify tilayer 2D materials and the underlying mechanism.
the most energetically favorable sites along the perimeter of the etched Few-layer graphene growth and etching on Pt substrates were also
holes. The formation of branching structures occurred when the rapid experimentally investigated [74]; as shown in Figs. 5(a)(b), the growth
diffusion of the etchant hindered the most energetically favorable re- rates of the ZZ edges of graphene displayed apparent anisotropy, with
moval of carbon atoms. It should be noted that the diffusion of active the lowest growth rates along the up-step and down-step directions. The
etchants on an isotropic liquid Cu surface was necessary for effective growth rates could be classified into six values based on the orientation
fractal etching with high symmetry. This fractal etching mode was the and the density of steps on the Pt surface. In addition, the difference in
first to produce the complicated etched graphene patterns and also pro- growth rates between the up-step and down-step directions was largest
vided new evidence for the diffusion-controlled etching mode. Large- in the first layer than in the second and third layers, indicating that
area aligned graphene arrays were created afterwards by using a simi- the substrate had a major impact on few-layer graphene growth, most
lar method [40]. As seen in Figs. 4(e)(f), graphene arrays formed with significantly on the bottom layer. In order to gain a better understand-
a decrease in H2 flow rate and increase in etched time, with all resid- ing of how the interaction between the graphene and substrate affects

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Fig. 4. Fractal etching obtained by varying the partial pressure of the etchants. (a)–(d) SEM images showing etched patterns under varied Ar/H2 flow ratio. [37]
Copyright 2013, American Chemical Society. (e)(f) Schematic and SEM images showing the large scale of graphene arrays. [40] Copyright 2015, Wiley-VCH. (g)
SEM image showing etched h-BN with fractal shapes. [70] Copyright 2015, Wiley-VCH. (h) Schematic showing the etching and growth process as a function of 𝑃H2 .
(i) Schematic showing a compact island (blue) evolving into a six-lobed shape (yellow) during etching-controlled growth process. (j) Schematic showing morphology
of CVD-grown graphene formed during the etching-controlled growth. [38] Copyright 2017, American Chemical Society.

the etching behavior, the etching process was simulated by reversing points were covered by the adlayers formed on the bottom h-BN mono-
the growth rates. The simulation results showed that the shape evolu- layer. As shown in Figs. 6(a)–(c), during the etching process, triangular
tion was determined by the fastest etching edges (approximately 19.1° holes parallel to the edges of adlayers occurred on the h-BN monolayer,
tilted edges defined by maximum density of kinks), as indicated by the while the size of adlayers was barely changed until the bottom layer
blue arrows in Fig. 5(c). The simulated Wulff construction (Fig. 5(d)) completely disappeared [39]. This unique etching behavior indicated
was in good agreement with the experimentally observed shape evo- that tight contact with the substrate was necessary for a high etching
lution (Fig. 5(e)). The island was elongated in the direction along the rate.
Pt terraces even though the etching at the perimeter of each individ- The impact of stacking sequence on etching behaviors of multilayer
ual layer occurred simultaneously; this was because the etching rate in WSe2 has also been explored [73]. Intricate WSe2 kirigami structures
the direction perpendicular to the Pt steps was much lower than that could be formed through in situ etching of multilayer WSe2 in a Se-poor
along the terrace for the first layer in direct contact with substrate. For environment after CVD growth. Three typical WSe2 kirigami structures
the second and third layer, the anisotropic etching was less noticeable with specific features (curved concave edges, panhandles, and sawtooth
[74]. Further DFT calculations revealed that the etching rate for the first corners) are depicted in Fig. 6(d). Through the combination of second-
graphene layer followed the following trend: up-step direction < down- harmonic generation imaging (Figs. 6(e)–(h)) and Raman spectroscopy
step direction < substrate terrace. The calculations were in good agree- analysis, it was found that all WSe2 kirigami structures shared the same
ment with the experimental observation, clarifying that the substrate’s bottom trilayer structure with AAB stacking. Based on the snapshots of
impact on etching rate originated from the strong interaction between WSe2 kirigami structures at different etching stages, the etching and
the substrate and graphene edge atoms. The substrate impact was weak- evolution process of complex WSe2 kirigami was proposed. As illus-
ened in the second and third graphene layers because the graphene ZZ trated in Figs. 6(i)(j), etching started from the three vertexes of the
edges were not in direct contact with the substrate. topmost monolayer to form a concave edge, followed by etched holes
The previously discussed nucleation point for the monolayer h-BN appearing in the middle monolayer. As the etching continued, the holes
growth was located at the crystal center, which was also a defect where evolved into the shape of an arrow, with etching occurring from the
the etching process could initiate as well. However, these nucleation middle monolayer’s vertex and expanding to connect to the arrow’s tail

