Article

pubs.acs.org/Langmuir

Effect of Pore Structure of Nanometer Scale Porous Films on the

Measured Elastic Modulus
Kris Vanstreels,*,† Chen Wu,†,‡ Mario Gonzalez,† Dieter Schneider,§ David Gidley,∥ Patrick Verdonck,†
and Mikhail R. Baklanov†
†
imec, Kapeldreef 75, 3001 Leuven, Belgium
‡
Katholieke Universiteit Leuven, 3000 Leuven, Belgium
§
Fraunhofer Institute for Materials and Beam Technology, Winterbergstraße 28, 01277 Dresden, Germany
∥
Downloaded via KING FAHD UNIV PETROLEUM & MINERALS on April 8, 2024 at 04:08:16 (UTC).

Department of Physics, University of Michigan, Ann Arbor, Michigan 48109-1040, United States
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

ABSTRACT: The impact of pore structure of nanoporous films on

the measured elastic modulus is demonstrated for silica-based
nanoporous low-k films that are fabricated using an alternative
manufacturing sequence which allows a separate control of porosity
and matrix properties. For this purpose, different experimental
techniques for measuring the elastic properties were compared,
including nanoindentation, laser-induced surface acoustic wave
spectroscopy (LAwave), and ellipsometric porosimetry (EP). The
link between the elastic response of these nanoporous materials and
their internal pore structure was investigated using positronium
annihilation lifetime spectroscopy (PALS), EP, and diffusion
experiments. It is shown that the absolute value of the Berkovich
indentation modulus is very sensitive to the local pore structure and
stiffness of the substrate and can be influenced by densification and/or anisotropic elasticity upon indentation, while on the other
hand spherical indentation results are less sensitive to the local pore structure. The comparison of Berkovich and spherical
indentation results combined with finite element simulations can potentially reveal changes in the internal structure of the film.
For nanoporous films with porosity above the percolation threshold, the elastic modulus results obtained with LAwave and EP
agree very well with spherical indentation results. On the other hand, below the percolation threshold, the elastic modulus values
determined by these techniques deviate from the spherical indentation results. This was explained in terms of specific technique
related effects that appear to be sensitive to the specific arrangement and morphology of the pores.

1. INTRODUCTION on mechanical properties. Ideally, to isolate the effects of

Porous materials are commonly found in nature, both in
biological systems and in natural minerals (bone, zeolites,
sponges, and rocks, among others) and as industrial materials
(ceramics, membranes, foams, cements, semiconductors, and
dielectrics, among others) for a multitude of purposes,
including liquid filtration, catalysis, microelectronics, tissue
engineering, and medical diagnosis, among others. These
materials consist of an organic or inorganic framework that
supports a porous structure. The size of the pores (voids) can
range from the macro-scale (>50 nm) down to the nano-scale
(<2 nm) depending on the application. The present tendency is
to develop and use thin porous films with small pore size below
10 nm. Such materials are necessary for sensors, catalysis,
microelectronics, and biotechnology. In order to successfully
implement these materials in specific applications, it is
important to understand how their mechanical properties
vary with porosity and their pore microstructure. Although
much advancement has been made in this field over the past 4
decades for a wide range of materials, there is relatively little
fundamental understanding of the effects of pore morphology
porosity alone, the different films should exhibit the same
matrix properties. In reality, this is seldom the case for
nanoporous films, and studying the effect of porosity on the
mechanical properties of nanoporous films is often complicated
by the difficulty to control the porosity and matrix properties
separately during fabrication.1,2 On the other hand, it is not
trivial to accurately measure the elastic modulus of nanometer
scale porous thin films.3−6 The measured elastic modulus of a
porous film is actually an effective modulus, which evolves
toward the elastic modulus of the matrix material near zero
porosity. An important challenge is that the actual techniques
used for characterizing bulk materials are hardly applicable in
the case of nanoporous thin films because of the small volume
size of the material under investigation. For this reason, several
advanced destructive and nondestructive techniques have been
developed to characterize the elastic properties of thin films on
Received: June 25, 2013
Revised: August 29, 2013
Published: September 2, 2013

