Research Article

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Step-Climbing Epitaxy of Layered Materials with Giant

Out-of-Plane Lattice Mismatch
Xuehan Zhou, Yan Liang, Huixia Fu, Ruixue Zhu, Jingyue Wang, Xuzhong Cong,
Congwei Tan, Congcong Zhang, Yichi Zhang, Yani Wang, Qijia Xu, Peng Gao,
and Hailin Peng*

and coupling of different materials, which

Heteroepitaxy with large lattice mismatch remains a great challenge for high- permits an improved functionality of con-
quality epifilm growth. Although great efforts have been devoted to epifilm ventional semiconductor platforms, such
growth with an in-plane lattice mismatch, the epitaxy of 2D layered crystals as III–V materials and various complex
on stepped substrates with a giant out-of-plane lattice mismatch is seldom oxide materials.[1] Moreover, many fasci-
nating discoveries in fundamental physics
reported. Here, taking the molecular-beam epitaxy of 2D semiconducting have involved interfaces, for example,
Bi2O2Se on 3D SrTiO3 substrates as an example, a step-climbing epitaxy through the engineering of symmetries
growth strategy is proposed, in which the n-th (n = 1, 2, 3…) epilayer climbs as well as the charge, spin, and orbital
the step with height difference from out-of-plane lattice mismatch and con- degrees of freedom of correlated elec-
tinues to grow the n+1-th epilayer. Step-climbing epitaxy can spontaneously trons.[2,3] Therefore, developing advanced
heteroepitaxial methods to obtain high-
relax and release the strain from the out-of-plane lattice mismatch, which
quality epitaxial films and heterojunctions
ensures the high quality of large-area epitaxial films. Wafer-scale uniform 2D has always been a core issue for both aca-
Bi2O2Se single-crystal films with controllable thickness can be obtained via demia and industry.
step-climbing epitaxy. Most notably, one-unit-cell Bi2O2Se films (1.2 nm thick) The presence of strain in epitaxial films
exhibit a high Hall mobility of 180 cm2 V−1 s−1 at room temperature, which is a fundamental challenge in heteroepi-
exceeds that of silicon and other 2D semiconductors with comparable thick- taxy. High-quality films with negligible
strain can be obtained when the in-plane
ness. As an out-of-plane lattice mismatch is generally present in the epitaxy lattice mismatch between epilayers and
of layered materials, the step-climbing epitaxy strategy expands the existing substrates is sufficiently small, as for the
epitaxial growth theory and provides guidance toward the high-quality syn- AlGaAs/GaAs system.[4,5] For situations
thesis of layered materials. in which the in-plane lattice mismatch
exceeds 10%, several lattice engineering
techniques have been proposed to reduce
1. Introduction the strain and number of dislocations, such as the domain
matching epitaxy (DME), introducing buffer layers (IBL), and
Being a key foundation technology of the modern electronic epitaxial lateral overgrowth (ELOG).[1] Recently, with the rapid
and optoelectronic industry, heteroepitaxy allows integration development of 2D materials, van der Waals (vdW) epitaxy has

X. Zhou, Y. Liang, J. Wang, X. Cong, C. Tan, C. Zhang, Y. Zhang, Y. Wang, H. Fu

Q. Xu, H. Peng Center of Quantum Materials and Devices
Center for Nanochemistry College of Physics
Beijing Science and Engineering Centre for Nanocarbons Chongqing University
Beijing National Laboratory for Molecular Sciences Chongqing 401331, P. R. China
College of Chemistry and Molecular Engineering R. Zhu, P. Gao
Peking University Electron Microscopy Laboratory
Beijing 100871, P. R. China School of Physics
E-mail: hlpeng@pku.edu.cn International Center for Quantum Materials
Y. Liang Peking University
Beijing National Laboratory for Condensed Matter Physics and Institute Beijing 100871, P. R. China
of Physics
Chinese Academy of Sciences
Beijing 100190, P. R. China
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adma.202202754.

DOI: 10.1002/adma.202202754

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attracted tremendous research interest owing to the possibility
it provides of growing heteroepitaxial films without strict in-
plane lattice match requirements.[6] Up to now, a variety of 2D
materials and III–V materials have been obtained through vdW
epitaxy, such as graphene[7] or hexagonal boron nitride (hBN)[8,9]
on Cu substrates, molybdenum disulfide (MoS2) on sapphire
substrates,[10,11] and remote epitaxy of GaAs.[12] Up to now, great
efforts have been devoted to epifilm growth with an in-plane
lattice mismatch. However, considering that the substrate sur-
face is usually not absolutely flat, the steps are inevitable on
the surface of single crystal substrates and an out-of-plane lat-
tice mismatch is generally present in the epitaxy of 2D layered
materials. Therefore, the systematic study of the effects caused
by out-of-plane lattice mismatch of stepped substrates on the
growth of epitaxial layers is critical to the high-quality synthesis
of 2D layered materials.
Here, we propose a new growth strategy, step-climbing epi-
taxy, in which the n-th (n = 1, 2, 3…) epilayer climbs the step
with height difference from out-of-plane lattice mismatch and
continues to grow the n+1-th epilayer. Taking the molecular
beam epitaxy (MBE) growth of 2D Bi2O2Se on 3D SrTiO3 sub-
strates as an example, we found that the strain is concentrated
in the first three layers of the 2D Bi2O2Se epifilm around the
steps of SrTiO3 substrates while the area away from the steps
maintains nearly perfect crystal structure with negligible strain.
Step-climbing epitaxy can spontaneously relax and release the
strain from the out-of-plane lattice mismatch, which ensures
the high quality of large-area epitaxial films. Wafer-scale uni-
form 2D Bi2O2Se single-crystal films with a controllable thick-
ness ranging from monolayer (ML) to several nanometers
can be obtained via step-climbing epitaxy. Most notably, one-
unit-cell (1-UC) Bi2O2Se films show a Hall mobility as high as
180 cm2 V−1 s−1 at room temperature, which exceeds that of
silicon and other 2D semiconductors with comparable thick-
ness and meets the requirements of future advanced semicon-
ductor process nodes.[13–15] Compared with conventional epitaxy
and vdW epitaxy, not only the in-plane lattice mismatch but also
the out-of-plane lattice mismatch is considered in step-climbing
epitaxy. Thus, the step-climbing epitaxy strategy considerably
expands the existing epitaxial growth theory and can be extended
to achieve high-quality preparation of other layered materials
such as [Bi2O2]-based layered materials[16] and iron-based layered
superconductors with similar skeletal structures.[17,18]
2. Results
Bi2O2Se is composed of strongly covalently bonded [Bi2O2]
layers and planar [Se] layers with a relatively weak electrostatic
interaction (space group I4/mmm). The in-plane lattice constant
is 3.88 Å, and the out-of-plane lattice constant is 12.16 Å.[19] The
thickness of ML Bi2O2Se is 6.08 Å, which consists of one com-
plete [Bi2O2] layer and one complete [Se] layer stacked along
the [001] direction (Figure 1a). 2D Bi2O2Se is a high-mobility