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Fig. 5. Post-growth etching of multilayer graphene. (a) SEM images showing the as-grown few-layer graphene on Pt substrate. The outlines of the flakes indicate the
ZZ edges. (b) Time-lapse SEM images showing the etching of monolayer graphene and the topmost layer in bilayer grahene and trilayer graphene The green arrows
indicate the up-step and down-step directions of Pt terraces. (c) Simulated polar plots obtained using the experimental etching rates. The fastest directions, indicated
by blue arrows, determine the shape evolution. (d) Simulated KWC of the etching process. (e) Experimentally observed shape evolution of the first, second, and third
graphene layers during etching. [74] Copyright 2016, Springer Nature.

as the panhandles formed. The sawtooth corners eventually formed in explored. As shown in Fig. 7(g), triangular holes on GBs were formed in
the bottom trilayer. Phase-field simulations of the etching process pro- h-BN crystals after etching [69]. A similar phenomenon was observed for
vided additional support for the above-mentioned hypothesized etching the etching of a monolayer GaSe domain formed by merging two single-
mechanisms [73]. crystal monolayers [72]. Separated small holes formed on the GB at the
initial etching stage (Fig. 7(h)), and then propagated into each crystal
2.2.3. Etching of polycrystalline 2D materials to form a trench along the GB. It is worth noting that the etched pattern
2D polycrystals often have line defects that form during the growth on each crystal from the boundary also were triangular (Fig. 7(i)). The
process where etching usually occurs, such as grain boundaries (GBs) geometry of the etched holes was governed by the orientation of the
[28,75-77]. The etching behavior of polygonal graphene flakes grown two merged GaSe crystals. Though the underlying etching mechanism
on a Cu substrate using CVD was investigated [61]. As shown in of 2D polycrystals is not well understood, investigations into the etching
Figs. 7(a)–(c), there were two types of etched patterns: 1) hexagonal behaviors and characteristics of 2D polycrystals have contributed signif-
holes with all interior angles equal to 120° and varied orientations cor- icantly to the understanding of the growth mechanism of 2D materials.
responding to different grains; 2) polygonal holes with some non-120°
interior angles at the center of a graphene flake that crossed a part of a 2.3. Thermal-annealing etching
continuous grain boundary. As the holes were terminated by ZZ edges,
the misalignment angles of GBs could be determined by measuring the Thermal annealing is a relatively simple and fast etching method
non-120° interior angles. Aligned symmetric holes with non-120° inte- used to create nanostructures with precisely controlled edges, such as
rior angles were also observed on graphene polycrystals grown on the GNRs [80], trenches [81,82], and holes [82-90], in an environment that
liquid Cu surface (Figs. 7(d)–(f)), confirming the presence of twinned usually contains oxygen. In this etching process, etching parameters
GBs [78]. The geometry of the polygons represented the second nucle- such as oxidation temperature, annealing duration, and oxygen concen-
ation site relative to the first island. Recently, well-defined twinned GBs tration are crucial for effectively controlling the etching of 2D materials.
in graphene were successfully prepared, and the twinned GBs could be For instance, heating highly oriented pyrolytic graphite (HOPG) sam-
selectively etched by hydrogen gas, because hydrogen preferentially ad- ples up to approximately 600 °C in an oxygen-containing environment
sorbs at high-energy twins [79]. resulted in an etched HOPG surface with hexagonal holes and trenches
Compared to the etching of graphene polycrystals, the etching of h- [82]. As shown in Fig. 8(a), there were three groups of hexagonal holes
BN polycrystals with specific shape and orientation has been thoroughly with AC edges that corresponded to different graphite crystallites. The