© 2013 American Chemical Society 12025 dx.doi.org/10.1021/la402383g | Langmuir 2013, 29, 12025−12035
Langmuir
substrates, ranging from mechanical tests, optical tests, laser
acoustics, and ultrasonics, among others.7 However, most of
these techniques are still not commonly known and require a
detailed analysis in order to obtain reliable results, especially in
the case of porous films. Complexities of measuring the elastic
modulus include substrate influences, material/probe inter-
actions, and data collection and analysis techniques. Moreover,
there is a lack of fundamental understanding on how the
measured elastic modulus value is influenced by the stiffness of
the matrix, porosity, pore structure, and specific technique-
related effects.
In this work, we compare destructive and nondestructive
experimental techniques that are based on different physical
principles to evaluate the elastic properties of nanometer scale
porous films containing a variety of porosity and pore
morphology: nanoindentation (NI), laser-induced acoustic
wave spectroscopy (LAwave), and ellipsometric porosimetry
(EP). Advantages, disadvantages, and limitations of these
techniques are discussed. Furthermore, the link between the
elastic response of a nanoporous material and its internal pore
structure is investigated using positronium annihilation lifetime
spectroscopy (PALS), EP, and diffusion experiments.
As a typical example of nanoporous films, we focus on silica-
based nanoporous dielectric materials with ultralow dielectric
constants. These materials are used in the semiconductor
industry to insulate the electrical interconnections between
different parts from the chip. The advantage of silica-based
materials is that their chemical properties are similar to SiO2,
making it possible to use traditional technology during their
integration. Over the past several decades, the semiconductor
industry has continuously demanded miniaturization of micro-
electronic devices and higher device density, mainly driven by
the need for increased performance, functionality, and reduced
cost. The introduction of mechanically robust materials with an
ultralow dielectric constant is one of the significant material
changes required to keep performance improvements on pace
with the increasing device density.8 An often-used way to
decrease the dielectric constant of dielectrics is by increasing
the porosity. However, the selection of potential candidates is
facing many challenges because lowering the dielectric constant
of these materials is often accompanied by the degradation of
their chemical and mechanical integrity.8 A factor that plays an
increasing role during the development and various integration
processes of these materials is thermomechanical stress, which
can cause cohesive failure and/or interfacial delamination due
to insufficient mechanical and fracture strength. When the
industry is moving toward more advanced porous dielectrics for
future technology nodes, the optimization of the matrix
mechanical properties and tailoring the pore morphology will
be a key for successful integration. Recently, an alternative
manufacturing sequence for SiCOH-type nanoporous low-k
films was developed that allows the fabrication of nanoporous
films with different porosity and pore structure but with same
matrix properties.9 These films are most suitable for a
comparative evaluation of the elastic properties using different
experimental techniques and to elucidate the impact of
porosity, matrix properties, pore structure, and technique-
related effects on the measured elastic modulus.
2. EXPERIMENTAL DETAILS
2.1. Preparation of Nanometer Scale Porous Films. Nano-
meter scale porous SiCOH-type dielectric films with porosity in the
range of 11%−45% were fabricated using a three-step sequence, as
12026
Article
proposed by Urbanowicz et al.10,11 First, the organosilica matrix
precursor (alkylsilanes) was codeposited with organic porogen (cyclic
hydrocarbons) by plasma-enhanced chemical vapor deposition
(PECVD) on 300 mm Si (100) wafers. Next, the films were exposed
to a He−H2 based plasma afterglow at 280 °C for 350 s to remove the
porogens from the film. Other film deposition conditions were detailed
elsewhere.7,10,11
Finally, an ultraviolet (UV)-assisted thermal cure using either a
broad band UV lamp (wavelength >200 nm) or narrow band UV lamp
(wavelength ∼172 nm) was applied to strengthen the skeleton.10 The
porosity of each film was controlled by changing the porogen loading
during the deposition process. The UV cure process conditions are
kept the same for all the exposed films. Recently, it was demonstrated
that such an approach results in constant matrix properties for
different porogen loads.9 A schematic representation of such films is
shown in Figure 1. The films typically contain an amount of closed and
Figure 1. Schematic representation of a typical SiCOH-type
nanoporous film fabricated on a silicon substrate.
open pores (interconnected network). Besides the artificially
introduced porosity using a certain porogen loading, the framework
or matrix material itself also contains a level of porosity that is defined
by the free volume related to the concentration of volumetric
terminating groups like Si-CH3 and Si−H. After the UV curing step,
the thickness, open porosity, and pore diameter of the films were
measured by EP.12
The film density was calculated based on mass and thickness
measurements. The mass was measured with a high resolution, 300
mm wafer compatible, in-line mass measurement system with an
accuracy better than 0.1 mg. Results of these measurements are
summarized in Table 1. The chemical bond structure of the films was
measured using Fourier transform infrared (FTIR) measurements.
FTIR measurements were performed with a resolution better than 1
cm−1 averaging 64 spectra within the 400−4000 cm−1 range. For every
FTIR analysis, the background spectrum and substrate spectrum
(silicon and 1 nm of thermal oxide) were subtracted. Figure 2
illustrates typical FTIR absorbance spectra of UV cured SiCOH-type
nanoporous thin films with different levels of porosity. The spectrum
reveals several broad absorption bands representing the diversified film
structures. The broad absorption band between 1200 and 950 cm−1
belongs to the Si−O−Si asymmetric stretching mode and consists of
overlapping peaks that correspond to Si−O−Si bonds in different
configurations, including various suboxidized states of the network
(1023 cm−1), SiO2-like network (1075 cm−1), and cage structure. The
C−Hx (x = 2 or 3) stretching band from 2990 to 2840 cm−1 consists
of different vibration modes, of which the asymmetric stretching of C−
H in C−H3 and asymmetric stretching of C−H in C−H2 are the two
main peaks that can be observed. The asymmetric stretching C−H2
vibration mode is a direct evidence of the presence of methylene
groups, which perform a cross-linking function in the films. In contrast,
methyl groups replace a bridging oxygen atom with a terminal group
and disrupt the network. Therefore, the relative ratio of methylene to
methyl groups in the structure of the films is crucial for the integrity of
the network. The absorption band between 900 and 700 cm−1 consists
of overlapping vibration modes from various bond structures. The
three sharp peaks at 840, 804, and 777 cm−1 are assigned to the
coupling of the Si−C stretching and the CH3 rocking modes in the
dx.doi.org/10.1021/la402383g | Langmuir 2013, 29, 12025−12035
Langmuir Article

Table 1. Summary of Physical Properties of UV-Cured integrity of the films.1,13 Qualitatively, this trend can be understood in
SiCOH-Type Nanoporous Filmsa terms of the amount of cage structures relatively to the network bonds
and the number of methylene relative to methyl groups in the
open pore structure of the films. More cage structures and a shift from methylene
thickness porosity diameter film density UV cure to methyl groups are found for higher porosity levels, indicating a
film (nm) (%) (nm) (g/cm3) wavelength
mechanical degradation of the structure of the film (Figure 2).
A1 196 5.9 n.a. 1.583 narrow band However, the exact shape of the elastic modulus versus porosity curve
(λ ∼ 172 nm) depends sensitively on its precise pore structure (pore shape, pore size,
A2 170 10.4 1.18 1.500 and pore interconnectivity).9
A3 220 24.0 1.40 1.289 2.2. Internal Pore Structure Characterization. The intercon-
A4 179 27.3 1.62 1.191 nectivity of the nanoporous thin films is characterized by using PALS,
A5 161 34.5 2.84 1.082 EP, and diffusion experiments.
A6 153 39.8 2.84 0.992 Positron annihilation lifetime spectroscopy (PALS) utilizing a
A7 147 44.5 3.30 0.905 focused beam of positrons is a nondestructive technique for
B1 223 10.9 1.04 1.466 broad band
characterizing pore size distribution and pore interconnectivity in
(λ > 200 nm) porous thin films.14 Positrons stopping in the target can capture an
B2 188 14.8 1.52 1.364 electron and form the electron-positron bound state (positronium).
B3 235 24.7 1.72 1.189
The positronium annihilation lifetime is directly related to the size of
pores in the 0.3−30 nm diameter range, and the diffusion of the
B4 206 31.4 2.66 1.031
positronium within the pores is related to the interconnectivity of the
B5 191 38.3 3.22 0.913 pores. Positronium diffusion is gauged by varying the positron beam
B6 186 43.9 3.42 0.806 implantation energy and hence the depth at which positronium is
B7 175 45.4 3.88 0.791 formed below the film surface. The lifetime spectrum is fitted to
a determine the relative fractions of positronium that annihilates in the
Thickness, open porosity, and pore diameter are measured by
ellipsometric porosimetry. film vs positronium diffusing to and escaping through the surface into
the surrounding vacuum. More details can be obtained from Gidley et
al.14
Ellipsometric porosimetry (EP) is a powerful nondestructive
technique that is suitable for in-line monitoring of porosity and pore
size distribution of low-k dielectric films.12,13,15−19 The ellipsometric
porosimeter EP-10 consists of a SENTECH 801 spectroscopic
ellipsometer (λ = 350−850 nm) and is mounted on a vacuum
chamber that can be filled with a solvent vapor (such as toluene or
water) in a controllable way as shown in the literature.15,20 Changes in
the optical characteristics of the sample during the adsorption/
desporption processes are measured by ellipsometry. By relating the
amount of vapor adsorbed in the films to the change in the sample’s
optical properties, the mean open porosity, pore size distribution, and
internal matrix properties can be extracted. More details can be
obtained from Baklanov and Mogilnikov.15
Molecular diffusion in a nanoporous film that contains both
micropores and mesopores is also capable of revealing its pore
interconnetivity, as shown in ref 21. Diffusion experiments are carried
out on nanoporous thin films by covering the films at the top surface
by a transparent Si3N4 barrier that is impermeable for solvent. The
Si3N4 barrier was deposited with PECVD using NH3, SiH4, and N2
gases. After deposition, the samples are cleaved and introduced in
liquid solvent. In this way, the solvent can only penetrate into the
porous films through the edges and subsequently diffuses laterally. The
transparency of the Si3N4 barrier allows the observation of diffusion as
a color change of the film during top down optical microscope
inspection. From diffusion theory it is known that the mean distance
traveled by a diffusion front is described by the equation