Figure 1. Schematic diagrams and DFT simulations of step-climbing epitaxy. a) Crystal structures of Bi2O2Se and SrTiO3, showing a negligible in-plane
lattice mismatch and a giant out-of-plane lattice mismatch of 55.7%. b) 3D schematic diagram and side view of step-climbing epitaxy. c) DFT simulations
of the terrace nucleation and step-edge nucleation, which show that the step edges are more favorable nucleation positions with a formation energy differ-
ence of 1.26 eV. d) DFT simulation showing the atomic configuration of the step-climbing epitaxy of bilayer Bi2O2Se on a stepped SrTiO3 substrate. Bottom:
bond length profiles of the top BiO layer, which reveals that only the Bi2O2Se lattices above the step are partially distorted to form a continuous film.

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layered semiconductor and shows potential applications in
logic,[20] memory,[21,22] and sensor[23–26] devices. One of the main
issues that hinders the wide application of 2D Bi2O2Se is the
controlled synthesis of wafer-scale high-quality thin films.[27]
Up to now, chemical vapor deposition (CVD),[28] MBE,[29]
pulsed laser deposition (PLD),[30] and cracking metal–organic
chemical vapor deposition (c-MOCVD)[31] have been adopted for
the growth of Bi2O2Se films on perovskite substrates. However,
wafer-scale Bi2O2Se films with a controllable thickness have
not been realized yet. Previous studies have demonstrated that
SrTiO3 single crystals, which exhibit a negligible in-plane lat-
tice mismatch with Bi2O2Se (0.5%), are suitable epitaxial sub-
strates.[28] However, the giant out-of-plane lattice mismatch
between Bi2O2Se and SrTiO3 (55.7%), which would directly
affect the nucleation and growth of epilayers around the steps
of SrTiO3 substrates, has not been systematically studied
during film epitaxy yet. Herein, we propose a step-climbing
epitaxy strategy, in which epilayers grow across the stepped
surfaces and form uniform films over the entire substrate
(Figure 1b). This growth strategy is beneficial for the realization
of quasi-strain-free Bi2O2Se epilayers at the wafer level. Indeed,
these steps typically exist in all single-crystal substrates; they
are caused by the inevitable miscut angle during the processing
of single-crystal substrates.[32] Therefore, the systematic study
of the Bi2O2Se film growth on SrTiO3 substrates to explore the
influence of the giant out-of-plane lattice mismatch will have a
significant impact on the high-quality synthesis of other layered
materials.
Nucleation is a crucial step for film growth. To simulate the
nucleation position of Bi2O2Se on SrTiO3 substrates, step-edge
nucleation and terrace nucleation models were constructed
(Figure 1c) by performing first-principles calculations using the
Vienna ab initio simulation package (VASP) in the framework
of the density functional theory (DFT) (more details can be
found in the Experimental Section). In the step-edge nucleation
model, the Bi and O atoms in Bi2O2Se bond with the O and
Ti atoms at the step edge of SrTiO3, which induces a decrease
in the formation energy by 1.26 eV with respect to the terrace
nucleation model. The calculation results indicate that the step
edges are more favorable nucleation sites. In addition, the epi-
taxy of the first Bi2O2Se layer on the lower terrace of the SrTiO3
substrate results in a reduction in the step height from 0.39 nm
(initial step height of SrTiO3) to 0.25 nm, which lays the foun-
dation for the epitaxy of the second Bi2O2Se layer and con-
tinuous Bi2O2Se film (Figure 1d). In the second Bi2O2Se layer,
the most stretched BiO bonds around the steps are stretched
from 0.23 nm (initial value) to 0.32 nm to climb the 0.25 nm
height difference between the SrTiO3 step and the first Bi2O2Se
layer. This reflects the high elasticity of [Bi2O2] layers in layered
materials, which is beneficial for the epitaxial growth of a con-
tinuous Bi2O2Se film on a stepped SrTiO3 substrate with giant
out-of-plane lattice mismatch.
To verify the step-climbing epitaxy proposed by DFT calcu-
lations, we systematically studied the nucleation and growth
behavior of Bi2O2Se epilayers on single-crystal SrTiO3 (001)
substrates in a homemade MBE facility (Figure S1, Supporting
Information). Using an optimized growth procedure (see the
Experimental Section and Figure S2, Supporting Information),
1 in. high-quality Bi2O2Se films on SrTiO3 wafers with a uni-
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form surface morphology can be obtained (Figure 2a,b). The
