Article

Cite This: J. Phys. Chem. C 2019, 123, 26467−26474 pubs.acs.org/JPCC

Atomistic Insights into Cu Chemical Mechanical Polishing

Mechanism in Aqueous Hydrogen Peroxide and Glycine: ReaxFF
Reactive Molecular Dynamics Simulations
Jialin Wen,*,† Tianbao Ma,*,† Weiwei Zhang,‡ Adri C. T. van Duin,*,‡,§ Diana M. van Duin,§
Yuanzhong Hu,† and Xinchun Lu*,†
†
State Key Laboratory of Tribology, Tsinghua University, Beijing 100084, China
‡
Department of Mechanical and Nuclear Engineering, Pennsylvania State University, University Park, State College, Pennsylvania
16802, United States
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§
RxFF_Consulting LLC, State College, Pennsylvania 16801, United States
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*
S Supporting Information

ABSTRACT: To clarify the chemical mechanical polishing (CMP) mechanism of Cu in

aqueous hydrogen peroxide and glycine, we developed a ReaxFF reactive force field to
describe the interaction between Cu, slurry (H2O, H2O2, and glycine), and the silica abrasive.
Based on this force field, we used molecular dynamics simulations to illustrate the chemistry at
the Cu/silica abrasive interface and Cu atom removal mechanism during the Cu CMP
process. Our results indicate that H2O easily chemically adsorbs on the Cu surface, and H2O2
can dissociate into hydroxyl radicals, forming Cu−OH. Besides, the OH-terminated silica
surface can chemically interact with the Cu substrate, leading to the formation of Cu−OH on
the Cu substrate. During the CMP process, Cu atoms on the substrate are effectively removed
due to the mechanical sliding process-induced chemical reactions, including mainly three
removal pathways: shear-induced glycine-adsorbed Cu atom removal process, shear-induced
OH-adsorbed Cu atom removal process, and shear-induced Cu atom removal process due to
the formation of interfacial Cu−O−Si bridge bonds. These results provide atomistic insights
into the chemical reactions under mechanical effects in the Cu CMP process, thus helping the slurry design and process
parameter optimization.

1. INTRODUCTION for this purpose.17−21 To reduce the corrosion of the Cu

Cu has been widely used as the interconnect material in the
integrated circuit (IC) semiconductor manufacturing process
due to its low resistivity and high electro-migration
resistance.1−5 Cu interconnections are patterned for the IC
chips using the damascene process,5,6 during which Cu is
deposited in dielectric grooves, and excessive Cu materials are
removed using the chemical mechanical polishing (CMP)
process. However, CMP is faced with challenges that defects,
such as dishing and erosion,7−9 are formed during this process,
resulting in the decrease of the reliability of interconnections.
Therefore, it is required to produce a surface without defects.
Besides, to satisfy the deposition process of the interlayer
dielectric, CMP is also required to achieve an atomically planar
surface.
During the CMP process, the pad and Cu-deposited wafer
interface is filled with slurry, which usually contains an
oxidizer, a complexing agent, an inhibitor, a buffering agent,
and abrasive particles. The oxidizer is used to speed up the
formation of an oxidized layer on the Cu surface, and hydrogen
peroxide (H2O2) is widely used as the oxidizer because it has
the high oxidizing ability and causes no contamination.10−19
The complexation agent is used to reduce the copper oxides
formed on the surface, and glycine (C2H5NO2) is usually used
surface, the inhibitor such as the benzotriazole is
used.11,12,16,22,23 The buffering agent is applied to maintain
the pH value of the slurry.14 The abrasive particles are used to
enhance the mechanical removal of the oxidized copper
surface, and both colloidal silica16,21,24−26 and alumina
particles13,18,20,27,28 are widely used. During the Cu CMP
process, both hydrogen peroxide and glycine play critical roles.
X-ray photoelectron spectroscopy results reveal that the
increase of hydrogen peroxide concentration leads to the
decrease of Cu removal rate because of the formation of less
soluble copper oxide, and the addition of glycine in the H2O2
containing slurry can help increase the removal rate due to the
formation of Cu−glycine complex compounds.18 Fourier
transform-electrochemical impedance spectroscopy was used
to probe the surface reactions between Cu, H2O2, and glycine,
and the results suggest that Cu−glycine complexes act as
catalysts for the reduction of H2O2 to hydroxyl radicals, which
enhance the oxidation of the Cu surface to form oxides, and
the oxides interact with glycine to form soluble Cu−glycine
Received: September 5, 2019
Revised: October 9, 2019
Published: October 10, 2019

