Professional Documents
Culture Documents
At present, the study of the behavior of polymeric films at nanoscale has become a very useful tool to understand how the
principal properties of polymers change as the structure decreases in size. The dependence of properties of the polymers with
the size of the arrangement, is important in the development of devices like nanostructured semiconductors, based on block
copolymers structures. Properties like Glass Transition Temperature , Loss and Storage energy moduli deviate significantly of
the bulk values, and the characterization of them let us manipulate the behavior of these devices. Through the experimentation,
was suggested that the elastic modulus of polymeric nanostructures is dimension dependent, decreasing as the beam width is
decreased below 50 nm. An initial analysis of thin films is developed using a simple model for the leveling of a Newtonian
Fluid, which allows the calculation of viscosity as a function of temperature. Then, a Numerical Solution (through the Radial
Basis Function Method) is implemented in order to find an approximation of the theoretical viscosity previously found. Thus,
the calculation of the viscosity in function, not only of temperature but also of the size of the arrangement, can be performed,
and the previous approximation is able to provide the Glass Transition Temperature as a function of the period of the film. The
behavior of the films is then simulated through RBF-Method;the heat rate-dependence of the leveling process is analized in a 80
nm Structure, and the behavior of a non-symmetric film is simulated for the same period.
1 Introduction
The material properties of polymeric structures exhibit size
dependence when one or more of the dimensions of the system are below 50-100 nm. However, in the most common applications of polymer films, the thickness of the systems does
not approach to this length scale, and the behavior explained
above doesnt affect the properties. On the other hand, in the
micro and nano-electronics industry, the changes in the behavior of thin films are associated with the decreasing in size of
the polymeric nanostructures, and it can deviate significantly
from the bulk one 14 . Thereby, the need of finding these properties becomes evident, but the measurement of them is actually a big trouble, because of the length scale does not let
make experiments easily in order to extract the properties.
Several experimental and theoretical studies have been developed in order to analyse the behavior of thin films on pata Departamento de Materiales, Universidad Nacional de Colombia, Sede
Medellin, Calle 75 79A-51, Bloque M17, Medellin, Colombia
b Institute for Molecular Engineering, Physical Science Division, The University of Chicago, Chicago, Illinois, 60637, United States.
c Materials Science Division, Argonne National Laboratory, 9700 South Cass
Avenue, Argonne, Illinois, 60439, United States
E-mail: daaolayamu@unal.edu.co
E-mail: nealey@uchicago.edu
E-mail: jphernandezo@wisc.edu
110 | 1
2 Experimental Section
The effects of antiplasticization on the mechanical properties
of dense arrays of poly(methyl methacrylate) (PMMA) beams
less than 75 nm in width were investigated by Delcambre 33,
through observation of the deformation and collapse of these
beams during lithographic processing. In that work, Delcambre observed the deformation and collapse of dense, lithographically fabricated grating nanostructures to quantify the
effects of an antiplasticizing additive 35, tris(2-chloropropyl)
phospate (TCPP), on the mechanical properties of PMMA
structures.
Spacing (S)
Beam Width
(BW)
Length (L)
Pitch = BW + S
Aspect Ratio
AS = H/BW
Height
(H)
Silicon Wafer
Figure 1. Schematic of Dense Arrays of Linear Nanostructures. The
Height (H), Beam Width (BW), Spacing (S), Pitch, Length (L) and Aspect
Ratio (AR) are defined as shown. 33
2|
110
Figure 2. Schematic of the Experimental SAXS Layoyt. Polymer grating samples were mounted on a heating stage in a transmission geometry.
