Reactive Molecular Dynamics Simulation of Si
Chemical Mechanical Polishing Process
Jialin Wen
State Key Laboratory of Tribology
Tsinghua University
Beijing, China
wenjI12@mails.tsinghua.edu.cn
Abstract- Reactive molecular dynamics simulations are used to
simulate the chemical mechanical polishing process of silicon
surface. The simulation process is carried out to investigate the
interaction between Si02 particle and Si surface in pure water.
Both chemical and mechanical effects under different pressure
between the silicon surface, water and a silica particle are
clarified. This is the first application of reactive molecular
dynamics simulation in the CMP area. According
simulation results, H20 molecules are adsorbed on both the Si
substrate and Si02 particle surface, OH groups and H atoms are
generated by the adsorption and dissociation of
Interaction of these two surfaces leads to the formation of
-Si-Si-O-Si- bond chain, and Si-Si bond of this bond chain is
easier to be broken rather than the Si-O bond under the
mechanical sliding effects, which leads to the removal of Si atoms.
Besides, different kinds of pressure are applied to the Si02
particle to investigate the role of mechanical pressure effects to
the CMP process, and the results show that higher pressure leads
to the removal of more Si atoms. This work sheds light on the
atomic chemical and mechanical details of the Si CMP process
and may provide efficient ways to design the slurry composites
and optimize the pressure applied in the CMP process.
I. INTRODUCTION
Chemical mechanical polishing (CMP) is a key step of
silicon process in semiconductor technology because it is
crucial to produce a defect free and flat enough surface for
further processing of microelectronic devices. According to
Xiao [1], when the patterning feature size is smaller than
0.25f1m, the surface topography must be controlled to less
than 2000 A to ensure the required photolithography
resolution, and the required planarization level can only be
achieved by using CMP processes.
During the CMP process, there exist complicated
interactions between wafer, slurry, abrasive particles and pad,
which lead to the removal of wafer materials. Microscopic
observations of polished surfaces have shown that material
removal in CMP occurs as a consequence of a combination of
chemical reaction of the slurry chemicals with the wafer
surface materials and the repeated rolling, indentation and
sliding effects of the abrasive particles against the wafer
surface.
In order to understand the chemical mechanical synergy
mechanism at the atomic scale, molecular simulations are
proposed to be an appropriate method to investigate this
mechanism instead. Despite most of the MD simulations
conducted to investigate the mechanical sliding, rolling and
impact effects of particles to the silicon or silicon dioxide
surface, the chemical effects are not involved
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XinchunLu
State Key Laboratory of Tribology
Tsinghua University
Beijing, China
xclu@tsinghua.edu.cn
simulation because of the limit of force fields of
classical molecular dynamics simulation, which cannot
describe chemical reaction during the simulation process.
To bridge the gap between the methods based on first
principles quantum mechanics and the classical MD
methods, some reactive force field with bond order
to the potentials have been proposed, one of them is the
ReaxFF force field, which is developed by van Duin et
al [2]. This is the first reactive force field that contains
water.
dynamics bonds and polarization effects in its
formulation, its flexibility and transferability allows
ReaxFF to be easily extended to many systems of
interest in various domains. In this paper, we used
reactive molecular dynamics simulation method which
is based on ReaxFF force filed to simulate the silicon
CMP process, aimed at exploring the chemical and
mechanical effects involved during this process. We
demonstrate the process of a silica particle slides on the
silicon surface under the aqueous environment.
II. Simulation Details
A. ReaxFF method
The path of the atoms in a MD simulation is followed
through space and time by integrating the equations of
motion. In this work, the forces on the atoms are derived
from the reactive force field (ReaxFF) potential. ReaxFF
is a general bond order dependent force field that
provides accurate descriptions of bond breaking and
bond formation. It differs from the traditional unreactive
force fields that the connectivity in ReaxFF is
determined by bond orders calculated from interatomic
distances that are updated every step, making it able to
describe the chemical reaction between atoms. The
overall system energy in ReaxFF reactive force field is
described using the following equation.
These energy terms are related to bond, lone pair,
overcoordination, undercoordination, valence angle,
conjugation, hydrogen bonding, as well as van der
Waals and Coulomb interactions. In order to calculate
the charge distributions, a charge equilibration method
(EEM) is utilized based on geometry and connectivity.
ReaxFF potential attempts to reproduce the energetics,
both thermodynamics as well as reaction barriers of
relevant materials by fitting against a training set
in the consisting of both quantum mechanics and experimental
 results. Its excellent accuracy and reasonable computational particle moves towards the Si surface until the normal
cost makes the ReaxFF method suited in describing the force of the system becomes stable, then the particle
complex reaction systems using molecular dynamics slides with a constant velocity of 10 mis, i.e., 0.1 Aips,
simulation. ReaxFF has been applied to various research areas along the sliding direction (x direction), whereas the
such as combustion chemistry [3], water/metal oxide fixed layer of the Si substrate is completely frozen
interaction [4]-[6], friction process [7]-[10]. The parallel throughout the whole simulation. In order to control the
implementation of the ReaxFF potential into the LAMMPS system temperature, the two thermostat layers are
[11] package enables
MD simulations involving large coupled to a Langevin thermostat method with a
numbers of particles (�106 atoms) for several nanoseconds, temperature damping constant of 100 fs. The remaining
making my simulation of the Si CMP system possible. atoms of the two free layers and water in the box are
free of constraints so that they can move freely due to
B. Model
the interatomic forces.
In this study, we perform large scale MD simulations of the
sliding process of an amorphous silica particle on a Si III. Results and Discussions
substrate under different normal loads in the aqueous
environment. The simulation model is presented in Figure 1. A. Surface Chemical state