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Fig. 6. Post-growth etching of multilayer h-BN and WSe2 . (a) Illustration showing the etching process of h-BN monolayers with multiple adlayers and (b)(c) SEM
images of h-BN crystal after etching. [39] Copyright 2017, American Chemical Society. (d) Illustration showing the etching process of multilayer WSe2 and (e)–(h)
second-harmonic generation images of WSe2 crystal after etching. (i) SEM image showing a WSe2 kirigami structure consisting of an upper monolayer with concave
edges, a middle monolayer with panhandles, and a bottom trilayer. (j) Schematic showing the evolution process of complex WSe2 kirigami with panhandles and
sawtooth corners. [73] Copyright 2018, American Chemical Society.

hexagonal holes most likely originated from the native defects arising Fig. 8(c). Unlike graphene, there are two types of MoS2 ZZ edges: Mo-ZZ
from dangling bonds at the sites [91] where oxidation reactions were and S-ZZ. According to the KWC theory [63,95], the edge structure of
more favorable than at the graphene sites with more stable in-plane C– the formed pits was determined by the slow-etching edges. To elucidate
C covalent bonds [92]. In addition, the etched trenches that originated the difference in the etching rate between the two types of ZZ edges,
from the GBs exhibited varying etching degrees. This difference was first-principles calculations were also performed. Based on the edge en-
most likely due to the different crystallographic structure of GBs, with ergy variations of etching Mo-ZZ and S-ZZ edges, the presence of the
disordered GBs and regular GBs undergoing strong and mild oxidation, plateau implied that ZZ-S edges had slower propagation rates, resulting
respectively. Ab initio and DFT calculations were also used to investi- in the formation of S-ZZ edges in the etched pits. For the CVD-grown
gate the mechanism of etching graphene in an oxygen-containing envi- monolayer MoS2 , a special positional relationship was discovered in the
ronment [93,94]. Based on the oxidation reaction of graphene, there are boundary structure between triangular pits and the triangular MoS2 do-
two binding types between O and C atoms, which result in the forma- main [85]. As shown in Figs. 8(d)–(g), the etched pits on a MoS2 domain
tion of carbonyl groups (in plane, IP) and epoxy groups (out of plane, with S-ZZ boundary were in the same direction as the MoS2 domain
OP). If enough energy is provided by heating, the C–C bonds can be (A-A etching), whereas the etched pits on a MoS2 domain with Mo-ZZ
broken, causing the IP O to remove C and leave the graphene surface boundary were in the opposite direction (A-B etching). In addition, a
as CO molecules. The remaining epoxy groups then transform into new difference in the etching behaviors of the outer boundary structure of
carbonyl groups and new OP bonds form due to an abundance of O MoS2 domain was found. For the A-A etching, the boundary structure
atoms. By repeating the above process, new IP carbon-oxygen bonds will can be clearly etched and eventually converted into Mo-ZZ in a saw-
be formed, resulting in the gradual removal of CO molecules from the tooth shape due to the poor stability of the S-ZZ boundary. For the A-B
surface. Consequently, etched graphene with AC edges will be formed. etching, the boundary structure can remain intact because of the outer
Notably, in the absence of the substrate effect during HOPG etching, boundary’s stable Mo-ZZ structure.
graphene defects with ZZ or AC edges will eventually evolve into stable During the thermal-annealing etching of 2D-TMDs, the gas atmo-
AC-terminated edges [81]. sphere is crucial for determining the termination of the holes. A novel
Thermal annealing can also be used to etch 2D transition metal method for controlling the etching of 2D-TMDs by manipulating the ter-
dichalcogenides (2D-TMDs), including exfoliated and CVD-grown MoS2 . minal atoms and shapes of the etched holes by adjusting gas atmosphere
During the etching process, only triangular pits with uniform size and has been developed [96]. In addition, the underlying mechanism was
orientation were observed on layered MoS2 sheets (Fig. 8(b)) [83]. The explored using DFT calculations; the terminal atoms of the holes were
formation of the pit nanostructures was caused by the anisotropic oxi- determined by the formation energies of different edges and the activi-
dation of MoS2 edges, which produced MoO3 and SO2 , as illustrated in ties of metal and chalcogen atoms under different atmospheres. First, in

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Fig. 7. Post-growth etching of polycrystalline 2D materials. (a)–(c) SEM images showing etched patterns of polycrystalline graphene flakes. The red and blue
hexagons represent the orientation of different grains in a polycrystalline graphene flake, and the dashed line indicates the GBs. [61] Copyright 2015, American
Chemical Society. (d)–(f) SEM images of etched polycrystalline graphene islands. [78] Copyright 2019, Wiley-VCH. (g) Optical microscopy image of etched h-BN
crystals with interconnected triangular holes on the GBs. [69] Copyright 2015, Springer Nature. (h) SEM image showing etched holes formed at the GBs propagating
into each GaSe crystal. (i) SEM image showing etched triangular holes formed at the boundaries of two merged triangular GaSe monolayers. [72] Copyright 2017,
American Chemical Society.