© 2019 American Chemical Society 26467 DOI: 10.1021/acs.jpcc.9b08466

J. Phys. Chem. C 2019, 123, 26467−26474
The Journal of Physical Chemistry C
Figure 1. Copper and silica interface with H2O, H2O2, and glycine molecules.
complexes.19 These experiments reveal some chemical aspects
in the Cu CMP process, and even though it is experimentally
demonstrated that the removal of Cu can be a combination of
chemical effect-induced surface modification and mechanical
removal of the oxidized surface,14 more detailed polishing
mechanisms are not addressed, such as the mechanical effects
on chemical reactions, which are very important because,
during the Cu CMP process, the Cu polishing rate is much
higher than the Cu dissociation rate.29
Since the Cu CMP process is a dynamical process and
cannot be easily studied in situ due to the inaccessible buried
interface, the optimization of the CMP process parameters
such as pressure, speed, and characteristics of slurry strongly
depends on a large number of trial and error experiments. To
realize the rational design and precise control of CMP
processes with high efficiency and fewer defects, these process
parameters must be established based on the elucidation of the
polishing mechanism. Accordingly, both empirical equa-
tions30−32 and theoretical models33−36 have been developed
to guide the control of CMP parameters for realizing an ideal
material removal rate. However, these models are lack of
insights into the atomistic removal mechanism involved in the
CMP process. To understand the mechanism at the atomistic
level, both atomic force microscopy (AFM) experiments37−41
and molecular dynamics (MD) simulations42−48 have been
employed to investigate the atomistic wear mechanism at the
particle and substrate interface. AFM experiments are helpful
in understanding the possible chemical reactions involved in
the CMP processes by analyzing the chemical species on the
substrate surface before and after the CMP processes, but they
cannot clarify the effects of mechanical force on chemical
reactions. Traditional MD simulations have been successful in
simulating the mechanical process in CMP; however, they fail
in describing the chemical reactions involved in the CMP
processes.
Recently, MD simulations based on the quantum chemistry
method49−56 and reactive force fields57−63 have been adopted
to study the mechanical sliding process in the chemical
environment and demonstrated their ability in elucidating the
interaction between chemical and mechanical effects. Accord-
ing to the tight-binding quantum chemistry MD simulation
results, both pH of the slurry and miller plane strongly
influence the oxidation process of Cu surfaces,64 and shear-
induced intrusion of O atoms adsorbed on the Cu surface into
the Cu bulk contributes to the removal of Cu atoms.56 Besides,
interfacial bridge bonds at the abrasive and substrate interface
play critical roles in the removal of substrate atoms.50,61,65 To
clarify the atomistic mechanism of Cu CMP in aqueous
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hydrogen peroxide and glycine, we use MD simulations based
on the ReaxFF reactive force field66 to investigate the
interfacial chemistry and material removal mechanism in the
Cu CMP process. The ReaxFF reactive force field can describe
chemical reactions, i.e., bond-forming and -breaking processes
occur in the Cu CMP process. Furthermore, MD simulations
can provide the evolution of the CMP system under
mechanical effects, thus helping gain insights into the
mechanical effects on chemical reactions in this process.
The Cu CMP system contains Cu, SiO2 (abrasive particle),
H2O, H2O2, and glycine. According to the experiments, the
interaction between Cu and H2O2 can lead to the production
of cuprous oxide (Cu2O) and cupric oxide (CuO) on the Cu
surface;13,14,19,20,67 therefore, the ReaxFF reactive force field
should be able to describe the interactions between SiO2, Cu,
Cu2O, CuO, H2O, H2O2, and glycine. To this end, we
developed the force field by training against the density
functional theory (DFT) calculation results about reactions
between slurry chemicals (H2O, H2O2, and glycine) and Cu/
Cu2O/CuO with the existing Si/O/H,68 Cu/O/H,69 and C/
O/H/N70 force fields. Then, we verified the developed force
field by comparing the binding energy values calculated using
ReaxFF and DFT methods as well as the structural parameters,
the details can be found in the Supporting Information. In the
following, we first describe the computational methods in
Section 2, and then we present the results and discussion in
Section 3. Conclusions are given in Section 3.2.
2. COMPUTATIONAL METHODS
Based on the two-body abrasion model between an abrasive
particle and the wafer surface33 and the atomistic contact
model under pressure,71 we constructed the atomistic
simulation model of the Cu CMP process, as illustrated in
Figure 1. The multilayer slab contains 3 parts, the Cu(111)
substrate, the SiO2 abrasive particle, and the slurry. The
Cu(111) substrate, cleaved from a bulk Cu material, contains
4369 atoms. The SiO2 abrasive surface is cleaved from the
quenched silica crystal, similar to the previous work.68 Since
the surface of the colloidal silica used in the Cu CMP process
is characterized with the Si−OH structure,72,73 the surface of
the SiO2 model is hydroxylated. The entire abrasive surface
contains 1296 Si, 2708 O, and 232 H. Besides, the slurry
contains 200 H2O, 10 H2O2, and 5 C2H5NO2. The size of the
simulation model box is 6.34 × 5.90 × 4.50 nm3.
For the purpose of MD simulations, the system is divided
into five layers: (1) rigid-body layer of the bottom Cu substrate
atoms, which is constrained to be stationary in the entire
simulations, (2) free Cu substrate layer with atoms allowed to
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move dynamically in the simulations, (3) slurry at the Cu/SiO2