During the process the H20 molecules first get close

to the silicon surface (Fig.2a), and then they are
adsorbed on the Si surface (Fig.2b), dissociate into H
atom and OH group, which are adsorbed on the Si
surface (Fig.2c).
(a) H20 (b) H20

Fig. l . Schematic of the model for reactive molecular dynamics simulation of

Si chemical mechanical polishing process. This figure is rendered using
OVITO [12].

Fig.2. Snapshots of H20 absorption and H20 dissociation process on

In this model, a
Si (l00) reconstructed surface with
Si surface at simulation time of (a) lOOps, (b) 200ps, and (c) 200.25ps
dimensions 76.8 X 76.8 X 13.6 A is chosen as the substrate, it
contains 11 Si layers with 4000 atoms. The substrate in this
Besides, during the process, the H20 molecules also
model is divided into three layers. The bottommost 2 Si layers move towards the SiO, surface (Fig.3b), and then they
is set as the fixed layer, the 3 Si layers just above the fixed are adsorbed on the Si02 surface (F ig.3c), dissociate into
layer is set as the thermostat layer, the rest of the Si layers are H atoms and OH groups, making the Si02 surface
set as the free layer. The amorphous silica particle is cleaved hydroxylated (Fig. 3d).
as a part of a spherical silica particle with a radius of 40A,
which is used as abrasive particles in the polishing slurry
during the CMP process, it contains 1368 atoms. It also
contains three layers, i.e. the rigid layer for applying normal
load on the particle, the thermostat layer and the free layer. A
liquid layer about 0.5nm thick with 1000 water molecules is
inserted between the silica particle and the Si substrate.

C. Simulation process

The simulations are performed using the LAMMPS code.

Periodic boundary conditions are applied to the x y direction
to mimic laterally infinite surface. A time step of 0.25fs is
used with the Verlet algorithm to integrate the trajectories. In
order to investigate the pressure effects to the material
removal process, different normal loads of 0.5GPa, 1GPa,
1.5GPa and 2 GPa are applied uniformly on the rigid layer of
the particle along the -z direction, which was able to move
along the normal direction.
Before the interaction process between the particle and Si
substrate, the system is relaxed at 300K with water molecules
to be considered as rigid bodies for 200ps. A free relaxation
period of 400ps is followed so that the water can react with
both silicon and silica surface to mimic the real situation that
silicon and silica surface are exposed in
environment during Si CMP process. After the relaxation
periods, the normal load is applied to the rigid layer so that the
Fig.3. Snapshots of H2O absorption and H20 dissociation process on
Si02 surface at simulation time of (b) 143.5ps, (c) 200ps, and (d)
200.25ps
B. Si atom removal process
During the sliding process, the Si atoms on the Si
surface are removed under the chemical and mechanical
effects at the interface. Figure 4 shows Si atom removal
process. At the beginning of the interaction, the Si02
surface is terminated with OH group (FigAb), then it
the aqueous reacts with the Si atom on the substrate surface to form
Si-O-Si bond and the H atom dissociates from this OH