Ar/H2 atmosphere, W atoms have a stronger interaction with H2 com- applied to the MoS2 and WSe2 , opening up new avenues for material
pared to S atoms, which results in a lower formation energy for the research and device fabrication.
W-ZZ edge compared to the S-ZZ edge. Consequently, the etched holes Since water can react with C atoms at high temperatures, it is also
terminate with the W-ZZ edge, forming forward triangular etched holes. an effective etchant for graphene [97-99]. As shown in Figs. 9(a)–(c),
Second, in a pure Ar atmosphere, Ar atoms do not interact significantly hexagonal graphene domains with smooth AC edges were created by
with the edge sites of W or S atoms. The formation energy of the W-ZZ introducing water vapor through Ar flow at temperatures between 850
and S-ZZ edges is close, leading to the formation of hexagonal etched and 1000 °C [100]. Graphene nanoribbon structures with AC edges
holes with alternating W-ZZ and S-ZZ edges. Third, in an Ar/S vapor at- could be also created by controlling the etching conditions (Fig. 9(d)).
mosphere, S vapor inhibits the desorption of S atoms, which results in a The mechanism behind the formation of AC-terminated edges was then
higher formation energy for the W-ZZ edge compared to the S-ZZ edge. explored by first-principles calculations. It was found that epoxy groups
Therefore, the etched holes terminate with the S-ZZ edge, forming re- would eventually survive the water vapor etching process at high tem-
verse triangular etched holes. This controlled etching process was also peratures, with most groups formed during the graphene oxidation be-

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Fig. 8. Controlled etching of graphite and MoS2 by thermal annealing in oxygen-containing environment. (a) AFM image showing two types of etched patterns on
the HOPG surface: wide trenches and hexagonal holes. Inset represents the orientation angles between three HOPG grains. [82] Copyright 2013, Elsevier Ltd. (b) AFM
image showing triangular pits with the same orientation formed on monolayer MoS2 . (c) Atomic mechanism of the formation of etched triangular pits on the MoS2
surface. The middle of the right panel shows the edge energy variations during oxidation, where the energy of the oxygen-intact edge is set at zero. [83] Copyright
2013, Springe. (d)(f) AFM height images and (e)(g) corresponding atomic model showing triangular MoS2 domain with ZZ-S and ZZ-Mo boundaries, respectively.
[85] Copyright 2020, Elsevier Ltd.

Fig. 9. Controlled etching of graphite and MoS2 by water vapor. (a) AFM image and (b) atomic resolution image of etched graphene. (c) Schematic showing AC-
terminated edge structure of the formed hexagonal pits. (d) SEM image showing as-prepared GNRs marked with white arrows. [100] Copyright 2014, Wiley-VCH.
(e) AFM image showing etched 2D triangular pits on MoS2 with different layers. (f) Schematic showing two types of triangular pits located on the adjacent MoS2
layers. (g) AFM image showing etched 3D hexagonal cavity on MoS2 . (h) Schematic showing the edge orientation of bilayer MoS2 for hexagonal pits formation. [42]
Copyright 2018, Elsevier Ltd.