Synchrotron X-Rays penetrated the sample and contacted the detector. 35,36
The shapes of antiplasticized PMMA grating nanostructured 80 nm to 400 nm in width were monitored upon heating in situ Small Angle X-Ray Scattering (SAXS) and ex situ
Atomic Force Microscopy (AFM), in order to quantify the
shape evolution, or leveling, of the nanoimprinted patterns as
a function of temperature and TCPP antiplasticizer concentration. Delcambre found that the nanostructures rapidly flowed
into flat films near a critical temperature, T f low , that decreases
monotonically with decreasing initial structure width, caused
by an increase in applied stresses with decreasing period due
to surface tension and a dimension-dependence of Tg . Also, it
was confirmed, through the topographical profiles determined
with SAXS and AFM, that leveling process is driven by surface tension at the air-polymer surface, and that the leveling
rate was less dependent on line width in TCPP-antiplasticized
structures than in structures composed of pure PMMA.
3 Theoretical Model
The focus of this work is the study of thin polymer films subjected to a temperature gradient. In the experimental section
of the research 33,36 , a PMMA sample was used to develop the
leveling in order to extract some important properties. The
system consists in a silicone substrate and a polymeric membrane; a sinusoidal shape is assumed for the last one. The
dimensions of the membrane are around 100 nm (see Fig. 3).
The arrangement has a residual height Hr and a length of repetition interval or Period P.
be neglected (Re 0), and the boundary conditions are determined by means of a stress balance at the interfaces 3840 :
P + 2 u = 0
u = 0,
u = 0
at the Substrate
[ n] = ( n)n,
(1)
(2)
(3)
uy
=0
x
(4)
n=s(n)n
air
polymer
-P + 2u=0
u=0
Figure 3. SEM Transversal Image. Silicon Substrate. Height of the
pattern (H) is 100 nm and the period (P) is 160 nm. The residual layer is 20
nm approximately. 36
u=0
Figure 4. Representation of the Geometry of the Membrane. The
For incompressible fluids, the pressure is not thermodynamic variable. It is a Lagrange multiplier that constrains the
velocity field in order to remain divergence-free. The boundary conditions for pressure were developed for the incompressible Navier-Stokes Equations 41 by Gresho et. al. The
leveling problem is represented by the Stokes Flow, which
leads to the Poisson Equation for the Pressure field:
2 P = 0
(5)
110 | 3
(r2 + c2 )m/2
100
80
80
60
60
40
40
20
20
20
60
100
40
20
20
40
20
60 60
100
80
80
60
60
40
40
20
20
40
20
20
40
20
60 60
(10)
gaussian
40
20
20
40
60
Thin-plate splines have been considered optimal for interpolation of multivariate functions but they only converge linearly. 44,45 In this work, the generalized thin-plate spline function is used to approximate the variables, due to the simplicity
in the formulation of the systems of equations, and it avoids
inclusion of the shape parameter c that is related with multiquadratic and gaussian functions. The implementation of the
RBF into the leveling problem started with the making of a
uniform grid and approaching the velocity and pressure functions, found in the Stokes Equations, as follows:
[
j
N
40
20
20
40
ux u
(11)
uy u
(12)
P P
(13)
20
60
er/c
(9)
(6)
generalized multiquadratic,
60
P
2 u 2 u
+
) j] = 0
j + (
x
x2
y2
(14)
P
2 u 2 u
+
) j] = 0
j + (
y
x2
y2
(15)
stant viscosity 7 105 Pa s and surface tension 0.0382 N/m. These values are
u
u
j +
j] = 0
x
y
(16)
u j = 0
N
[ p j +(2
(17)
nx ny + (2
u
u
u
j )nx nx +2 (
j +
j)
x
y
x
u
j )ny ny ] = 2H
y
f (x) j (kx x j k)
at the Substrate
(7)
where N is the number of total collocation points, j s are unknown coefficients and (kx x j k) is the Radial Basis Function. Commonly used RBFs include: 42,43
2a
r log r
4|
(8)
[(2
j
u
u
u
j )nx ny + (
j +
j )(n2y n2x )
x
y
x
(2
u
j )nx ny ] = 0
y
u j =
j
N
u
P
j =
j = 0
x
j x
RBF is able to predict the theoretical behavior of the viscosity, previously found with the Orchards Model.
2
10
Orch.