low-temperature growth of 2D layered Bi2O2Se is promising to
meet the complementary metal oxide semiconductor (CMOS)
process compatibility requirements when combined with the
direct growth of high-κ SrTiO3 epifilms on Si substrates[33] or
the transfer of SrTiO3 gate dielectric epifilm onto Si wafer by
exploiting the sacrificial layer.[34] The single crystallinity of a
10 nm-thick film was confirmed via high-resolution X-ray dif-
fraction (XRD) and electron backscatter diffraction (EBSD). The
film is oriented along the c-axis since all peaks except for the
SrTiO3 substrate peaks can be indexed to the (00n) reflections
of tetragonal Bi2O2Se (Figure S3a, Supporting Information).
XRD 2θ mapping of the Bi2O2Se (002) peak shows a high uni-
formity of the epitaxial films (Figure S3b, Supporting Infor-
mation). The rocking curve (ω-scan) of the Bi2O2Se (002) peak
with a full width at half maximum (FWHM) of 0.10° indicates
the highly crystalline nature of Bi2O2Se thin films (Figure S3c,
Supporting Information). Besides, the in-plane texture of the
Bi2O2Se thin films was measured via XRD azimuthal φ scans of
the off-axis (103) peak. The Bi2O2Se film grown on the SrTiO3
substrate shows very sharp and strong peaks with 90° intervals,
indicating a single-crystalline tetragonal structure (fourfold
symmetry) without any in-plane misorientation (Figure S3d,
Supporting Information). Reciprocal space mapping of the
Bi2O2Se film and SrTiO3 substrate peaks shows that the in-
plane epitaxial mismatch between them is very small, and the
in-plane strain is maintained during the epitaxial growth,
which further verifies the high quality of epitaxial Bi2O2Se films
(Figure S3e, Supporting Information). Moreover, the EBSD
maps of the Bi2O2Se thin film show a uniform distribution with
no angular variations on the millimeter scale, which further
confirms the out-of-plane and in-plane single-crystallinity of the
Bi2O2Se films (Figure S4, Supporting Information).
The surface morphology evolution of the Bi2O2Se film at
different growth stages is explored to illustrate the nucleation
and growth processes (Figure 2c). The atomic force micro­
scopy (AFM) image shows that the nucleation occurs along the
step edges, which further proves the validity of the step-edge
nucleation model. The initial growth of ML Bi2O2Se islands
on the SrTiO3 terraces is anisotropic and proceeds at a faster
rate along the step edge than in the perpendicular direction,
following a step-flow growth mode similar to that of GaN
grown by MBE.[35] As the coverage increases, these isolated ML
Bi2O2Se islands coalesce together and form a pseudocontin-
uous layer that covers the SrTiO3 substrate surface completely
and replicates the terrace morphology strictly. In other words,
the ML Bi2O2Se film is discontinuous on the atomic scale when
encountering the steps of the SrTiO3 substrate.
As the growth time increases, new 2D Bi2O2Se islands with
a height of 0.6 nm appear at the lower terrace edges of the
Bi2O2Se layer. The edges of these 2D islands on the Bi2O2Se
layers are regular and parallel to each other; their orientation
reflects the in-plane lattice direction of the SrTiO3 substrate. In
addition, these new 2D Bi2O2Se islands on the second layer are
grown from the growth front of the first Bi2O2Se layer on the
upper terrace and spontaneously climb the step with height dif-
ference from the out-of-plane lattice mismatch, which is a key
feature of step-climbing epitaxy. The above experimental results
are consistent with the theoretical simulations. Note that the
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Figure 2. Step-climbing epitaxy of 2D layered Bi2O2Se films on stepped SrTiO3 substrates. a) Photograph of a 1 in. Bi2O2Se film on the SrTiO3 wafer.
b) Optical microscopy (OM) image of the Bi2O2Se film. c) Schematic diagram of step-climbing epitaxy and AFM topography of the MBE-grown 2D
layered Bi2O2Se films at different growth stages. i) Surface morphology of single-TiO2-teminated SrTiO3 substrates, showing ordered terraces with a
step height of 0.39 nm. ii) The isolated 2D Bi2O2Se islands nucleate at the step edges. iii) ML Bi2O2Se film. iv) ML Bi2O2Se film with new 2D islands.
v) 25 nm-thick layered Bi2O2Se film. The step-climbing epitaxy adopts a layer-by-layer growth mode, showing clear step heights of 0.39 and 0.61 nm
originating from the SrTiO3 substrate and ML Bi2O2Se, respectively. Besides, the height of 0.22 nm originates from the height difference between 1-UC
SrTiO3 and ML Bi2O2Se.