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ing removed [101-103]. According to first-principles calculations of those with Mo atoms. However, the role of the transition metal atoms
binding energy between epoxy oxygen atoms and ZZ or AC GNR, AC- in SF6 plasma etching has to be further investigated.
terminated edges were more likely to form because oxygen and AC GNR There were two types of etched structures in multilayer TMDs:
have a lower binding energy. hexagonal ZZ-terminated holes and inner perimeters (Figs. 11(a)–(d),
Through elevating the temperature, MoS2 could be controllably (f)) and AC-terminated dots and outer perimeters (Fig. 11(f)), in agree-
etched by water vapor to create 1D nano-channels, 2D in-plane triangu- ment with Wulff constructions illustrated in Fig. 11(g). Considering the
lar pits (Fig. 9(e)), and 3D vertical hexagonal cavities (Fig. 9(g)) on its energy-favorable AA’ stacking sequence and DFT simulations [108-110],
basal planes [42]. Monolayer triangular pits could be formed at an etch- ZZ edges terminated with chalcogen atoms were the most stable (the
ing temperature of 600 °C. Due to the AB stacking of MoS2 , as illustrated slowest etching edges), and the etched triangular holes would be ro-
in Fig. 9(f), the pits on adjacent layers had the same edge termination tated 180° in alternating layers, resulting in the formation of hexag-
(ZZ-S) with opposite directions. When the etching temperature was in- onal holes with chalcogen-terminated ZZ edges (Fig. 11(h)). A facile
creased up to 700 °C, multilayered (>10) hexagonal cavities formed. and controllable etching strategy for MoSe2 flakes and other 2D TMDs
The cavities originated from larger triangular pits on the topmost layer was developed by modulating the oxygen plasma pretreatment followed
of MoS2 and evolved into hexagonal shapes as a result of a 2H-stacking by CVD growth and etching time adjustments [111]. As confirmed by
sequence of MoS2 (Fig. 9(h)). Therefore, the edge termination of this DFT calculations, the etching process preferentially occurred along the
3D structure could be divided into two categories: alternative ZZ-S and zigzag edges due to their lower binding energy and greater stability,
ZZ-Mo for hexagonal pits in plane and ZZ-S or ZZ-Mo for deeper layers which results in the formation of hexagonal holes with zigzag edges.
out of plane. The above results demonstrated that water vapor etching This strategy provided a valuable insight into the influence of oxygen
of MoS2 was greatly influenced by temperature. plasma pretreatment and understanding of the etching behavior of 2D
TMDs.
2.4. Plasma etching The four main anisotropic etching methods discussed in this review
offer unique advantages and challenges for processing 2D materials. To
Graphene can be anisotropically etched using hydrogen plasma, and facilitate the selection of an appropriate etching method, a compari-
more significantly, graphene with smooth ZZ edges may be prepared son including the aspect of etching nanostructures, applicable materi-
[29,104,105]. Previous studies have demonstrated that the etching pro- als, precision, impact on material properties, and the complexity of the
cess in the basal plane of graphene samples usually originated from fabrication process is summarized in the Table 1.
the native defect sites, which resulted in randomly distributed etched
holes, pits, or trenches [66]. This obstacle could be overcome by in- 3. Applications
troducing artificial defects as seeds for initiating the etching reaction
[32,104]. Using lithographically defined circular holes in graphene as As discussed above, anisotropic etching facilitates the creation of a
artificial defects to seed the hexagon growth during etching (Figs. 10(a)– variety of 2D material nanostructures with specific edges and shapes
(d)), a variety of patterned graphene nanostructures with desired place- that are less likely to be created by growth. In addition, etching is a
ments, controlled sizes/shapes, and identical ZZ edges were successfully simple method for 2D material characterization, including identifica-
achieved through hydrogen plasma anisotropic etching at a tempera- tion and artificial location of defects, and assessment of boundary struc-
ture of 450 °C [32]. These unique graphene nanostructures with dis- tures based on certain etching features. Furthermore, the investigation