TG
10
10
10
(21)
10
10
10
330
340
350
360
370
390
400
410
420
0.1
0.2
u [nm/s]
The theoretical velocities of the system can be calculated using the analytical model of Orchard. By this way, it is possible
to use the results of the experimental leveling developed by
Delcambre explained in the experimental section of this paper, where the height of the structure was measured through
the in situ monitoring with the Small Angle X-Ray Scattering, as it was decreasing in function of temperature, in order
to obtain a characteristic curve for the viscosity as a function
of temperature, by minimizing the residual error between the
experimental velocity calculated from the measured height of
the experiments and the theoretical velocity found based on
the Orchard Model. This calculation was developed through a
least square minimization between the experimental and theoretical velocities, using the MINPACK library 47, with the purpose of find values of viscosity, which allowed minimize that
residual error.The analysis explained above is able to provide a
continuous viscosity profile that passes through the glass transition, observed at the inflexion point.
380
0.3
0.4
0.5
u Orch.
u
RBF.
0.6
0.7
330
340
350
360
370
380
390
400
410
420
10
Orch.
RBF.
1
10
10
10
10
10
10
330
340
350
360
370
380
390
400
410
420
110 | 5
h
h
= uy ux
(22)
t
x
where h is the height function that represents the free surface, and ux and uy are the fluid velocity components. With
the purpose of avoid temporal instabilities in the simulation,
an adaptive time-step is implemented as a function of the maximum velocity in the film, as follows:
tadapt. =
k
umax.
(23)
ki j (x j xi ) = 0
(24)
110
yix =
yixx =
1
(y 8yi1 + 8yi+1 yi+2 )
12h i2
(26)
1
(yi2 + 16yi1 30yi + 16yi+1 yi+2 ) (27)
12h2
2 yn+1
2 yn
i
= (1 ) 2i +
2
x
x
Ni
2 ynj
2
j=1 x
Ni
(28)
(29)
10
10
10
0.000494
t = 240 s.
t = 0 s.
0.0108
120
120
0.00862
0.000395
10
100
100
80
80
0.00646
0.000296
60
60
0.00431
0.000198
10
10
40
40
0.00215
9.88e05
20
20
0
60
40
20
20
40
60
3.81e12
60
40
20
20
40
60
6.1e11
12
10
t = 360 s.
120
0.33
t = 390 s.
120
0.594
330
340
350
360
370
380
390
400
410
420
100
100
0.475
0.264
80
80
0.198
0.356
60
60
0.132
0.238
40
lated with the BCs established in the leveling problem in an indirect way. For
Stokes Flow, it is equal to zero, and the RBF approximation leads to a good
40
0.0661
0.119
20
20
0
60
40
20
20
40
60
t = 410 s.
120
5.22e09
60
0.626
40
20
20
40
60
t = 488 s.
120
approach of the solution of the Poisson Equation for the Pressure Field.
6.14e09
0.0521
100
100
0.0416
0.501
80
80
0.0312
0.375
In this section will be performed a simulation showing the dependence of the leveling of a 80 nm film, with the heat rate of
the arrangement (5 K/min, 10 K/min, 20 K/min).
60
60
0.0208
0.25
40
40
0.0104
0.125
20
20
0
60
40
20
20
40
60
3.5e09
60
40
20
20
40
60
1.88e10
0.9
1
80nm
120nm
160nm
0.8
0.9
0.7
0.8
0.6
0.7
0.5
0.6
0.4
0.5
0.3
0.4
0.2
0.3
0.1
0
330
0.2
340
350
360
370
380
390
400
410
420
0.1
0
330
340
350
360
370
380
390
400
410
420
110 | 7
0.1
01
02
03
04
05
06
07
08
09
1
330
340
350
360
370
380
390
400
410
420
Figure 14. T vs. T for Films with a period of 80 nm, 120 nm and
160 nm .The gradient of Viscosity allows to calculate the Glass Transition
10
80nm
120nm
10
125
TG Bulk : 121 C
160nm
120
10
115
10
110
105
T [C]
10
100
10
95
10
90
85
10
330
340
350
360
370
380
390
400
410
420
80
50
100
150
200
250
300
350
400
Period [nm]
110
Conclusions
Acknowledgements
The authors acknowledge to S.P. Delcambre for the experimental results used in this work. D.A.O-M is grateful to D.