L = 2(Dt )1/2 (1)

where D is a diffusion coefficient and t is the diffusion time. By

Figure 2. FTIR absorption spectra of PECVD SiCOH-type nano-
porous films with different levels of porosity using broad band UV
cure.
Si−(CH3)x (x = 1−3). T-groups correspond to a structure where three
oxygen and one organic group are connected to a single silicon atom,
i.e., O3Si−CH3, while D- and M-groups respectively represent O2Si−
(CH3)2 and OSi−(CH3)3. It is obvious that the introduction of
porosity into the films has detrimental effects on the mechanical
measuring the diffusion distance of the solvent as a function of time,
the diffusion coefficient of the solvent can be calculated. In this work,
isopropanol (IPA) was used as a solvent, which has a molecule size of
about 0.46 nm.22
2.3. Measuring Elastic Properties of Nanoporous Thin Films.
The elastic modulus of the nanoporous thin films is measured by NI,
LAwave, and EP. Nanoindentation is a powerful technique for
measuring elastic properties of thin films.23 In this work, a
nanoindenter XP system (MTS Systems Corporation) with a dynamic
contact module (DCM) and a continuous-stiffness measurement
(CSM) option was used under a constant strain rate condition (0.05
s−1). Indentation experiments were performed using two indenter tip
geometries: a standard diamond Berkovich indenter tip and a sapphire