morphology control of Bi2O2Se grown by MBE is very sensitive
to growth temperature and Bi flux rate (Figure S5, Supporting
Information). By controlling the growth temperature, time and
Bi flux rate precisely, a layer-by-layer growth of the Bi2O2Se
film can be realized via step-climbing epitaxy, permitting one
to achieve an accurate thickness control (Figure S6, Supporting
Information). For example, a 25 nm-thick Bi2O2Se film can be
obtained after a growth of 22 h. The AFM topography of five
different sites on the MBE-grown Bi2O2Se wafer shows similar
morphological characteristics, which proves the universality of
step-climbing epitaxy at the wafer level (Figure S7, Supporting
Information).
In order to reveal the structural details of step-climbing epi-
taxy, cross-sectional aberration-corrected scanning transmis-
sion electron microscopy (STEM) images were systematically
collected from the Bi2O2Se/SrTiO3 interface, especially around
the steps. The high-angle annular dark-field (HAADF) STEM
images show a sharp interface between Bi2O2Se and SrTiO3,
and a high-quality crystal structure with no defects is observed.
At the terrace positions, the Bi atoms are clearly aligned with
the Sr atoms at the interface, indicating a nearly perfect in-
plane lattice match (Figure 3a and Figure S8a, Supporting
Information). Three typical HAADF-STEM images around the
steps show the TiO2-termianated SrTiO3 surface marked with
blue balls, illustrating the universal step-climbing epitaxy of
the Bi2O2Se epilayers over the entire substrate (Figure 3b–d).
In order to identify the atomic structure of the Bi2O2Se film
around the steps, an atomic-resolved HAADF-STEM image
was acquired, in which all atoms can be precisely referred to
components of Bi2O2Se or SrTiO3 (Figure 3e). The image
clearly shows that the edge of the first Bi2O2Se layer on the
lower terrace is bonded with the step edge of SrTiO3. Then,
the first Bi2O2Se layer on the upper terrace climbs the step and
continues to grow a second Bi2O2Se layer on the lower terrace,
which is in agreement with the step-climbing epitaxy strategy
proposed above. By analogy, the n-th (n = 1, 2, 3…) Bi2O2Se layer
climbs the step with height difference from out-of-plane lat-
tice mismatch and continues to grow the n+1-th Bi2O2Se layer,

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Figure 3. Cross-sectional STEM characterization of the MBE-grown Bi2O2Se film on the SrTiO3 substrate. a) Low-resolution cross-sectional HAADF-
STEM image of a 25 nm-thick Bi2O2Se epilayer on the SrTiO3 substrate. b–d) Three typical atomic-resolution HAADF-STEM images around different
steps. The blue balls indicate the interface where the SrTiO3 substrate terminates with the TiO2 layer. e) HAADF-STEM image with an atomic model
superimposed, corresponding to the white rectangle in (b). f) Relative deviation of the nearest neighbor Bi atomic distance profiles along the [100] axis
for three layers of Bi2O2Se. g) Atomic-resolution HAADF-STEM images of the Bi2O2Se film around a step, indicating that the distortion in the Bi2O2Se
layers decreases as the film thickness increases.

which approximately replicates the morphological characteris-
tics of the bottom layers.
In order to quantitatively analyze the distortion of the
Bi2O2Se lattice around the steps, we define ΔXBiBi as the
relative deviation of the nearest neighbor Bi atomic distance
profiles along the [100] axis (Figure 3f). ΔXBiBi is defined
according to ΔXBiBi = ( X Bi–Bi − X 0,Bi–Bi ) /X 0,Bi–Bi , where XBiBi is
the nearest neighbor Bi atomic distance projected onto the [100]
axis extracted from the HAADF image (Figure 3e), and X 0,Bi–Bi
is the nearest neighbor Bi atomic distance projected onto the
[100] axis without lattice distortion or strain. The largest ΔXBiBi
value is 24% for the first Bi2O2Se layer and decreases to ≈2% for
the third Bi2O2Se layer, which suggests the high elasticity of the
[Bi2O2] layers and indicates that the distortion near the steps in
the Bi2O2Se layers decreases with increasing film thickness. As
the film thickness increases, the upper films basically replicate
the morphology of the bottom layers albeit with a wider lattice
relaxation range and a negligible lattice deformation.
To gain a deeper insight into the step-climbing epitaxy, the
geometric phase analysis (GPA) was adopted for the HAADF
image to elucidate the interfacial strain distribution in the
epitaxial film. The strain mapping along the x-axis parallel to
SrTiO3 [100] reveals that the Bi2O2Se film has a nearly identical
lattice spacing to that of SrTiO3, except for the step position,
indicating that the Bi2O2Se/SrTiO3 interface is of high quality
and free of dislocations (Figure S8a–c, Supporting Informa-
tion). The GPA line profiles show that the strain is mainly con-
centrated within several nanometers of the step (Figure S9a,b,
Supporting Information). Along the z-axis parallel to SrTiO3
[001], the lattice spacing is homogenous in the upper Bi2O2Se
film but increases significantly near the interface; this increase
originates from the out-of-plane lattice mismatch between the
Bi2O2Se epilayers and the SrTiO3 substrates. Furthermore,
the strain directions in the Bi2O2Se epilayers around the steps
along the x- and z-axes are opposite, which indicates that the
distortion directions of the in-plane and out-of-plane lattices
are opposite (Figure S9a–d, Supporting Information). The GPA
results suggest that the strain in the Bi2O2Se film is concen-
trated within about three layers of the interface, while the area
away from the steps and upper film retains a nearly perfect
crystal structure with negligible strain. We also conducted 2D
Raman mapping of Bi2O2Se film grown on SrTiO3 substrates
by MBE. The Raman shift of Bi2O2Se film at terraces and steps
shows no significant difference, which suggests that the strain
in a 10 nm-thick Bi2O2Se film is undetectable at the resolu-
tion of micro-Raman spectroscopy (Figure S10, Supporting
Information).
Step-climbing epitaxy not only provides a high crystalline
quality but also ensures an excellent uniformity of the elec-
trical properties. Multiple devices and arrays can be fabricated
on the wafer-scale Bi2O2Se films (Figure 4a; see more details
in the Experimental Section).[25,26] To investigate the electrical
uniformity of the Bi2O2Se films, 10 nm-thick films were pat-
terned into 800 µm-long and 30 µm-wide rectangles, and metal
electrodes were deposited for resistance measurements (the red
rectangle indicated in Figure 4a). Figure 4b shows the resistance