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 group to adsorb on the HD molecule, forming H30+ (FigAc). to Figure 7, the area of the original sites of the removed
With the Si02 particle sliding on the Si surface, the first Si-Si atoms becomes larger as the pressure increases.
bond of the Si surface is broken under this mechanical effect Chemical mechanical polishing experiment shows that
(FigAd). Following is another Si-Si bond broken under the Si (100) removal rate will increase if the pressure
further mechanical sliding effects of Si02 particle, with a new increases [13].
Si-Si bond formed (FigAe). The new Si-Si bond is then
stretched during the sliding process (FigAf) and broken 60

(FigAg) because of the stretch process. During this process, 52

50
the -Si-Si-O-Si- bond chain is formed under the chemical (J)
E
effects at the interface, and the Si-Si bond of this chain is � 40
._ 40
(J)
broken under the mechanical sliding effect, which means that "0
III
the Si-Si bond is easier to be broken than the Si-O bond in this E; 30 27
E
bond chain. @
'0 20 17
Q;
-"
5 10
z

0.5 1.0 1.5 2.0

Pressure (GPa)

Fig.6. Number of removed Si atoms under different kinds of pressure

Fig.4. Silicon atom removal process. (a) Front view the interaction moment of
Si02 particle, H20 and Si substrate. Following are the pictures showing the
L
trajectOlY of the atoms in the square region at different time: (b) SI6.75ps, (c)
826.25ps, (d) 855ps, (e) 883.75ps, (f) 927ps, (g) 927.25ps.

Some of the Si atoms that are removed from the surface

becomes part of the Si02 particle (Fig.Sa), while some of them
do not become part of the particle, the Si atom is adsorbed by
two H atoms and two OH groups, it becomes part of the slurry
L
(Fig.Sb), which may be washed away because during the CMP (c11.5GPa (dI2.OGPa
process the slurry flows and is renewed. At the same time,
Fig.7. Original sites of the removed atoms (green colored) on the Si
some atoms of the Si02 particle become part of the Si substrate under different kinds of pressure
substrate surface (Fig.Sc).
D. Discussion
(b) Si atom becomes part (c) Some atoms of the Si02 particle (a) Si atom becomes part
of the slurry become part of the Si surface of the Si02 particle
The simulation results reveal the atomic details of Si
CMP process, showing both chemical and mechanical
effects involved in this process. The chemical effects of
H20 effects make the Si and Si02 surface adsorbed by
H atoms or OH groups, further leading to the linkage of
the two surfaces, and the mechanical effects of the Si02
particle lead to the removal of Si atoms on the Si
surface.
Besides, the pressure of the interface plays an
important role in the CMP process, higher pressure may
Fig.5 Atom transfer during the sliding process ( l 261.75ps)
lead to the larger contact area between the two surfaces,
C. Pressure effects on the Si atom removal process which may lead to the forming and breaking of more
bond chains that link the two surfaces, and thus more
In order to investigate the pressure effect to the Si CMP
removed atoms from the surface. It is noteworthy that a
process, 4 different kinds of pressure is applied to the rigid
relatively thin water layer with a thickness of about
layer of Si02 particle, after a sliding distance of soA, different
O.Snm is used in the simulation considering limitation of
numbers of atoms are removed. As you can see from Figure 6,
computing power, thus the hydrodynamic effects of
the number of Si atoms significantly increases with the
water may be neglected.
pressure increasing. The atoms that are considered removed
because their displacement at this sliding distance is larger IV. Conclusions
than 2.sA, which is around the Si-Si bond length. According
Reactive molecular dynamics simulations are

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 conducted to investigate the Si CMP process by a Si02
particle sliding on the Si surface in pure water. The role of
chemical and mechanical synergy effects are
illustrated that H20 molecules can adsorb on the Si and Si02
particle surface and H atoms and OH groups are generated by
the dissociation of H20 molecules, then the two surfaces
interact with each other to form -Si-Si-O-Si- bond chain, the
Si-Si bond of this chain will be broken under the mechanical
sliding effect of Si02 particle, leading to the removal of Si
atoms on the Si surface. Besides, pressure plays a significant
role in the CMP process that higher pressure leads to the
removal of more Si atoms from the Si surface. To the best of
our knowledge, this is the first application of ReaxFF reactive
molecular dynamics simulation in the area of chemical
mechanical polishing and it shows satisfying simulation
performance in the temporal and spatial scales, which are
important for the simulation CMP process. In the future, OR­
ions or H+ ions can be added to the simulation system to
investigate the effects of pH value to the CMP process for the
design of compositions of efficient slurry.
ACKNOWLEDGMENT
The authors greatly appreciate the financial support of
national Natural Science Foundation of China (91323302).
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