12027 dx.doi.org/10.1021/la402383g | Langmuir 2013, 29, 12025−12035

Langmuir
spherical indenter tip. The Berkovich tip is a three-sided pyramid that
maintains a self-similar geometry to very small scales and is one of the
most frequently used indenter tips for nanoindentation testing to
measure elastic properties on the nanometer scale. On the other hand,
spherical indentation experiments allow to stay completely in the
elastic range if the indenter radius is large enough and the applied
loads are low enough. For this reason, a large radius (compared to the
film thickness) of 250 μm was selected. For each nanoporous film, 25
indentation experiments are performed with both indenter tip
geometries. For indentation experiments using Berkovich tip
geometry, both the depth of penetration (h) and the applied load
(P) were monitored as the indenter tip is pressed into each sample.
Next, a load versus depth curve was generated from the collected data.
At the maximum indentation depth, the load was kept constant for 10
s. No significant creep was observed in all samples. During the
subsequent unloading segment, the tip is withdrawn to 10% of the
maximum load and then held in contact with the surface for 60 s. The
latter was used to correct the thermal drift. From the experimentally
obtained load−displacement curve, elastic modulus (E) and hardness
(H) can be calculated based on their relationship with the contact area
and the measured contact stiffness (S)
2 Figure 3. (a) Schematic of 3-dimensional indentation model. (b)
S=β Er A
π (2)
Pmax
H=
A (3)
where A is the projected contact area of the indenter with the sample
surface, β = 1.034, and Er is the reduced elastic modulus defined by
⎡ 1 − υ2
1 − υi 2 ⎤
−1
Er = ⎢ + ⎥
⎣ E Ei ⎦ (4)
The reduced elastic modulus takes into account the fact that the elastic
displacements occur in both the sample, with elastic modulus E and
Poisson’s ratio ν, and the indenter tip with elastic constants Ei (1140
GPa) and νi (0.07). The contact area (A) was determined from the
indenter tip shape calibration.24,25
The contact stiffness was determined during the loading segments
of the indentation tests using the CSM mode, in which a small
oscillation with known frequency, amplitude, and phase is superposed
on the nominal applied indentation force. The resulting displacement
response of the indenter and the phase angle between the force and
displacement are measured continuously as a function of the
indentation depth. In this way, the indentation modulus can be
continuously determined as a function of the indentation depth. To
validate the recorded load−displacement data obtained with the
Berkovich tip geometry, three-dimensional finite element modeling
(FEM) simulations of the indentation process were performed (Figure
3a). All simulations were done using the commercial finite-element
code MSC.MARC. Because of the unique symmetry of the Berkovich
indenter, only one-sixth of the mesh is needed. The contact region
between the indenter tip and the thin film is finely meshed in order to
ensure the simulation accuracy at low indentation depths. The
indenter is constrained to move in the thickness direction with a
displacement control at a constant strain rate. The reaction force of the
system and the displacement of the indenter are taken at each
increment. The mechanical behavior of the silicon substrate is
modeled as isotropic, linear-elastic. The thickness of substrate and
the width of thin film and substrate are designed large enough to
ensure that the correct response is sensed by the indenter. The thin
film is considered as a homogeneous isotropic elastic−plastic material
where no hardening effect is allowed. The interface between the thin
film and the substrate is considered as perfectly bonded; therefore, no
delamination is allowed. After defining the geometry and boundary
conditions of the FEM model, simulations are performed for both
loading and unloading processes by carefully selecting the material
properties of the film (effective elastic modulus and yield stress) and
comparing the simulations with the experimental results. This process
is repeated iteratively until a best fit of the experimental results is
12028
Article
Principle of FEM fitting procedure.
found (Figure 3b). For spherical indentation experiments, a zero point
correction was performed by fitting the first 30 nm of the load−
displacement data with the formula P = C(h − h0)3/2 according to the
force−displacement dependency for a Hertzian contact (spherical tip
or flat surface) until an optimum was reached. Here P, h, and h0 are
respectively the applied load on the sample, indentation depth, and
zero point correction. It was shown elsewhere that such a back-
extrapolation method results in an accurate determination of the zero
position.26 After the zero point correction, a 2-dimensional
axisymmetric FEM model of the spherical indentation process is
used to fit the experimentally obtained load−displacement curve and
calculate the elastic modulus of the corresponding film.
This FEM model assumes that the nanoporous film behaves like a
macroscopically homogeneous isotropic material. Homogeneity of the
film can only be assumed when the characteristic length, which defines
the dimension in which the stress−strain analysis is nearly
homogeneous, is large compared to the pore dimension and film
thickness. This is true in case of a spherical indenter with a tip radius
of 250 μm. In this case, an average effective modulus value is calculated
from the load−displacement curves. Figure 4a shows an example for
the measurement of a 220 nm thick low-k film with 24% of porosity
and a maximum force of 6 mN. The zero position h0 was shifted to the
right side until a least-squares fit gives the best agreement between the
fitted curve and the measurement data, as illustrated on Figure 4b.
The laser-induced acoustic wave spectroscopy (LAwave) technique
is based on high frequency surface acoustic waves, whose wave energy
is concentrated at the surface of the material, therefore making them
very sensitive to surface films.27 The acoustic waves are generated by a
short laser pulse in a wide spectral range. Elastic vibrations propagate
along the material surface with a wave amplitude in the range of a few
angstroms and that exponentially decays within the material. For a
homogeneous and isotropic material, the phase velocity c of the surface
acoustic wave can be approximated by
0.87 + 1.12υ E
c=
1+υ 2ρ(1 + υ) (5)
In the case of a thin film on a substrate, the film acts as a perturbing
parameter on the wave phase velocity. The phase velocity c depends
on the film thickness, the internal film stress, the acoustic frequency,
and the elastic parameters and density of both film and substrate
material. This dependence is described elsewhere by a more complex
theory.28 Higher frequency waves are more influenced by the film and
propagate with a velocity closer to that of the film, while lower
frequency waves penetrate deeper into the substrate material and
dx.doi.org/10.1021/la402383g | Langmuir 2013, 29, 12025−12035
Langmuir
Figure 4. (a) Experimental data from the end of the approach segment
and the start of the loading segment and fit curve for Hertzian contact
before zero-point correction. (b) Fitting of the measurement data
using a 2D FEM model (inset).
propagate with a velocity closer to that of the substrate. This results in
a frequency-dependent phase velocity of the surface waves, also termed
dispersion. The experimentally measured dispersion as a spectrum of
phase velocity is fitted by a theoretical curve derived from physical
principles of the elastodynamic theory, yielding the elastic modulus,
density, and/or thickness of the film. The theoretical fitting considers
the nanoporous film as a homogeneous isotropic elastic material. This
fitting procedure depends on many parameters, including the film
density, film thickness, the elastic properties of the film, and substrate
properties. In order to obtain the elastic film properties, most of these
parameters need to be measured by other techniques since it is not
possible to fit so many parameters. For the fitting process, the
measured film density, film thickness (Table 1), and Poisson’s ratio ν
= 0.25 were taken as input parameters. Details of the procedure to
measure the dispersion curve and the theoretical analysis are described
elsewhere.27,28
Ellipsometric porosimetry (EP) is a nondestructive technique that
allows the measurement of the effective pore size and open porosity
based on penetration and condensation of organic vapor in the pores.
It was recently reported that this technique can also be used to
evaluate the mechanical properties of porous films by analysis of film
thickness evolution during EP measurements.13 By coupling the
expression of the Kelvin12 and Young−Laplace29 equations, a model
was obtained describing the evolution of the film thickness when
capillary stress reversibly contracts the film.
P relationship
d = d0(1 − πi /E) = d0 − k 0 ln
P0 (6)
This expression links the film thickness (d) at fixed relative solvent
pressure (P/P0), the unstressed film thickness (d0), the elastic modulus
(E), and the microscopic capillary pressure (πi) across the liquid−air
interface. Fitting the experimental curve describing the change of the
film thickness versus the relative pressure with eq 6 results in the value
for k0 and allows the determination of E
d0RT
E=
k 0VL (7)
12029
Article
where R is the ideal gas constant, T the temperature, and VL the
molecular volume of the adsorbate. Such a fit model depends on the
validity of the Kelvin equation and if capillary condensation promotes
monotonic thickness decrease and increase. More details are described
elsewhere.12,13,15
3. RESULTS AND DISCUSSION
We first focus our attention on the analysis of the nano
indentation measurements to estimate the indentation modulus
of nanoporous films.
Figure 5 illustrates the indentation modulus as a function of
the normalized indentation depth for nanoporous films with
Figure 5. Comparison of the indentation modulus as a function of the
normalized indentation depth for different porous low-k films using a
Berkovich indenter geometry. For each film, 25 indentation modulus
depth profiles were performed.
different porosity using a Berkovich tip. It is evident from this
figure that the experimental indentation modulus increases with
increasing indentation depth. This trend is ascribed to the
presence of a hard and stiff substrate, also referred to as
substrate effect.23,30,31 In fact, the spatial extent of the elastic-
deformation field upon indentation extends well beyond the
actual depth of indentation and eventually may reach the
interface with the substrate and result in an overestimation of
the true indentation modulus of the film. A common-held rule
is that the substrate effects become less important when the
indentation depth is less than 10% of the film thickness.
Although this is true for many film/substrate systems, the exact
range may differ depending on the ratio of the elastic modulus
of film and substrate. A possible way to minimize the substrate
effect is by using very shallow indentation depths for the
extraction of the indentation modulus. One needs to keep in
mind that this can only result in meaningful data if the contact
area-to-depth relationship is accurate enough at these shallow
depths. In the case of a perfect Berkovich tip this relationship
would be given by A(hc) = 24.5hc2.23 In reality, the actual shape
of the indenter tip deviates from the ideal shape; hence, an
expanded equation is often used to describe the area-to-depth
A(hc) = 24.5hc 2 + C1hc1 + C2hc1/2 + C3hc1/4 + ...
+ C8hc1/128 (8)
where C1−C8 are calibration constants of the indenter tip that
need to be determined by performing independent indentation
on a bulk material that is mechanically isotropic and has a
known indentation modulus that does not vary with
indentation depth. Typically, fused silica is selected for tip
calibration. In a previous work, it was demonstrated that by
dx.doi.org/10.1021/la402383g | Langmuir 2013, 29, 12025−12035
Langmuir Article

optimizing the calibration constants C1−C8 and studying the

effect of test parameters and analysis techniques on the
measured indentation modulus, reliable stiffness values were
obtained for indentation depths as small as 15 nm.32 Therefore,
the reported indentation modulus of thin nanoporous films in
this work is estimated at indentation depths between 5% and
8% of the film thickness (Table 1). To validate the
experimentally obtained results, 3-dimensional FEM simula-
tions of the Berkovich indentation process were performed.
Figure 6 illustrates the experimentally obtained load−displace-

Figure 7. Experimentally obtained indentation modulus depth profile

of a nanoporous dielectric film using a Berkovich tip geometry and the
corresponding depth profile obtained from FEM simulations. The
experimental indentation modulus depth profile is the average of 25
experiments.

modulus depth profile in case of a 24.5% naoporous film using

CSM mode with the FEM simulated indentation modulus
depth profile. Good agreement is found between the experi-
ments and the FEM simulations. Similar agreement was also
found in case of nanoporous films with higher porosity.
From this we can conclude that the obtained results by
Berkovich indentation at shallow depths (∼5% of the film
thickness) were not severely influenced by the substrate
stiffness. However, the results obtained by spherical indentation
are about 2−4 times lower compared to Berkovich indentation
results, where the biggest difference was found for lower
porosity levels, as indicated in Figure 8. A possible explanation
for the difference between Berkovich indentation and spherical

Figure 6. (a) Experimentally obtained load−displacement curves and

corresponding best fit using FEM simulation. (b) Comparison of the
experimental indentation modulus and the values obtained from the
best fit using FEM simulation. For each sample, 25 indents were
performed.