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Figure 4. Electronic properties of single-crystal Bi2O2Se thin films. a) Photograph of the device array patterned on a 1-in. Bi2O2Se film on the SrTiO3
wafer. b) Linear relationship between the resistance and the Bi2O2Se pattern length. Inset: OM image of a device used for resistance measurements
corresponding to the red rectangle indicated in (a). c) Normalized longitudinal resistance as a function of the effective magnetic field (Bcosθ) measured
at a varying tilt angle θ. The angular dependence of the SdH oscillations in the Bi2O2Se two-dimensional electron gas (2DEG) confirms the 2D nature
of the 4-UC Bi2O2Se thin film. d) Room-temperature Hall mobility of the MBE-grown 2D Bi2O2Se as a function of the film thickness. For comparison,
previously reported values for hBN-encapsulated MoS2 (En-MoS2),[37] MoS2 and WSe2 on SiO2 substrates[38,39] and Si[15] are plotted.

as a function of the rectangle length; the data can be well fitted
with a straight line, indicating that the resistivity is homoge-
neous. In addition, an array of four-terminal devices for resis-
tivity measurements was fabricated using the multiple overlay
exposure technique. Figure S11b (Supporting Information)
presents the resistivity (ρ) distribution of 36 devices (the black
rectangle indicated in Figure 4a) with a 5 µm channel length
in a 1.5 × 2.4-mm2 area (Figure S11a, Supporting Information),
which suggests the high uniformity of the Bi2O2Se film.
As 2D Bi2O2Se is a promising channel material for next-
generation low-power electronics,[27,28] we also evaluated the
intrinsic electrical properties of the epitaxial Bi2O2Se films.
The Bi2O2Se film was fabricated into standard Hall bar devices
(more details can be found in the Experimental Section). The
high mobility of Bi2O2Se films enables the observation of Shub-
nikov–de Haas (SdH) quantum oscillations in a Hall bar device
with 4 µm-long, 2 µm-wide, and 4-UC-thick channel (Figure 4c).
Note that the SdH oscillations originate from the formation of
Landau levels, which requires ωcτ > 1. Here, ωc is the cyclotron
frequency, and τ is the mean free path. The above condition is
equivalent to μB > 1, where μ is the mobility, and B is the mag-
netic field. Bmin is estimated to be around 2.5 T; therefore, the
mobility is higher than 4 × 103 cm2 V−1 s−1 (1.8 K). The low-
temperature and room-temperature Hall mobility (µHall) of
the above 4-UC-thick sample extracted from the Hall curve is
7678 cm2 V−1 s−1 (1.8 K) and 280 cm2 V−1 s−1, respectively. The
2D nature of the Bi2O2Se film was also confirmed through the
angular dependence of the SdH oscillations; thus, the epitaxial
Bi2O2Se films represent a new high-mobility 2D material system
for exploring novel physics. Besides, the room-temperature µHall
values of MBE-grown Bi2O2Se films with a thickness ranging
from 2 to 6 UC exceed 280 cm2 V−1 s−1 while the room-temperature
µHall of the 1-UC Bi2O2Se film reduces to 180 cm2 V−1 s−1
(Figure 4d). The decrease of carrier mobility in the 1-UC
Bi2O2Se film is presumably due to the scattering caused by the
strain around the steps mentioned above. Nevertheless, consid-
ering the ultrasmall effective mass,[19,29,36] electrons in ultrathin
Bi2O2Se films exhibit remarkably high mobility, which exceeds
that of silicon[15] and other 2D semiconductors[37–39] with com-
parable thickness. In the future, it is expected that the carrier