tinct characteristics show great potential for the construction of future of etching behaviors has yielded a wealth of knowledge for the compre-
graphene devices in the field of electronic and spintronics [12,106]. It hension of the growth mechanisms and the guiding relevance for the
should be noted that only graphene nanostructures with ZZ edges can be controlled growth of 2D materials. In this section, the applications of
created utilizing these two steps (artificial defect patterning followed by etching will be discussed in more detail.
hydrogen-plasma etching) due to the thermodynamically favorable etch- Etching usually initiates from defect sites, such as point and line de-
ing reaction, as ZZ edges are more likely to occur at the lowest etching fects. Therefore, etching as-grown 2D materials is an effective was to
rate. The etching process was further investigated and revealed in detail identify the existence of defects and check the quality of the crystal [33].
using a remote hydrogen plasma approach [105]. Fig. 10(e) shows five As illustrated in Fig. 12(a), hexagonal holes could be formed at the cen-
circular pits patterned on trilayer graphene, with the centers oriented in ter of the graphene flake by hydrogen etching. As a result of regrowing
AC direction. The etched nanostructure was initially hexagonally shape the etched domain, the as-formed holes were filled in and disappeared,
(Fig. 10(f)) before merging between adjacent pits to form a hexagonal resulting in the formation of a new hexagonal graphene flake without
domain with ZZ edges (Fig. 10(g)). As the anisotropic etching continued, defects (Fig. 12(b)). Consequently, the second etching only occurred in
the corners of the graphene domain were “flattened”, and edges with AC the perimeter of the graphene, as shown in Fig. 12(c), confirming the
orientation were newly formed at the corners of the hexagonal domain complete healing of point defects in the graphene center. Etching not
(Fig. 10(h)). In another case, sawtooth-like edges with a ZZ termination only improves the growth quality, but it also helps to increase the size
were gradually flattened, resulting in the formation of AC edges in a ki- of as-grown graphene domains. Fig. 12(d) showed that a large-area (ap-
netically controlled process (Figs. 10(i)–(l)). These experimental results proximately 3 mm) defect-free single-crystal monolayer graphene do-
indicated that the evolution of graphene shape during etching process main was created by combining CVD growth and the etching-regrowth
was influenced by its intrinsic properties, with AC edges being the most process, which simultaneously healed the structural defects. A field ef-
reactive edges in hydrogen plasma etching. fective transistor fabricated by the as-grown monolayer graphene exhib-
Utilizing a pure sulfur hexafluoride (SF6 ) plasma, several TMDs were ited high carrier mobility (approximately 13000 cm2 V−1 s−1 ) due to its
successfully etched [107]. As illustrated in Figs. 11(a)–(d), hexagonal defect-free nature [112]. Large-size single-crystalline graphene was also
holes with ZZ edges were created as a result of the slow and fast etching successfully realized by lowering the nucleation density with assistance
rates along the direction orthogonal to the ZZ and AC edges, respec- of the oxidative etching (Fig. 12(e)) [113]. In addition, a H2 O-assisted
tively, with an included angle of 30°. The etching rate in the shape of low-pressure CVD approach was developed to control the growth of
six wagon wheels, due to the sixfold symmetry, is shown in the polar plot high-quality bilayer graphene on Cu foil, which was achieved by in-
(Fig. 11(e)) to highlight the relationship between etching rate and crys- jecting intermittent pulses of water vapor during a CVD process at low
tal orientation. The order of anisotropy degree of etching for four TMDs pressure [114]. Water etching of the graphene edges prevented the top
was WS2 > WSe2 > MoTe2 > MoS2 , which may be due to the relative layer’s expansion, while facilitating the nucleation and growth of the
stability of AC and ZZ edges [39]. It is worth noting that TMDs with W second layer (Fig. 12(f)). The utilization of anisotropic etching in crys-
atoms (WS2 and WSe2 ) exhibited larger anisotropic etching degree than tal growth opens up new opportunities for the production of desired 2D