ment curve for a 25% and 44% nanoporous film at shallow

indentation depths and the corresponding best fit using FEM
simulation.
During these simulations, the film thickness and hence also
the substrate effect were taken into account. As illustrated in
Figure 6a, the shape of the loading and unloading curve could
nicely be simulated for both low and high porosity films, and
the corresponding indentation modulus extracted from the
simulations revealed a one-to-one relationship with the
experimentally obtained values at shallow indentation depths
(Figure 6b). Based on the experimental values of the
indentation modulus obtained at shallow indentation depths,
the load−displacement curves at larger indentation depths can
also be simulated taking into account the substrate stiffness and
film thickness (Table 1).
From this, the corresponding indentation modulus is Figure 8. Experimentally obtained indentation modulus as a function
calculated at each depth, based on the relationship between of open porosity as measured by Berkovich indentation and spherical
the indentation depth (h), the contact area (A), and the indentation tests for (a) broad band UV cured or (b) narrow band UV
stiffness (S), which can be derived from each unloading curve cured nanoporous films. For each nanoporous film, 25 indents were
(eqs 2 and 4). Figure 7 compares the experimental indentation performed for both tip geometries.

12030 dx.doi.org/10.1021/la402383g | Langmuir 2013, 29, 12025−12035

Langmuir
indentation results may be related to densification of the porous
film upon Berkovich indentation. In fact, the stresses in the film
that are associated with Berkovich indentation can actually
cause the pore structure to collapse, thereby creating a region of
reduced porosity, i.e., a densified zone, underneath the indenter
tip. This in turn generates a densification-induced stiffness
gradient, which can lead to an overestimation of the indentation
modulus of the films, as was reported by several authors.33−36
To illustrate this, Figure 9 shows the calculated out-of-plane
Figure 9. Calculated stress distributions underneath the Berkovich
indenter: (a) out-of-plane stress distribution (b) in-plane stress
distribution.
and in-plane stress distributions underneath the Berkovich
indenter in case of a 220 nm thick nanoporous film with 25%
porosity. The stress distributions are visualized as 2-dimen-
sional sections of the 3D FEM model, i.e., the xy-plane for the
in-plane stress distribution and xz′-plane for the out-of-plane
stress distribution (Figure 3a).
The size and shape of the stress field were calculated at
indentation depths of 3, 8, and 15 nm. Clearly, both the size
and shape of the stress distribution change with increasing
indentation depth, while the maximum stress values underneath
the indenter tip can reach values up to 1.36 GPa for the out-of-
plane stress and about 480 MPa for the in-plane stress, even at
indentation depths as shallow as 3 nm. These localized large
stress values suggest that the pore structure may collapse upon
indentation and in this way influence the experimentally
obtained loading and unloading curves, even at the very shallow
depths. As a result, the elastic response of the film upon
indentation that is measured and the corresponding elastic
modulus extracted by either the quasi-static Oliver−Pharr
analysis, the more advanced CSM technique, or by FEM
simulations may overestimate the elastic properties of the
nanoporous film because such effects are not taken into account
by any of these analysis tools. Moreover, it was reported in the
literature that also the geometrical size and shape of the
distribution patterns of these densified zones underneath the
indenter tip can have a severe impact on the extracted
indentation modulus.36 Quantitative estimation of such an
effect is difficult to achieve since it depends on the penetration
depth, the extension and shape of the densified zone, and the
ratio between the elastic modulus of the nanoporous film and
those of the densified regions. However, qualitatively this can
be investigated by comparing the relative indentation modulus
obtained by spherical and Berkovich indentation experiments,
as illustrated on Figure 10a. The relative indentation modulus
values are obtained by normalizing the absolute values (Figure
12031
Article
Figure 10. (a) Indentation modulus obtained by spherical and
Berkovich indentation experiments, normalized to the absolute values
at zero porosity (see Figure 8). (b) Positronium intensity as a function
of the open porosity.
8) to the elastic modulus of the matrix, obtained by empirical
extrapolation to zero porosity, i.e.
E = E0(1 − P)n (9)
where E0 is elastic modulus of the matrix and n is a fitting
parameter which describes the shape of the curve. For films
with porosity above 25%, the BB UV cured and NB UV cured
films follow a similar linear trend. Interestingly, a clear
transition is found near 25% of porosity, below which the
slope of the linear relationship increases for both UV cure
conditions. This transistion correlates very well with the
connectivity threshold or percolation threshold that was
observed by PALS technique (Figure 10b) and agrees well
with the reported values of other nanoporous dielectric films in
the literature. 37−39 The PALS data showed no pore
interconnection (no positronium escaping into vacuum) in
the case of films with porosity below 25%.
For these films, the pores are considered to be closed for
PALS because positronium (Ps) is not able to diffuse and
escape. Near 25% of porosity, clearly Ps was detected through
weakly interconnected pores into vacuum. In this case, the pore
interconnection length, which is defined as the mean depth
when the deduced Ps escape fraction into vacuum is 50%, was
close to the limit of resolution (∼5 nm). Therefore, the pores
are considered to be almost closed for PALS.
For a 31% porous film, the interconnection length is about
140 ± 25 nm, which is close to the film thickness (Table 1),
and hence the pores are considered to be almost percolated.
For films with higher porosity, all pores are interconnected.
Besides PALS, also diffusion experiments were carried out on
nanoporous thin films using isopropanol as a solvent. Figure
11a shows the measured diffusion distance of isopropanol
(IPA) as a function of the square root of time for nanoporous
films with different open porosity. The corresponding diffusion
dx.doi.org/10.1021/la402383g | Langmuir 2013, 29, 12025−12035
Langmuir Article