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mobility in ultrathin Bi2O2Se devices can be further optimized
by fabricating the device with a short channel on the terrace
to eliminate the scattering around the steps. These excellent
intrinsic electrical properties make 2D Bi2O2Se a competitive
candidate for future electronics.
3. Conclusion
We have proposed an advanced heteroepitaxy strategy, namely,
step-climbing epitaxy, based on the MBE growth of 2D Bi2O2Se
epilayers on SrTiO3 substrates with a negligible in-plane but giant
out-of-plane lattice mismatch. Taking advantage of step-climbing
epitaxy, uniform wafer-scale Bi2O2Se films with controllable thick-
ness in the range from ML to several nanometers can be obtained.
1-UC Bi2O2Se films show a Hall mobility as high as 180 cm2 V−1 s−1
at room temperature, which exceeds that of silicon and other
2D semiconductors with comparable thickness. By taking into
account the out-of-plane lattice mismatch in step-climbing epi-
taxy, our work expands the existing epitaxial growth theory. Our
findings may be useful in achieving the high-quality synthesis of
other layered materials, which is crucial for the development of
the semiconductor industry and the discovery of novel physics.
4. Experimental Section
First-Principles DFT Calculations: The projector-augmented wave
pseudopotential with a plane-wave basis set was used in the DFT
calculations.[40] The plane-wave cutoff energy was set to 400 eV. A
SrTiO3 nanoribbon with a width of 15.6 Å placing on four periodic layers
of SrTiO3 was used to model the stepped SrTiO3 substrate, where the
two upmost SrTiO3 layers and Bi2O2Se were relaxed until the force
on each atom is less than 0.02 eV Å−1 with an energy convergence of
10−5 eV, while the bottom two SrTiO3 layers were fixed as bulk. The in-plane
lattice constant of the unit cell is 46.86 Å × 3.90 Å and a vacuum region
of ≥20 Å was chosen to exclude periodic interactions in z direction. A
1 × 8 × 1 Monkhorst–Pack k-mesh was used to sample the 2D Brillouin
zone. The formation energy is defined as Ef = EBOS/STO − EBOS − ESTO,
where EBOS/STO, EBOS, and ESTO are the calculated energies of the Bi2O2Se
nanoribbon attached to the stepped SrTiO3 substrate, the Bi2O2Se
nanoribbon, and the stepped SrTiO3 substrate.
Bi2O2Se Film Growth and Characterization: The Bi2O2Se films were
grown in a homemade oxide molecular beam epitaxy (OMBE) system
equipped with O2, Bi (99.999%), and Se (99.999%) sources. The base
pressure was better than 5 × 10−10 mbar. Single-slide-polished SrTiO3
with a thickness of 0.5 mm were used as the substrates. The substrates
were heated by radiation heating method and the temperature was
measured via an infrared pyrometer. Before the growth of Bi2O2Se
films, the SrTiO3 substrates were pretreated in ultrahigh vacuum (UHV)
at 950 °C for 50 min to obtain single TiO2-terminated surface. Then
the substrates were annealed at 600 °C under the oxygen pressure of
1.3 × 10−4 mbar for 15 min to eliminate oxygen vacancies formed in
the first step annealing. The Bi2O2Se film growth was performed by
coevaporating Bi and Se under the above oxygen pressure with growth
temperature keeping at 380 °C. The Bi source was set at 610 °C with a
flux of ≈0.75 Å min−1 measured via quartz crystal oscillator (QCO). To
stop the growth, the Bi and Se shutters were closed simultaneously and
the sample was cooled naturally to room temperature.
A Bruker Nanoscope system (Dimension Icon) working in ScanAsyst
mode was used to obtain the AFM images. The XRD measurements
were performed using a Rigaku SmartLab (9 kW) X-ray diffractometer via
a Ge (220) × 2 crystal monochromator. The atomic-resolution STEM was
conducted on an aberration-corrected transmission electron microscope
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FEI Titan Cubed Themis G2 at 300 kV. The Raman spectra were collected
with a confocal Raman spectrometer (Jobin Yvon LabRAM HR800) using
a He–Ne laser (532 nm).
Device Fabrication and Measurement: The array of four-terminal and
multiple-terminal devices was fabricated with multiple overlay exposure.
The MBE-grown 10 nm-thick Bi2O2Se film was firstly patterned into
discrete 40 × 20 or 800 × 30 µm2 rectangles by laser direct writing
(LDW) and wet chemical etching (WCE) method. The etchant is dilute
H2O2 and protonic mixture acid (H2SO4:H2O2:H2O = 1:2:4).[40] Then
a second LDW process was applied to create a photoresist mask that
exposed electrodes for depositing 7/45 nm Pd/Au electrodes by e-beam
evaporation. The position for the second laser direct writing was strictly
aligned with the previous patterns with the help of cross marks. The
maskless laser direct writing instrument used was Heidelberg MLA150.
The Hall devices were fabricated directly on Bi2O2Se films grown on
SrTiO3 substrates. The MBE-grown Bi2O2Se films were firstly patterned
into discrete 40 × 20 µm2 rectangles by LDW and WCE method. Second,
alignment marker arrays were predefined onto the SrTiO3 substrates with
standard photolithography technique. The photolithography instrument
used was SUSS MA6 Gen4. Then Hall bar patterns can be obtained by
standard electron beam lithography (EBL) and ion beam etching (IBE)
with poly(methyl methacrylate) (PMMA) mask. The IBE instrument
used was LKJ-150. Finally, EBL (Quanta 250FEG) was used to write
multiple metal contacts for six-terminal Hall-bar devices. Ohmic contact
was formed using Pd/Au metal electrodes (7 nm/45 nm) by e-beam
evaporation (DE400). The instruments used for resistance measurement
at room temperature were Lakeshore CRX-VF and KeySight B1500A and
the instruments used for low-temperature transport measurement were
Quantum Design DynaCool-9 and Attocube AttoDry2100.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
X.Z., Y.L., and H.F. contributed equally to this work. The authors
acknowledge Molecular Materials and Nanofabrication Laboratory (MMNL)
in the College of Chemistry and Molecular Engineering at Peking University
for the use of instruments. This work was supported by the National
Natural Science Foundation of China (21733001, 21920102004, 52021006,
and T2188101), Beijing National Laboratory for Molecular Sciences
(BNLMS-CXTD-202001), and the Tencent Foundation (XPLORER PRIZE).
Conflict of Interest
The authors declare no conflict of interest.
Data Availability Statement
The data that support the findings of this study are available from the
corresponding author upon reasonable request.
Keywords
bismuth oxyselenide, epitaxial growth, high mobility, layered materials,
wafer-scale single-crystal thin films
Received: March 25, 2022
Revised: July 19, 2022
Published online: September 15, 2022
© 2022 Wiley-VCH GmbH