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Fig. 10. Patterning graphene with controlled edges through hydrogen plasma etching. (a)–(d) AFM images showing various patterned graphene nanostructures with
hexagonal shape, waved ribbon array, isolated triangular dots, and GNR with a width of ∼5 nm after anisotropic etching. [32] Copyright 2011, Wiley-VCH. (e)–(h)
and (i)–(l) SEM images showing the creation of AC edges evolving from ZZ edges of trilayer graphene in a kinetically controlled process. [105] Copyright 2018,
Springer.

material nanostructures with superior qualities, sizes, and other charac- junctions along ZZ directions than AC directions. Moreover, as shown in
teristics for applications in the field of electronic device design. Fig. 13(f), the width of h-BN stripes grown along AC edges of an etched
Besides assisting in situ growth of 2D materials, anisotropic etch- dodecagon graphene was larger than that along ZZ edges, indicating
ing can also be used in the construction of templates for 2D material that h-BN growth rates varied with edge configuration. In addition to
growth. Since graphene and h-BN have a close lattice match (1.7%), they the growth of h-BN on graphene, in-plane epitaxial growth of mono-
can serve as growth template for each other. According to a theoretical layer GNRs with ZZ edges and controlled width in etched h-BN nano-
study, it is possible to modify the electronic and magnetic properties of trenches were achieved (Fig. 13(g)) [71]. High on–off ratios (>104 ) were
h-BN sheets by embedding graphene flakes of varying sizes and shapes observed in the fabricated GNR field effect transistors with sub-10 nm
[18]. This is extremely promising for the fabrication of 2D electronic de- features due to the tunable band gap of the as-grown GNRs. This trial
vices with unique performances. The fabrication process for heteroepi- will eventually lead to an alternative avenue for creating the graphene-
taxial growth of h-BN from the edges of pre-existing graphene crystals BN heterostructure via graphene growth on single-crystal h-BN.
on Cu foil is shown in Fig. 13(a) [115]. The monolayer graphene crystal As discussed above, anisotropic etching is a powerful means to ma-
was first etched with hydrogen to form hexagonal holes with ZZ edges nipulate the edge structure and morphology of 2D materials, thereby
(Fig. 13(b)), then fully covered with epitaxially grown h-BN (Fig. 13(c)). producing various nanostructures with well-defined edges. Their result-
Importantly, the crystalline orientation of h-BN was entirely determined ing properties and functions, such as tunable band gaps, magnetic mo-
by the graphene seed. The graphene/h-BN boundary was revealed to be ments, and carrier mobilities allow for the fabrication of efficient elec-
ZZ edges. Furthermore, utilizing hydrogen etching, various geometric tronic and optoelectronic devices [12,16,24,29,115], and the defects-
structures of graphene were successfully created as the templates for the rich edge-enhanced catalytic activity for hydrogen evolution reactions
subsequent h-BN growth process [116]. The h-BN stripes were uniformly [4,25,42], opens up a wide range of applications in various fields. Over-
grown along the six ZZ edges of the etched inner hexagonal graphene all, the ability to control the edge structure and morphology of 2D ma-
hole (Fig. 13(d)) and along the AC edges of the etched outer graphene terials through anisotropic etching holds great potential for creating ad-
(Fig. 13(e)). However, the edges of h-BN stripes grown along etched vanced materials and devices with tailored properties for various appli-
outer graphene have a larger roughness than those grown along etched cations. Further research and development in this area are expected to
inner holes, demonstrating the better quality of graphene/h-BN hetero- unlock new possibilities in nanotechnology and material science.

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Y. Zhang, Q. Liu, D. Zhang et al. ChemPhysMater 3 (2024) 341–356

Fig. 11. Anisotropic etching of various TMDs by SF6 plasma. (a)–(d) TEM images showing the etched hexagonal holes for WS2 , WSe2 , MoTe2 , and MoS2 , respectively.
(e) The relationship between crystal orientation angle and etching rate for four TMD crystals. (f) TEM images showing the detailed edge structures in WS2 . The zoomed-
in TEM images (right) show the AC and ZZ corners marked by green and blue squares in the left panel. (g) Schematic showing the edge orientations of etched TMD
monolayers according to KWC theory. (h) Schematic showing the edge orientation and morphology evolution of etched TMD multilayers. [107] Copyright 2021,
American Chemical Society.

4. Summary and perspective ricate 2D material nanostructures with specific characteristics through
solely the growing process. Anisotropic etching is a versatile and sim-
The extraordinary physical and chemical performance of 2D mate- ple technique for micro-engineering 2D materials. So far, anisotropic
rials originating from their unique layered structures results in a wide etching has not only been used in materials processing, but it also
range of potential applications in electronics, optoelectronics, optics, plays an important role in the characterization and synthesis of 2D
and other fields. Well-defined edge structures, shapes, and sizes are materials, identifying defects and boundary structures, understanding
very important for the optimal performance of 2D materials in prac- the growth mechanism, assisting the controlled growth, among other
tical applications. However, it is significantly more challenging to fab- functions. Thus, a thorough understanding of anisotropic etching in

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Table 1
Summary of advantages and challenges of the four etching methods.