substrate is extremely difficult to achieve because the

anisotropic elastic response itself may depend on the pore
morphology, the Berkovich tip geometry, and the complex
stress fields that are generated underneath the Berkovich tip
upon indentation. Even in the case of a transversely isotropic
material, where the physical properties of the film are
symmetric about an axis that is normal to a plane of isotropy,
solving the inverse problem by fitting the experimental load−
displacement curves would not yield an unambiguous result
because in this case there are five independent unknown elastic
constants to be determined (from a total of 21 independent
constants in the case of a fully anisotropic material) instead of
two in the case of an isotropic material. On the other hand, the
assumption that the nanoporous film behaves like a
homogeneous isotropic material is only true if the in reality
heterogeneous film can be replaced by a continuous film with
an effective modulus that contains the properties of porosity.
This approach is only valid when the characteristic length is
large compared to the dimension of the pores. Otherwise,
additional interactions between the strain fields around the
pores have to be taken into account which make the effective
modulus theory far more complicated. In case of spherical
indentation with 250 μm tip radius, the stress−strain fields are
Figure 11. (a) Diffused distances of IPA in nanoporous dielectric films large compared to the pore dimension. However, problems can
with different open porosity. Diffusion coefficients were calculated arise in case of Berkovich indentation, where the stress−strain
form the line slopes using eq 1. (b) Diffusion coefficient as a function fields become comparable to the pore dimension at shallow
of open porosity for all studied films with varied open porosity. indentation depths (Figure 9).
In the second part of this paper, we now focus on the
comparison of nanoindentation results to those obtained by
coefficients were calculated from the line slopes (Figure 11b). nondestructive techniques like LAwave and EP. Figure 12a
These results illustrate that molecular (isopropanol) diffusion is shows the dispersion curves as measured by the LAwave
still observed at porosity values significantly below the PALS’s technique for nanoporous films of different porosity fabricated
percolation threshold. This agrees with earlier observations by on (100) silicon. The elastic modulus of the films were
Mogilnikov et al.,40 in which they showed that the PALS obtained by fitting the theoretical curves to the measured
percolation threshold in porous dielectric films only reflects the
interconnectivity of mesopores (2−50 nm size), while below
the percolation threshold the pores are still interconnected
through intrinsic micropores (<2 nm). From this, we can
conclude that the observed transition in Figure 10a near
porosity close to 25% can be attributed to the percolation of
mesopores and a change in microstructure, evolving from a film
containing mesopores that are interconnected with micro-
porous channels at porosities below 25%, to a film which
contains heavily interconnected mesopores at higher porosity
levels. Since the size and shape of the densified zones upon
Berkovich indentation depend on the level of porosity inside
the film and the specific pore morphology, the observed
changes in pore structure may also cause the difference between
Berkovich and spherical indentation results to evolve with
porosity (Figure 8). Besides densification effects, another
contributing factor to the observed difference between spherical
indentation and Berkovich indentation may be related to the
fact that by introducing nanopores into the film, the elastic
response of the film may not be isotropic but anisotropic,
depending on the specific arrangement and morphology of the
pores. Since all analysis tools (quasi-static Oliver−Pharr
analysis, the CSM technique, and FEM simulations)
presuppose a homogeneous elastic isotropic behavior of the
nanoporous film, this may lead to erroneous results. Although
in the literature some efforts have been made to analyze Figure 12. (a) Surface wave velocity spectra, wave velocity versus
indentation results of anisotropic materials in the case of frequency, measured on thin nanoporous with different layer thickness
conical, parabolical, and spherical indenters,41−44 quantification and film porosity. (b) Comparison of the elastic modulus obtained by
of such effects in the case of nanoporous films on a stiff LAwave and spherical indentation.