interface, (4) free silica layer with atoms allowed to move
dynamically in the simulations, (5) rigid-body layer of the
amorphous silica, which is laterally movable. Periodic
boundary conditions were applied in both x- and y-directions.
Four steps were carried out to mimic the sliding process of the
silica particle on the Cu surface: (1) move silica vertically
toward the Cu surface, compressing the slurry at the interface
until the normal force reaches the normal load (6.0 GPa) to be
applied to the silica, (2) apply a normal load to the top rigid
body of silica along the z-direction, (3) equilibrate the
compressed system for 25 ps, (4) slide the silica laterally
along the x-axis direction at the speed of 40 m/s, i.e., 0.4 Å/ps
for 300 ps. Large-scale Atomic/Molecular Massively Parallel
Simulator74,75 was applied to perform the simulations and
Verlet algorithm was adopted to integrated the atom
trajectories, using NVT ensemble with the Nose−Hoover
thermostat with a time step of 0.25 fs. The temperature was
controlled to be 300 K with a damping constant of 100 fs.
Snapshot pictures of all simulations are produced using
Ovito.76
Figure 3. Chemical interaction between H2O2 and Cu. (a) Before the
3. RESULTS AND DISCUSSION chemical adsorption of H2O2 on the Cu surface. (b) Chemical
adsorption of H2O2 on the Cu surface. (c) Dissociation of H2O2 on
3.1. Interfacial Chemistry in the Cu CMP Process. the Cu surface, (d) ReaxFF-NEB calculation of reaction paths for the
During the CMP process, H2O molecules can chemically H2O2 evolution at the Cu surface (0 K).
adsorb on the Cu surface, as shown in Figure 2a,b, because the
small energy barrier (ΔE5 = 3.04 kcal/mol), as shown in
Figure 3d, demonstrating that H2O2 can easily dissociate on
the Cu surface. Apart from the direct interaction between Cu
and H2O2 that leads to the dissociation of H2O2, proton-
transfer processes between H2O2 and H2O chemically
adsorbed Cu surface (Figure 4a,b) as well as between H2O2,

Figure 2. ReaxFF-NEB calculation of reaction paths for the H2O

evolution at the Cu surface (0 K). (a) Initial configuration of the H2O
and Cu surface. (b) Chemical adsorption of H2O on Cu. (c) The
transition state of the dissociation of H2O on Cu. (d) The final state
of the dissociated H2O on Cu.