www.advancedsciencenews.com
[1] H. Kum, D. Lee, W. Kong, H. Kim, Y. Park, Y. Kim, Y. Baek,
S. H. Bae, K. Lee, J. Kim, Nat. Electron. 2019, 2, 439.
[2] H. Y. Hwang, Y. Iwasa, M. Kawasaki, B. Keimer, N. Nagaosa,
Y. Tokura, Nat. Mater. 2012, 11, 103.
[3] P. Zubko, S. Gariglio, M. Gabay, P. Ghosez, J. M. Triscone, Annu.
Rev. Condens. Matter Phys. 2011, 2, 141.
[4] Y. J. Chung, K. A. V. Rosales, K. W. Baldwin, P. T. Madathil,
K. W. West, M. Shayegan, L. N. Pfeiffer, Nat. Mater. 2021, 20, 632.
[5] A. Koma, J. Cryst. Growth 1999, 201, 236.
[6] M. Wang, M. Huang, D. Luo, Y. Li, M. Choe, W. K. Seong, M. Kim,
S. Jin, M. Wang, S. Chatterjee, Y. Kwon, Z. Lee, R. S. Ruoff, Nature
2021, 596, 519.
[7] L. Wang, X. Z. Xu, L. N. Zhang, R. X. Qiao, M. H. Wu, Z. C. Wang,
S. Zhang, J. Liang, Z. H. Zhang, Z. B. Zhang, W. Chen, X. D. Xie,
J. Y. Zong, Y. W. Shan, Y. Guo, M. Willinger, H. Wu, Q. Y. Li,
W. L. Wang, P. Gao, S. W. Wu, Y. Zhang, Y. Jiang, D. P. Yu,
E. G. Wang, X. D. Bai, Z. J. Wang, F. Ding, K. H. Liu, Nature 2019,
570, 91.
[8] T. A. Chen, C. P. Chuu, C. C. Tseng, C. K. Wen, H. S. P. Wong,
S. Y. Pan, R. T. Li, T. A. Chao, W. C. Chueh, Y. F. Zhang, Q. Fu,
B. I. Yakobson, W. H. Chang, L. J. Li, Nature 2020, 579, 219.
[9] T. T. Li, W. Guo, L. Ma, W. S. Li, Z. H. Yu, Z. Han, S. Gao, L. Liu,
D. X. Fan, Z. X. Wang, Y. Yang, W. Y. Lin, Z. Z. Luo, X. Q. Chen,
N. X. Dai, X. C. Tu, D. F. Pan, Y. G. Yao, P. Wang, Y. F. Nie,
J. L. Wang, Y. Shi, X. R. Wang, Nat. Nanotechnol. 2021, 16, 1201.
[10] J. H. Wang, X. Z. Xu, T. Cheng, L. H. Gu, R. X. Qiao, Z. H. Liang,
D. D. Ding, H. Hong, P. M. Zheng, Z. B. Zhang, Z. H. Zhang,
S. Zhang, G. L. Cui, C. Chang, C. Huang, J. J. Qi, J. Liang, C. Liu, Y.
G. Zuo, G. D. Xue, X. J. Fang, J. P. Tian, M. H. Wu, Y. Guo, Z. X. Yao,
Q. Z. Jiao, L. Liu, P. Gao, Q. Y. Li, R. Yang, et al., Nat. Nanotechnol.
2022, 17, 33.
[11] Y. Kim, S. S. Cruz, K. Lee, B. O. Alawode, C. Choi, Y. Song,
J. M. Johnson, C. Heidelberger, W. Kong, S. Choi, K. Qiao,
I. Almansouri, E. A. Fitzgerald, J. Kong, A. M. Kolpak, J. Hwang,
J. Kim, Nature 2017, 544, 340.
[12] S. Manzeli, D. Ovchinnikov, D. Pasquier, O. V. Yazyev, A. Kis, Nat.
Rev. Mater. 2017, 2, 17033.
[13] Y. Liu, X. D. Duan, Y. Huang, X. F. Duan, Chem. Soc. Rev. 2018, 47,
6388.
[14] Y. Liu, X. D. Duan, H. J. Shin, S. Park, Y. Huang, X. F. Duan, Nature
2021, 591, 43.
[15] Y. Liang, X. H. Zhou, W. Li, H. L. Peng, APL Mater. 2021, 9, 060905.
[16] W. H. Zhang, Y. Sun, J. S. Zhang, F. S. Li, M. H. Guo, Y. F. Zhao,
H. M. Zhang, J. P. Peng, Y. Xing, H. C. Wang, T. Fujita, A. Hirata,
Z. Li, H. Ding, C. J. Tang, M. Wang, Q. Y. Wang, K. He, S. H. Ji,
X. Chen, J. F. Wang, Z. C. Xia, L. Li, Y. Y. Wang, J. Wang, L. L. Wang,
M. W. Chen, Q. K. Xue, X. C. Ma, Chin. Phys. Lett. 2014, 31, 017401.
[17] Q. M. Si, R. Yu, E. Abrahams, Nat. Rev. Mater. 2016, 1, 16017.
[18] J. X. Wu, H. T. Yuan, M. M. Meng, C. Chen, Y. Sun, Z. Y. Chen,
W. H. Dang, C. W. Tan, Y. J. Liu, J. B. Yin, Y. B. Zhou, S. Y. Huang,
H. Q. Xu, Y. Cui, H. Y. Hwang, Z. F. Liu, Y. L. Chen, B. H. Yan,
H. L. Peng, Nat. Nanotechnol. 2017, 12, 530.
[19] T. R. Li, T. Tu, Y. W. Sun, H. X. Fu, J. Yu, L. Xing, Z. Wang,
H. M. Wang, R. D. Jia, J. X. Wu, C. W. Tan, Y. Liang, Y. C. Zhang,
C. C. Zhang, Y. M. Dai, C. G. Qiu, M. Li, R. Huang, L. Y. Jiao,
K. J. Lai, B. H. Yan, P. Gao, H. L. Peng, Nat. Electron. 2020, 3, 473.
Adv. Mater. 2022, 34, 2202754 2202754 (8 of 8)
15214095, 2022, 42, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adma.202202754 by National Center For, Wiley Online Library on [18/03/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