12032 dx.doi.org/10.1021/la402383g | Langmuir 2013, 29, 12025−12035

Langmuir Article

dispersion curves. The theoretical fitting considers the

nanoporous film to behave like a homogeneous isotropic
material, where the pores are randomly distributed in volume
and size. In this case, an effective modulus is calculated from the
dispersion curves, representing this material from a macro-
scopic point of view.28,45
The assumption that the film can be considered as
homogeneous is justified because the LAwave wavelength
(∼25 μm) is much larger compared to the dimension of the
pores (∼2 nm). In this case, the stress−strain fields are large
compared to the pore dimension. On the other hand, by
assuming isotropy in the surface acoustic waves dispersion
model, the LAwave technique provides an average value of the
elastic modulus for an isotropic film. The extrapolated
dispersion curves to zero frequency reveals the wave velocity
of the (100) silicon substrate that is measured along the (100)
direction. This value agrees very well with the theoretical value
of the wave velocity as reported by Coufal et al.46 As shown in
Figure 12b, good agreement was found between LAwave and
spherical indentation results for films with open porosity above
30%, which is close to the observed PALS percolation threshold
(Figure 10). This correlation between both techniques was also
demonstrated by Chudoba et al. in the case of dense hard
materials on silicon substrates.47 Although LAwave and
spherical indentation are based on completely different physical Figure 13. (a) Relative change of the film thickness during toluene
principles, both techniques calculate an average effective adsorption and desorption. The film thickness is normalized to the
modulus value by assuming that the nanoporous film can be film thickness at relative toluene pressure equal to 1. The change of the
considered as a homogeneous elastic isotropic material. The film thickness is fitted by eq 6. (b) Comparison of the elastic modulus
obtained by EP and spherical indentation.
good agreement between both techniques therefore suggests
that for films with open porosity above 30% this approach is
valid. On the other hand, for nanoporous films with open adsorption (open dots) and desorption (closed dots) in case of
porosity below 30%, the measured effective modulus by 24.7% and 43.9% nanoporous dielectric films. The best fit of
LAwave appears to be higher compared to the effective the experimental curves by eq 6 yields the coefficient k0, which
modulus obtained by spherical indentation. A possible reason is then used for calculation of the elastic modulus using eq 7.
for this difference may be related to anisotropic elastic behavior Figure 13b compares the elastic modulus values obtained with
of these nanoporous films due to the specific arrangement and EP and spherical indentation for films with different levels of
morphology of the pores. Some researchers have studied the porosity. A good agreement was found between EP and
effect of anisotropy on surface acoustic waves, but they mainly spherical indentation data for films with porosity above 30%,
focus on single crystals using either analytical or numerical while for films with porosity below 30% the extracted elastic
methods.48,49 In case of a transversely isotropic symmetry, the modulus values using EP deviate from those obtained with
longitudinal and transverse elastic modulus of the film may spherical indentation. This can be explained by the fact that the
differ from the measured effective modulus obtained by nanoporous films with porosity below 30% mainly contain
spherical indentation and LAwave using a homogeneous elastic micropores with a pore diameter below 2 nm (Table 1). In this
isotropic model. Quantitative estimation of such anistropic case, the Kelvin equation12 is no longer valid because the values
effects from the measured dispersion curves is extremely of the surface tension and the molar volume deviate from those
difficult. This is because for a transverse isotropic symmetry, of the bulk liquid adsorptive. Moreover, also the concept of a
there are five independent unknown elastic constants instead of meniscus would eventually become meaningless. Therefore, the
two in the case of an isotropic material. Although a theoretical fitting of the relative film thickness versus relative toluene
model can be made to calcultate the dispersion curve for this pressure curves is in fact no longer valid.
problem, it would not make much sense because the inverse
problem would not yield unambiguous results. The same 4. CONCLUDING REMARKS
problems are encountered during the FEM fitting procedure for In this work, we compared destructive (NI) and nondestructive
the spherical indentation data. (LAwave and EP) experimental techniques which are based on
Therefore, it is unclear whether a higher effective modulus completely different physical principles for the calculation of
measured by LAwave compared to spherical indentation the elastic properties of nanometer scale porous films.
(Figure 12b) would suggest that spherical indentation is Nanoindentation using a Berkovich tip geometry tends to set
more sensitive to the longitudinal elastic modulus compared to an upper limit on the elastic modulus, rather than give an
the LAwave technique in the case of a transversely isotropic absolute value. Moreover, we have shown that in this case, the
symmetry. Nevertheless, the observed trends shown in Figure absolute value of the indentation modulus is very sensitive to
12b support the idea that anisotropic elasticity of the the local pore structure and stiffness of the substrate and can be
nanoporous film may contribute to the observed higher elastic influenced by densification and/or anisotropic elasticity upon
modulus obtained by Berkovich indentation. Figure 13a shows indentation. On the other hand, spherical indentation with a
the relative thickness change of the film during toluene large tip radius, combined with FEM results, is less sensitive to
12033 dx.doi.org/10.1021/la402383g | Langmuir 2013, 29, 12025−12035
Langmuir
the local pore structure. The characteristic length, which defines
the dimension in which the stress−strain analysis is nearly
homogeneous, may also play an important role. For spherical
indentation with a large tip radius, the stress−strain fields are
large compared to the pore dimension, while for Berkovich
indentation the stress−strain fields become comparable to the
pore dimension at shallow indenation depths. This complicates
the effective modulus theory and may lead to an overestimation
of the elastic properties. Careful examination of the internal
pore structure and interconnectivity of the investigated
nanometer scale porous films was performed by PALS and
EP and revealed a clear correlation between the internal pore
structure of these films and their mechanical properties. It was
demonstrated that the comparison of Berkovich and spherical
indentation results can potentially reveal changes in the internal
structure of the film. Nondestructive techniques like LAwave
and EP agree very well with the obtained spherical indentation
data for nanoporous films with porosity above the percolation
threshold. On the other hand, for films with porosity below the
percolation threshold, the extracted elastic modulus values
using LAwave and EP deviate from the spherical indentation
results. In the case of LAwave, a possible reason for this can be
related to anisotropic elastic behavior due to the specific
arrangement and morphology of the pores. In the case of EP,
this can be explained by the fact that the concept of this
technique and the assumptions that are made are no longer
valid. On the basis of this comparative study, we can conclude
that carefull nanoindentation combined with FEM simulations
offers the best approach for a complete mechanical character-
ization of nanometer scale porous films.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: kris.vanstreels@imec.be (K.V.).
Notes
The authors declare no competing financial interest.
■
REFERENCES
(1) Grill, A.; Patel, V. Ultralow-k dielectrics prepared by plasma-
enhanced chemical vapor deposition. Appl. Phys. Lett. 2001, 79, 803−
805.
(2) Urbanowicz, A.; Vanstreels, K.; Shamiryan, D.; De Gendt, S.;
Baklanov, M. R. Effect of porogen residue on chemical, optical, and
mechanical properties of CVD SiCOH low-k materials. Electrochem.
Solid-State Lett. 2009, 12 (8), H292−H295.
(3) Zhou, W.; Bailey, S.; Sooryakumar, R.; King, S.; Xu, G.; Mays, E.;
Ege, C.; Bielefeld, J. Elastic properties of porous low-k dielectric nano-
films. J. Appl. Phys. 2011, 110, 043520.
(4) Bailey, S.; Mays, E.; Michalak, D. J.; Chebiam, R.; King, S.;
Sooryakumar, R. Mechanical properties of high porosity low-k
dielectric nano-films determined by Brillouin light scattering. J. Phys.
D: Appl. Phys. 2013, 46, 045308.
(5) Guo, X.; Jakes, J. E.; Nichols, M. T.; Banna, S.; Nishi, Y.; Shohet,
J. L. The effect of water uptake on the mechanical properties of low-k
organosilicate glass. J. Appl. Phys. 2013, 114, 084103.
(6) Zin, E. H.; Bang, W. H.; Ryan, E. T.; King, S. W.; Kim, C.-U.
Study of viscoplastic deformation in porous organosilicate thin films
for ultra low-k applications. Appl. Phys. Lett. 2013, 102, 221909.
(7) Baklanov, M. R; Ho, P. S.; Zschech, E. In Advanced Interconnects
for ULSI Technology; Wiley: New York, 2012; Chapter 10, pp 339−
367.
(8) Maex, K.; Baklanov, M. R.; Shamiryan, D.; Iacopi, F.;
Brongersma, S. H.; Yanovitskaya, Z. S. Low dielectric constant
materials for microelectronics. J. Appl. Phys. 2003, 93 (11), 8793−
8841.
12034
Article
(9) Vanstreels, K.; Wu, C.; Verdonck, P.; Baklanov, M. R. Intrinsic
effect of porosity on mechanical and fracture properties of nanoporous
ultralow-k dielectrics. Appl. Phys. Lett. 2012, 101, 123109.
(10) Urbanowicz, A. M.; Vanstreels, K.; Verdonck, P.; Shamiryan, D.;
De Gendt, S.; Baklanov, M. R. Improving mechanical robustness of
ultralow-k SiOCH plasma enhanced chemical vapor deposition glasses
by controlled porogen decomposition prior to UV-hardening. J. Appl.
Phys. 2010, 107, 104122.
(11) Urbanowicz, A. M.; Verdonck, P.; Shamiryan, D.; Vanstreels, K.;
Baklanov, M. R.; De Gendt, S. U.S. Patent No. 20110006406, 2011.
(12) Baklanov, M. R.; Mogilnikov, K. P.; Polovinkin, V. G.; Dultsev,
F. N. Determination of pore size distribution in thin films by
ellipsometric porosimetry. J. Vac. Sci. Technol., B: Nanotechnol.
Microelectron.: Mater., Process., Meas., Phenom. 2000, 18, 1385−1391.
(13) Mogilnikov, K. P.; Baklanov, M. R. Determination of Young’s
modulus of porous low-k films by ellipsometric porosimetry.
Electrochem. Solid-State Lett. 2002, 5 (12), F29−F31.
(14) Gidley, D. W.; Peng, H.-G.; Vallery, R. S. Positron annihilation
as a method to characterize porous materials. Annu. Rev. Mater. Res.
2006, 36, 49−79.
(15) Baklanov, M. R.; Mogilnikov, K. P. Non-destructive character-
isation of porous low-k dielectric films. Microelectron. Eng. 2002, 64,
335−349.
(16) Boissiere, C.; Grosso, D.; Lepoutre, S.; Lionel, N.; Brunet
Bruneau, A.; Sanchez, C. Porososity and mechanical properties of
mesoporous thin films assessed by environmental ellipsometric
porosimetry. Langmuir 2005, 21, 12362−12371.
(17) Ravikovitch, P. I.; Neimark, A. V. Density functional theory
model of adsorption deformation. Langmuir 2006, 22 (26), 10864−
10868.
(18) Dendooven, J.; Kilian, D.-C.; Levrau, E.; Van Hove, R.; Sree, S.
P.; Baklanov, M. R.; Martens, J. A.; Detavernier, C. In-situ monitoring
of atomic layer deposition in nanoporous thin films using ellipsometric
porosimetry. Langmuir 2012, 28, 3852−3859.
(19) Baklanov, M. R.; Green, M.; Maex, K. In Dielectric Films for
Advanced Microelectronics; Wiley: New York, 2007; pp 85−131.
(20) Baklanov, M. R.; Mogilnikov, K. P.; Le, Q. T. Quantification of
processing damage in porous low dielectric constant films. Micro-
electron. Eng. 2006, 83, 2287−2291.
(21) Shamiryan, D.; Baklanov, M. R.; Lyons, P.; Beckx, S.; Boullart,
W.; Maex, K. Diffusion of solvents in thin porous films. Colloids Surf.,
A 2007, 300, 111−116.
(22) Zhu, G.; Li, Y.; Zhou, H.; Liu, J.; Yang, W. FAU-type zeolite
membranes synthesized by microwave assisted in situ crystallization.
Mater. Lett. 2008, 62, 4357−4359.
(23) Fischer-Cripps, A. C. In Nanoindentation, 2nd ed.; Springer:
New York, 2004; pp 69−110 and 132−143.
(24) Oliver, W. C.; Pharr, G. M. An improved technique for
determining hardness and elastic modulus using load and displacement
sensing indentation experiments. J. Mater. Res. 1992, 7, 1564−1583.
(25) VanLandingham, M. R. Review of instrumented indentation. J.
Res. Natl. Inst. Stand. Technol. 2003, 108, 249−265.
(26) Chudoba, T.; Schwarzer, N.; Richter, F. Determination of elastic
properties of thin films by indentation measurements with a spherical
indenter. Surf. Coat. Technol. 2000, 127, 9−17.
(27) Schneider, D.; Siemroth, P.; Schülke, T.; Berthold, J.; Schultrich,
B.; Schneider, H. H.; Ohr, R.; Petereit, B.; Hilgers, H. Quality control
of ultra-thin and super-hard coatings by laser-acoustics. Surf. Coat.
Technol. 2002, 153, 252−260.
(28) Farnell, G. W.; Adler, E. L. In Physical Acoustics; Mason, W. P.,
Thurston, R. N., Eds.; Academic Press: New York, 1972; Vol. IX.
(29) Adamson, A. W. In Physical Chemistry of Surfaces, 5th ed.; John
Wiley & Sons Inc.: New York, 1990.
(30) Knapp, J. A.; Follstaedt, D. M.; Myers, S. M.; Barbour, J. C.;
Friedmann, T. A. Finite-element modeling of nanoindentation. J. Appl.
Phys. 1999, 85 (3), 1460−1474.
(31) Fischer-Cripps, A. C. Critical review of analysis and
interpretation of nanoindentation test data. Surf. Coat. Technol.
2006, 200, 4153−4165.
dx.doi.org/10.1021/la402383g | Langmuir 2013, 29, 12025−12035
Langmuir Article