chemical adsorption of an H2O molecule on the Cu surface is

exothermic (ΔE1 = −14.99 kcal/mol) with no energy barrier.
Although the dissociation reaction of H2O on the surface is
exothermic (ΔE3 = −13.58 kcal/mol), the energy barrier is up
to 27.86 kcal/mol (ΔE2), which leads to the dissociation of
H2O to be unfavorable at the room temperature. The water
dissociation energy barrier is consistent with the energy barrier
(27.67 kcal/mol) obtained from DFT calculation,77 validating
the applicability of our force field for the description of the
interaction between Cu and H2O.
Besides, we observed that an H2O2 molecule can dissociate
into 2 OH on the Cu surface, forming Cu−OH, as shown in
Figure 3. The H2O2 molecule can also adsorb on the surface
exothermically (ΔE4 = −9.66 kcal/mol) with no energy
barrier. Different from H2O, the H2O2 dissociation on the Cu
surface is highly exothermic (ΔE6 = −136.88 kcal/mol) with a
26469
Figure 4. Chemical interaction between H2O2, Si−OH of the silica
surface, and the H2O chemically adsorbed Cu surface at the interface.
(a, b) Proton-transfer process between H2O2 and H2O chemically
adsorbed Cu surface, (c, d). The proton-transfer process between
H2O2, Si−OH of the silica surface, and a H2O molecule chemically
adsorbed Cu surface.
Si−OH of the silica surface, and the H2O chemically adsorbed
Cu surface (Figure 4c,d) can also lead to the dissociation of
H2O2 and the formation of Cu−OH on the Cu surface. During
our simulation, there are 2 H2O2 molecules dissociating in the
first pathway, while 8 H2O2 molecules dissociate in the second
pathway, demonstrating that the second pathway is the main
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process for the dissociation of H2O2 at the silica and Cu

interface.
In addition, the amine and carboxyl functional groups of
glycine can both chemically interact with the Cu surface,
forming the Cu−N and Cu−O bonds, respectively. According
to the ReaxFF-NEB calculation results shown in Figure 5, the