Etching method Advantages Challenges

TM-nanoparticle-catalyzed • Good control over etching direction and shape • Limited by the availability of suitable catalysts
etching • Can produce well-defined nanostructures like GNRs • Complexity in controlling nanoparticle distribution
• Controlled etching rate • Potential contamination from metal residues

Post-growth etching • Feasible for single, few-layer, and polycrystalline 2D materials • Substrate-dependent etching rate and patterns (few-layer
• Precise patterns definition controlled by grown parameters materials)
• Limited to materials with suitable CVD growth methods

Thermal-annealing etching • Relatively simple setup and fast process with high precision • Limited to materials that can react with gas atmosphere
• Controllable for producing nanostructures with specific edge • Potential thermal damage to the material due to the high
terminations temperature

Plasma etching • Clean and high etching rates • Requires expensive specialized equipment
• High anisotropy and precision • Potential plasma damage to sensitive material
• Good for producing nanostructures with specific edge
terminations

Fig. 12. The role of anisotropic etching in assiting the controlled graphene growth. (a) SEM image showing single-crystal graphene flakes after hydrogen etching
and (b) regrowth. (c) SEM image showing a near-hexagonal single-crystal graphene domain obtained by etching the regrown graphene domain using hydrogen. [33]
Copyright 2013, National Academy of Sciences. (d) SEM images showing large single-crystal graphene flakes obtained via growth assisted by hydrogen etching. [112]
Copyright 2014, American Chemical Society. (e) SEM images showing large single-crystal graphene flakes obtained via growth assisted by oxygen etching. [113]
Copyright 2016, Wiley-VCH. (f) Bernal-stacked bilayer graphene grown via a H2 O-assisted low-pressure CVD process. [114] Copyright 2018, American Chemical
Society.

2D materials is critical for both the growth and processing of 2D these factors on the etching behaviors of different 2D materials requires
materials. further exploration.
In the past decade, various anisotropic etching methods have been Thermal annealing etching is a relatively simple method that of-
developed, with a focus on 2D materials represented by graphene, MoS2 , ten uses oxidation reactions under elevated temperatures to remove C
and h-BN. For example, metal-nanoparticle catalytic etching offers many atoms from graphene and Mo or S atoms from MoS2 samples. Graphene
possibilities for meeting the processing requirements of graphene. In nanostructures with AC edges and MoS2 nanostructures with either Mo-
particular, post-growth etching has been widely used for graphene tai- terminated or S-terminated edges can be created through controlled an-
loring. Thus far, several factors were found to be critical to the etching nealing etching. Although thermal annealing methods can create vari-
process of graphene, including the substrate, partial pressure of etchant, ous nanostructures with controlled edge termination on 2D material sur-
layer stacking sequences, and buffer gas types. However, due to the com- faces, more precise control of the positions of etched nanostructures on
plex composition of 2D materials (such as h-BN and GaSe), the effect of 2D material surfaces is significant for the further development. Hydro-

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Fig. 13. The role of anisotropic etching in constructing the template for growth of 2D materials. (a) Schematic showing the fabrication procedure of a graphene/h-BN
heterostructure. (b) SEM image showing a hydrogen-etched graphene domain with hexagonal holes. (c) SEM image showing the etched holes in a graphene island
fully covered by h-BN. [112] Copyright 2014, American Association for the Advancement of Science. (d) SEM images showing h-BN stripes grown parallel to ZZ edges
of etched holes and (e) outer AC edges of etched graphene. (f) SEM image showing h-BN stripes grown along both ZZ and AC edges of etched dodecagonal graphene.
[116] Copyright 2019, Wiley-VCH. (g) AFM image showing GNRs obtained by in-plane epitaxial growth on h-BN nano-trenches produced through Ni-nanoparticle
catalytic etching. [71] Copyright 2017, Springer Nature.

gen plasma etching with artificial defect patterning assistance is an ef- Deliang Zhang: Writing – review & editing, Formal analysis. Yue Hong:
fective strategy for creation of 2D nanostructures with desired positions. Writing – review & editing, Formal analysis. Qiang Li: Writing – review
With this method, various graphene nanostructures with desired place- & editing, Supervision, Funding acquisition, Conceptualization.
ments, controlled sizes/shapes, and identical ZZ edges can be achieved.
In addition to the edges with ZZ termination, other orientation-specific Acknowledgements
edges are also created via other types of plasma etching.
To summarize, several anisotropic etching methods have been de- This work was financially supported by the Natural Science Founda-
veloped for the processing of 2D materials to promote their use in na- tion of Shandong Province (No. ZR2023MB028), the Grant for Taishan
noelectronics applications. The exploration of anisotropic etching of 2D Scholar Advantage Characteristic Discipline of Shandong Province, the
materials not only sheds light on their intrinsic properties, but also pro- Start-up Grant for QiLu Young Scholars of Shandong University.
vides deeper understanding of their growth mechanism. Furthermore, References
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