Calle, A. Martiliano, H.A. Castano, for helpful discussions
and support.
(36)
y =
R
xy = 0
(37)
The condition of no-shear stress at the free boundary now
yields:
An Kn + Dn = 0
(38)
With the normal stress balance, we obtain:
Bn =
uy =
P + 2 u = 0
u = 0
An = Bn
(31)
If the pressure term is eliminated of the equation (22) using the divergence of the velocity field, yields the biharmonic
equation:
2 2 = 0
(32)
Suppose that the form of the free surface is arbitrary, and
that it extends in the x-direction. Then, the solution of (23)
may be sought in the form of Complex Fourier Series:
= eiKK n x [An Cosh(Kn y) + Bn Sinh(Kn y)
+ Cn y Cosh(Kn y) + Dn y Sinh(Kn y)] (33)
The coefficients An , Bn , Cn and Dn are calculated using
both, the free and fixed boundary conditions. At the surface,
there is no shear stress component tangential to the liquid-air
interface, but a stress of magnitude /R ( : Surface Tension
and R: Radius of Curvature of the Free Surface) exists normal to the interface. The stress components at the surface are
related by:
(34)
(35)
(39)
(30)
where ux is the x-component of the velocity and uy is the ycomponent. The Reynolds number of the system is zero, because there is not presence of inertial forces, due to the characteristic length of the system is very small. Taking into consideration this condition is obtained the Stokes Equation and
the divergence of velocity field:
an
2
Tanh( ) Sech2( )
1 + 2Sech2( )
1
1 + 2Sech2( )
(41)
Tanh( ) Sech2( )
1 + 2Sech2( )
(42)
Cn = Kn Bn
Dn = Kn Bn
(40)
Kn f ( )
dt)
(43)
where = Kn Hr .
References
1 R. S. Tate, D. S. Fryer, S. Pasqualini, M. F. Montague, J. J. de Pablo and
P. F. Nealey, The Journal of Chemical Physics, 2001, 115, 99829990.
2 M. P. Stoykovich, K. Yoshimoto and P. F. Nealey, Applied Physics A:
Materials Science and Processing, 2008, 90, 277283.
3 R. a. Riggleman, K. Yoshimoto, J. F. Douglas and J. J. De Pablo, Physical
Review Letters, 2006, 97, 14.
4 T. R. Bohme and J. J. De Pablo, Journal of Chemical Physics, 2002, 116,
99399951.
5 C.-c. Liu, A. Ramrez-Hernandez, E. Han, G. S. W. Craig, Y. Tada,
H. Yoshida, H. Kang, S. Ji, P. Gopalan, J. J. D. Pablo and P. F. Nealey,
Macromolecules, 2013, 46, 14151424.
6 G. Liu, F. Detcheverry, A. Ramrez-Hernandez, H. Yoshida, Y. Tada, J. J.
de Pablo and P. F. Nealey, Macromolecules, 2012, 45, 39863992.
7 S. O. Kim, H. H. Solak, M. P. Stoykovich, N. J. Ferrier, J. J. De Pablo and
P. F. Nealey, Nature, 2003, 424, 411414.
8 A. Chakrabarti and H. A. O. Chen, Journal of Polymer Science: Part B:
Polymer Physics, 1998, 36, 31273136.
9 M. P. Stoykovich, H. Kang, K. C. Daoulas, G. Liu, C.-C. Liu, J. J.
de Pablo, M. Muller and P. F. Nealey, ACS nano, 2007, 1, 16875.
10 R. a. Segalman, Materials Science and Engineering: R: Reports, 2005,
48, 191226.
110 | 9
10 |
110