www.advmat.de
[20] Z. Y. Zhang, T. R. Li, Y. J. Wu, Y. J. Jia, C. W. Tan, X. T. Xu,
G. R. Wang, J. Lv, W. Zhang, Y. H. He, J. Peng, C. Ma, G. Q. Li,
H. Z. Xu, L. P. Shi, H. L. Peng, H. L. Li, Adv. Mater. 2018, 31, 1805769.
[21] T. Ghosh, M. Samanta, A. Vasdev, K. Dolui, J. Ghatak, T. Das,
G. Sheet, K. Biswas, Nano Lett. 2019, 19, 5703.
[22] J. B. Yin, Z. J. Tan, H. Hong, J. X. Wu, H. T. Yuan, Y. J. Liu, C. Chen,
C. W. Tan, F. R. Yao, T. R. Li, Y. L. Chen, Z. F. Liu, K. H. Liu,
H. L. Peng, Nat. Commun. 2018, 9, 3311.
[23] Q. D. Fu, C. Zhu, X. X. Zhao, X. L. Wang, A. Chaturvedi, C. Zhu,
X. W. Wang, Q. S. Zeng, J. D. Zhou, F. C. Liu, B. K. Tay, H. Zhang,
S. J. Pennycook, Z. Liu, Adv. Mater. 2019, 31, 1804945.
[24] T. Tong, Y. F. Chen, S. C. Qin, W. S. Li, J. R. Zhang, C. H. Zhu,
C. C. Zhang, X. Yuan, X. Q. Chen, Z. H. Nie, X. R. Wang, W. D. Hu,
F. Q. Wang, W. Q. Liu, P. Wang, X. F. Wang, R. Zhang, Y. B. Xu, Adv.
Funct. Mater. 2019, 29, 1905806.
[25] S. P. Xu, H. X. Fu, Y. Tian, T. Deng, J. Cai, J. X. Wu, T. Tu, T. R. Li,
C. W. Tan, Y. Liang, C. C. Zhang, Z. Liu, Z. K. Liu, Y. L. Chen, Y. Jiang,
B. H. Yan, H. L. Peng, Angew. Chem., Int. Ed. 2020, 59, 17938.
[26] T. R. Li, H. L. Peng, Acc. Mater. Res. 2021, 2, 842.
[27] C. W. Tan, M. Tang, J. X. Wu, Y. N. Liu, T. R. Li, Y. Liang, B. Deng,
Z. J. Tan, T. Tu, Y. C. Zhang, C. Liu, J. H. Chen, Y. Wang, H. L. Peng,
Nano Lett. 2019, 19, 2148.
[28] Y. Liang, Y. J. Chen, Y. W. Sun, S. P. Xu, J. X. Wu, C. W. Tan, X. F. Xu,
H. T. Yuan, L. X. Yang, Y. L. Chen, P. Gao, J. D. Guo, H. L. Peng, Adv.
Mater. 2019, 31, 1901964.
[29] Y. K. Song, Z. J. Li, H. Li, S. J. Tang, G. Mu, L. X. Xu, W. Peng,
D. W. Shen, Y. L. Chen, X. M. Xie, M. H. Jiang, Nanotechnology
2020, 31, 165704.
[30] M. Kang, H. J. Chai, H. B. Jeong, C. Park, I. Y. Jung, E. Park,
M. M. Çiçek, I. Lee, B. S. Bae, E. Durgun, J. Y. Kwak, S. Song,
S. Y. Choi, H. Y. Jeong, K. Kang, ACS Nano 2021, 15, 8715.
[31] F. Sanchez, C. Ocal, J. Fontcuberta, Chem. Soc. Rev. 2014, 43, 2272.
[32] J. Lapano, M. Brahlek, L. Zhang, J. Roth, A. Pogrebnyakov, R. Engel-
Herbert, Nat. Commun. 2019, 10, 2464.
[33] J. K. Huang, Y. Wan, J. J. Shi, J. Zhang, Z. H. Wang, W. X. Wang,
N. Yang, Y. Liu, C. H. Lin, X. W. Guan, L. Hu, Z. L. Yang,
B. C. Huang, Y. P. Chiu, J. Yang, V. Tung, D. Y. Wang, K. Kalantar-
Zadeh, T. Wu, X. T. Zu, L. Qiao, L. J. Li, S. Li, Nature 2022, 605, 262.
[34] M. H. Xie, S. M. Seutter, W. K. Zhu, L. X. Zheng, H. Wu, S. Y. Tong,
Phys. Rev. Lett. 1999, 82, 2749.
[35] C. Chen, M. X. Wang, J. X. Wu, H. X. Fu, H. F. Yang, Z. Tian, T. Tu,
H. Peng, Y. Sun, X. Xu, J. Jiang, N. B. M. Schröter, Y. W. Li, D. Pei,
S. Liu, S. A. Ekahana, H. T. Yuan, J. M. Xue, G. Li, J. F. Jia, Z. K. Liu,
B. H. Yan, H. L. Peng, Y. L. Chen, Sci. Adv. 2018, 4, eaat8355.
[36] X. Cui, G. H. Lee, Y. D. Kim, G. Arefe, P. Y. Huang, C. H. Lee,
D. A. Chenet, X. Zhang, L. Wang, F. Ye, F. Pizzocchero, B. S. Jessen,
K. Watanabe, T. Taniguchi, D. A. Muller, T. Low, P. Kim, J. Hone,
Nat. Nanotechnol. 2015, 10, 534.
[37] B. W. H. Baugher, H. O. H. Churchill, Y. F. Yang, P. Jarillo-Herrero,
Nano Lett. 2013, 13, 4212.
[38] N. R. Pradhan, D. Rhodes, S. Memaran, J. M. Poumirol, D. Smirnov,
S. Talapatra, S. Feng, N. Perea-Lopez, A. L. Elias, M. Terrones,
P. M. Ajayan, L. Balicas, Sci. Rep. 2015, 5, 8979.
[39] G. Kresse, J. Furthmuller, Phys. Rev. B 1996, 54, 11169.
[40] J. X. Wu, Y. J. Liu, Z. J. Tan, C. W. Tan, J. B. Yin, T. R. Li, T. Tu,
H. L. Peng, Adv. Mater. 2017, 29, 1704060.
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