Figure 6. Chemical interaction between silica surface (Si−OH) and

Cu. (a) Structure before the chemical adsorption of Si−OH on the
Cu surface, (b) chemical adsorption of Si−OH on the Cu surface, (c)
structure before the dissociation of Si−O bond, and (d) dissociation
of Si−O bond and formation of the Cu−OH on the Cu surface.
Figure 5. ReaxFF-NEB calculation of reaction paths for the glycine
3.2. CU ATOM REMOVAL MECHANISM
evolution at the Cu surface (0 K).
During the sliding process, Cu atoms from the substrate are
removed. To illustrate the material removal mechanism
involved in this process, we tracked the removal process of
chemical adsorption process of the glycine on the Cu surface is the Cu atoms that are removed at the sliding interface, and it
exothermic (ΔE8 = −11.00 kcal/mol) with a small energy indicates that glycine molecules, copper hydroxylation, and
barrier (ΔE7 = 0.77 kcal/mol), demonstrating that glycine can hydroxylated silica surface play significant roles in the removal
chemically adsorb on the Cu surface easily. Besides, the glycine process of Cu atoms. As can be seen from Figure 7 and Video
molecules can also attach to the substrate through the nitrogen
atom and one oxygen atom of the carboxyl group, which has
also been reported in the study of the adsorption of glycine on
the Cu surface.78 The formation of Cu−N leads to the
extrusion of the adsorbed Cu atom, which assists the Cu atom
removal process, as further illustrated below. We have also
performed MD simulations of the interaction between glycine
molecules and Cu(111) substrate under 300 K (See Video S1),
which clearly shows that both Cu−N and Cu−O bonds can be
formed between Cu and glycine at the room temperature.
Besides, the extrusion of N-chemisorbed Cu atoms has also
been observed, demonstrating that the Cu−N bond is stronger
than the Cu−O bond, and N of glycine plays a significant role
in the Cu CMP process, which can also be speculated from the
difference of the binding energies of Cu−glycine(N) (−18.5
kcal/mol) and Cu−glycine(O) (−6.95 kcal/mol) on the Cu
substrate calculated using the DFT method at the PBE/TZP
level with D3 dispersion correction. According to the Figure 7. Cu atom partial charge during the interaction between Cu
and glycine and the removal of Cu from the surface during the sliding
experimental results that the Cu dissociation rate is much process. (a) Chemical adsorption of H2O on the Cu surface, (b) after
higher in the solution containing ethylenediamine than that the desorption of H2O from the Cu surface, (c) chemical adsorption
containing glycine or acetic acid in the neutral condition,29 the of glycine molecule on the Cu surface, and (d) dissociation of Cu
−NH2 functional group is much more efficient in the removal from the surface that leads to the formation of Cu−glycine complex
of the Cu atoms compared to the −COOH group, which is compound.
also confirmed by our simulation results.
Finally, since the silica surface is easily terminated with OH S2, once glycine molecule chemically adsorbs on the Cu
in the aqueous environment, OH-terminated silica surface can surface, and after a sliding period, the adsorbed Cu atom is
chemically interact with the Cu surface, as shown in Figure 6. removed, forming the Cu−glycine complex compound at the
When two surfaces are close to each other, the formation of sliding interface. During this process, the surface Cu atom
Cu−OH−Si interfacial bridge bond was observed. During the initially absorbs the H2O molecule, as shown in Figure 7a, and
sliding process, this bridge bond is strained, leading to the during the slide, the desorption of H2O leads to the decrease of
breakage of the Si−O bond and formation of the Cu−OH Cu partial charge, as shown in Figure 7b. When the glycine
bond on the Cu surface. molecule chemically adsorbs on the bare Cu atom and as the
26470 DOI: 10.1021/acs.jpcc.9b08466
J. Phys. Chem. C 2019, 123, 26467−26474
The Journal of Physical Chemistry C
sliding process goes on, the partial charge of the Cu atom
dramatically increases until it is fully removed from the Cu
surface, as shown in Figure 7c,d.
To confirm that glycine molecules at the sliding interface
can enhance the removal of Cu atoms, we compared the Cu
dissociation energy barrier in the conditions of that with and
without glycine adsorption. As illustrated in Figure 8, when
Figure 8. Energy profiles of (a) the dissociation of a Cu atom from
the Cu substrate and (b) the dissociation of a Cu atom from the Cu
substrate during the adsorption of a glycine molecule using ReaxFF-
NEB calculations (0 K).
there is no adsorption of glycine, the dissociation of a Cu atom
from the substrate is highly endothermic (ΔE10 = 41.78 kcal/
mol) with a high-energy barrier (ΔE9 = 61.91 kcal/mol),
which leads to the dissociation of Cu to be unfavorable at low
temperatures. While with the adsorption of a glycine molecule,
the energy barrier (ΔE11 = 18.54 kcal/mol) of the dissociation
of the adsorbed Cu atom is significantly reduced by 43.37 kcal/
mol, demonstrating the effect of glycine molecules in the Cu
CMP process. It should be noted that although the chemical
adsorption of glycine can reduce the energy barrier of the
dissociation of the Cu atom from the substrate, this process
still has a relatively high-energy barrier (ΔE11 = 18.54 kcal/
mol), and it may be difficult to happen at low temperatures, so
that it requires the mechanical sliding process at the interface.
As has been mentioned above, with the dissociation of H2O2
and interaction with the hydroxylated silica surface, Cu−OH
(Figure 10a) forms on the Cu substrate. During the interfacial
sliding process, the H2O molecule interacts with the
hydroxylated Cu atom, leading to the removal of Cu atom