(32) Vanstreels, K.; Urbanowicz, A. M. Nanoindentation study of

thin plasma enhanced chemical vapor deposition SiCOH low-k films
modified in He/H2 downstream plasma. J. Vac. Sci. Technol., B:
Nanotechnol. Microelectron.: Mater., Process., Meas., Phenom. 2010, B28
(1), 173−179.
(33) Chen, X.; Vlassak, J. J. Numerical study on the measurement of
thin film mechanical properties by means of nanoindentation. J. Mater.
Res. 2001, 16 (10), 2974−2982.
(34) Chen, X.; Xiang, Y.; Vlassak, J. J. Novel technique for measuring
the mechanical properties of porous materials by nanoindentation. J.
Mater. Res. 2006, 21 (3), 715−724.
(35) Xiang, Y.; Chen, X.; Tsui, T. Y.; Jang, J.-I.; Vlassak, J. J.
Mechanical properties of porous and fully dense low-κ dielectric thin
films measured by means of nanoindentation and the plane-strain
bulge test technique. J. Mater. Res. 2006, 21 (2), 386−395.
(36) Lu, X.; Xiao, P.; Li, H. Effect of densification distribution on the
Young’s modulus of porous coatings after nano-indentation. Acta
Metall. Sin. (Engl. Lett.) 2012, 25 (5), 383−390.
(37) Sun, J. N.; Gidley, D. W.; Hu, Y. F.; Frieze, W. E.; Yang, S.
Characterizing porosity in nanoporous thin films using positronium
annihilation lifetime spectroscopy. Mater. Res. Soc. Symp. Proc. 2002,
726, Q10.5.1−Q10.5.12.
(38) Wang, C. L.; Weber, M. H.; Lynn, K. G.; Rodbell, K. P.
Nanometer-scale pores in low-k dielectric films probed by positron
annihilation lifetime spectroscopy. Appl. Phys. Lett. 2002, 81, 4413−
4415.
(39) Padovani, A. M.; Rhodes, L.; Allen, S. A. B.; Kohl, P. A.
Chemically bonded porogens in methylsilsesquioxane: II. electrical,
optical, and mechanical properties. J. Electrochem. Soc. 2002, 149 (12),
F171−F180.
(40) Mogilnikov, K. P.; Baklanov, M. R.; Shamiryan, D.; Petkov, M.
P. A discussion of the practical importance of positron annihilation
lifetime spectroscopy percolation threshold in evaluation of porous
low-K dielectrics. Jpn. J. Appl. Phys., Part 1 2004, 43 ((1)), 247−248.
(41) Delafargue, A.; Ulm, F.-J. Explicit approximations of the
indentation modulus of elastically orthotropic solids for conical
indenters. Int. J. Solids Struct. 2004, 41, 7351−7360.
(42) Nakamura, T.; Gu, Y. Identification of elastic−plastic
anisotropic parameters using instrumented indentation and inverse
analysis. Mech. Mater. 2007, 39, 340−356.
(43) Vlassak, J. J.; Ciavarella, M.; Barber, J. R.; Wang, X. The
indentation modulus of elastically anisotropic materials for indenters
of arbitrary shape. J. Mech. Phys. Solids 2003, 51 (9), 1701−1721.
(44) Swadener, J. G.; Pharr, G. M. Indentation of elastically
anisotropic half-spaces by cones and parabolae of revolution. Philos.
Mag. A 2001, 81 (2), 447−466.
(45) Schneider, D.; Schwarz, T.; Schultrich, B. Determination of
elastic modulus and thickness of surface layers by ultrasonic surface
waves. Thin Solid Films 1992, 219, 92−102.
(46) Coufal, H.; Meyer, K.; Grygier, R. K.; Hess, P.; Neubrand, A.
Precision measurement of the surface acoustic wave velocity on silicon
single crystals using optical excitation and detection. J. Acoust. Soc. Am.
1994, 95 (2), 1158−1160.
(47) Chudoba, T.; Griepentrog, M.; Dück, A.; Schneider, D.; Richter,
F. Young’s modulus measurements on ultra-thin coatings. J. Mater. Res.
2004, Vol 19 (1), 301−314.
(48) Viktorov, I. In Rayleigh and Lamb Waves; Plenum: New York,
1967.
(49) Farnell, G. W. In Physical Acoustics; Mason, W. P., Thurston, R.
N., Eds.; Academic: New York, 1970; Vol. 6, p 109.

12035 dx.doi.org/10.1021/la402383g | Langmuir 2013, 29, 12025−12035