from the substrate, forming the HO−Cu−H2O cluster at the
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sliding interface, as shown in Figure 9 and Video S3. During
this process, the H2O molecule can chemically adsorb on the
Figure 9. Cu atom partial charge during the interaction between Cu−
OH and H2O and the removal of Cu atom from the surface. (a) OH-
adsorbed Cu surface, (b) chemical adsorption of H2O on the Cu
surface, (c) chemical adsorption of another H2O molecule on the Cu
surface, (d) dissociation of Cu from the surface that leads to the
formation of HO−Cu−H2O and (e) HO−Cu−H2O at the sliding
interface.
Cu atom, causing the increase of the Cu partial charge, as
shown in Figure 9b,c. With the dissociation of the Cu atom
from the substrate, the partial charge of the removed Cu atom
increases further until it is fully removed from the substrate, as
shown in Figure 9d,e.
The interaction between the hydroxylated silica surface and
Cu atom can also lead to the removal of Cu atoms, as shown in
Figure 10 and Video S4. When the hydroxylated silica surface
approaches the Cu substrate (Figure 10a), the Cu−O−Si
interfacial bridge bond forms at the sliding interface (Figure
10b). As the sliding process continues, the Cu atom is removed
from the substrate (Figure 10c) and remains on the silica
surface (Figure 10d). During this process, Cu partial charge
gradually increases until it is fully removed from the surface,
Figure 10. Cu atom partial charge during the interaction between Cu
and silica surface that leads to the removal of Cu atom from the
surface. (a) Cu atom and silica surface atoms, (b) formation of
interfacial Cu−O−Si bond, (c) dissociation of Cu−Cu bond due to
the sliding process, and (d) Cu completely dissociates from the Cu
surface and remains at the silica surface.
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demonstrating that the Cu atom undergoes an oxidation
process.
4. CONCLUSIONS
In this work, molecular dynamics simulations based on a newly
developed ReaxFF reactive force field have been employed to
investigate the mechanism of the Cu CMP process in aqueous
hydrogen peroxide and glycine. The interfacial chemical
reactions at the silica abrasive and Cu substrate interface
have been investigated. It demonstrates that H2O, H2O2,
glycine, and silica surface can chemically interact with the Cu
surface. More specifically, H2O is likely to chemically adsorb
on the Cu surface, forming Cu−H2O. H2O2 easily dissociates
into 2 hydroxyl radicals, which adsorb on the Cu surface,
forming Cu−OH. In addition, glycine can chemically adsorb
on the Cu surface to form the Cu−N and Cu−O bonds.
During the sliding process, the hydroxylated silica surface with
Si−OH groups can chemically interact with the Cu substrate
to form Cu−OH−Si bridge bonds at the interface, and the
bridge bonds can be mechanically strained to be broken,
leading to the formation of Cu−OH on the Cu surface. Both
the glycine molecules and hydroxylation of Cu surface play
significant roles in the removal of Cu atoms during the CMP
process. Chemical absorption of glycine can significantly
reduce the dissociation energy barrier of Cu from the substrate,
leading to the removal of Cu atoms much easier under the
sliding process. Besides, the interaction between H2O and Cu−
OH under the shear effects at the sliding effects can also lead
to the removal of Cu atoms. In addition, the chemical reaction
between the hydroxylated silica surface and Cu substrate,
which leads to the formation of interfacial Cu−O−Si bridge,
can induce the dissociation of Cu−Cu bonds from the
substrate, resulting in the removal of Cu atoms. All these three
kinds of Cu removal pathways demonstrate the significance of
synergetic roles of chemical and mechanical effects in the Cu
CMP process. Our results have illustrated the chemical
reactions and atom removal mechanism during the Cu CMP
process, which can help design the slurry compositions and
optimize the Cu CMP process.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.jpcc.9b08466.
Comparisons of the binding energies of slurry chemical
species (H2O, H2O2, and glycine) on the Cu/Cu2O/
CuO surfaces, the properties of H2O, H2O2, glycine,
silica, and Cu calculated using ReaxFF reactive force
field with experimental and DFT results (PDF)
ReaxFF reactive force field parameters for C/H/O/N/
Si/Cu (TXT)
Video S1: Interaction between glycine molecules and
Cu(111) substrate at 300 K (MP4)
Video S2: Shear-induced glycine-adsorbed Cu atom
removal process (MP4)
Video S3: Shear-induced OH-adsorbed Cu atom
removal process (MP4)
Video S4: Shear-induced Cu atom removal process due
to the formation of interfacial Cu−O−Si bridge bonds
(MP4)
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■ AUTHOR INFORMATION
Corresponding Authors
*E-mail: alwynwen@mail.tsinghua.edu.cn (J.W.).
*E-mail: mtb@mail.tsinghua.edu.cn (T.M.).
*E-mail: acv13@psu.edu (A.C.T.v.D.).
*E-mail: xclu@tsinghua.edu.cn (X.L.).
ORCID
Jialin Wen: 0000-0002-0674-5439
Tianbao Ma: 0000-0001-8016-9241
Weiwei Zhang: 0000-0002-5255-7340
Adri C. T. van Duin: 0000-0002-3478-4945
Xinchun Lu: 0000-0002-1630-7651
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
We thank Dr. Yun Kyung Shin of Pennsylvania State
University for the instruction of the ReaxFF-NEB method.
This work was supported by the China Postdoctoral Science
Foundation (2019M650655) and the National Natural Science
Foundation of China (Grant 51935006, 91323302). ACTvD
acknowledges funding from NSF DMR 1609107. Simulations
were carried out on the “Explorer 100” cluster system of
Tsinghua National Laboratory for Information Science and
Technology.
■
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26474 DOI: 10.1021/acs.jpcc.9b08466

J. Phys. Chem. C 2019, 123, 26467−26474