Sensors and Actuators A 316 (2020) 112384

Contents lists available at ScienceDirect

Sensors and Actuators A: Physical

journal homepage: www.elsevier.com/locate/sna

Tailoring material properties of electrochemically deposited Al film

from chloroaluminate ionic liquid for microsystem technology using
pulsed deposition
Muhammad Salman Al Farisi a,∗ , Takashiro Tsukamoto a , Shuji Tanaka a,b
a
Department of Robotics, Graduate School of Engineering, Tohoku University, Sendai 980-8579, Japan
b
Micro System Integration Center (SIC), Tohoku University, Sendai 980-8579, Japan

a r t i c l e i n f o a b s t r a c t

Article history: To practically utilize an electrochemically deposited Al film in microsystems, its material properties have
Received 18 August 2020 to be elucidated, along with the influence of different deposition conditions. In this study, microstructure,
Received in revised form 11 October 2020 electrical, mechanical and thermal properties of electrochemically deposited Al film from a chloroalumi-
Accepted 12 October 2020
nate ionic liquid electrolyte are comprehensively investigated. The nanoindentation hardness and elastic
Available online 20 October 2020
modulus of the film varied between 486–908 MPa and 41–102 GPa, respectively, depending on the depo-
sition condition. The electrical resistivity and the coefficient of thermal expansion varied between 51–160
Keywords:
n m and 2–20 ppm/K, respectively. The results are compared to those of Al thin films deposited using
Aluminum
Electrochemical deposition other techniques. The characterized properties were found to be associated to the microstuctures of
Ionic liquid the deposits, which can be tailored by the deposition conditions. The microstructures of the deposits
Chloroaluminate were comprehensively characterized by cross-sectional scanning electron microscope (SEM) and elec-
Recurrent galvanic pulse plating tron backscatter diffraction (EBSD) spectroscopy. These results are useful as a design guide for the future
Design guide applications of the film.
© 2020 Elsevier B.V. All rights reserved.

1. Introduction usually limited in the order of several 10 nm/min. Therefore, the

Aluminum is the most abundant as well as the most heavily
used non-ferrous metallic material. Its metal and alloys are being
utilized for a wide variety of applications, starting from building
industries, home appliances, transportation and even microelec-
tronics, including the micro-electro mechanical system (MEMS)
and microsystems. In microsystems, aluminum is widely used as
wiring material, owing to its high electrical conductivity and low
cost [1].
Metallic thin films have been conventionally grown on sub-
strates by physical vapor deposition (PVD) [2], chemical vapor
deposition (CVD) [3], or electrochemical deposition technique [4].
In the microsystems, Al films are typically deposited using PVD
techniques, either sputtering or evaporation methods [5,6]. These
methods were able to realize a uniform film with high purity
under a moderate temperature. However, both techniques have
to be performed under high vacuum, which increases the fabri-
cation cost. In addition, the deposition rate of both techniques are
∗ Corresponding author.
E-mail address: salman@mems.mech.tohoku.ac.jp (M.S. Al Farisi).
deposition process of a relatively thick film of several ␮m remains
challenging. Furthermore, the films deposited by sputtering or
evaporation methods are usually patterned using either etching or
lift-off method. Therefore, these methods are not suitable to form
thick microstructures provided that a huge portion of the deposited
film is wasted.
A molded electroplating technique is commonly utilized to
make thick microstructures with high aspect ratio in microelec-
tronics and microsystems [7]. Examples of application span from
the packaging technologies, including for the through Si via fill-
ing [8], wafer-level bonding with hermetic encapsulation [9,10]
and flip-chip bumping [11], to the structural material of MEMS
devices, including accelerometers [12], angular rate sensors [13],
micro-mirrors [14], thermal actuators [15], energy harvester [16],
voltage sensors [17], relays [18] and high-frequency devices [19].
Furthermore, electrochemical deposition technique offers selective
deposition to match a particular pattern and good controllability of
properties of the resulting deposit [4].
The material properties of electrochemically deposited Au
[20,21], Cu [22,23] and Ni [24,25] metals and alloys have been
extensively studied over the past years. Consequently, these metals
and alloys have become the most commonly used electrochemi-

https://doi.org/10.1016/j.sna.2020.112384
0924-4247/© 2020 Elsevier B.V. All rights reserved.
M.S. Al Farisi, T. Tsukamoto and S. Tanaka
cally deposited materials in MEMS and microsystems. Considering
material cost and complementary metal oxide semiconductor
(CMOS) process compatibility, Al is a potential alternative. How-
ever, Al has an extremely negative standard potential of Al3+ /Al
couple (−1.67 V vs. normal hydrogen electrode), and thus having a
high tendency to oxidize under exposure to the most used electro-
plating solvent, water. This prevented Al reduction process, which
is an indispensable governing process to form an Al deposit on
the cathode using electroplating technique in a standard aqueous
media.
Various non-aqueous media have been extensively investi-
gated for Al electroplating, mainly as anti-corrosion protective
coatings for structural materials such as carbon steel [26,27],
magnesium alloys [28] and lightweight alloys [29]. Among dif-
ferent media, ionic liquids are particularly attracting due to their
nature of high thermal stability, high electrical conductivity, low
vapor pressure and wide electrochemical window [30]. Past stud-
ies have focused on the utilization of aluminum halides, such as
N-alkylpyridinium halides [31], N-alkylpyrrolidinium halides [32],
trialkyl-arylammonium halides [33], and N,N -dialkylimidazolium
halides [28].
Among various ionic liquids, a mixture of AlCl3 and 1-ethyl-3-
methylimidazolium chloride ([EMIm]Cl) is particularly promising
for Al electroplating, owing to its ability to maintain the liquid
state over a wider composition range, relatively wider electri-
cal potential window and lower viscosity [26]. Recently, the
microstructuring of the film deposited from such an ionic liquid has
been reported, aiming for the microsystems application [34]. How-
ever, for practical application in MEMS and microsystems, clear
understanding of various behavior of the film is necessary. To date,
its mechanical, electrical and thermal properties have not been
studied yet. Therefore, in this study, material properties of the film
are comprehensively investigated.
2. Experimental method
2.1. Specimen preparation
A single-crystal Si plate (P-type 100, thickness 400 ␮m), which
is widely used in semiconductor industry, is selected as the sub-
strate for film deposition. Fig. 1 illustrates the fabrication process
of the test specimens. Cr/Au thin films of 20/180 nm were sub-
sequently deposited on the substrate by magnetron sputtering
(CFS-4ES, Shibaura Mechatronics Corp., Japan). The Cr film acts
as an adhesion promotion layer and the Au layer plays a role as
an electrically conductive layer for the seed layer for the electro-
chemical deposition process. The presence of the Cr layer between
the Si substrate and the Au film provided a strong adherence with
high temperature and long term stability [36]. The electrochemical
deposition process was carried out from a commercially avail-
able AlCl3 -1-ethyl-3-methylimidazolium chloride ([EMIm]Cl) ionic
liquid electrolyte with 3:2 concentration ratio (EP-0001, IoLiTec
GmbH, Germany). The process was performed in a 2-electrodes
system with a 99.9% Al plate (Nilaco Corp., Japan) as the anode as
schematically shown in Fig. 2 a. Prior to the electrochemical deposi-
tion process, the Al electrode was thoroughly cleaned using organic
solvents and deionized water in an ultrasonic bath for over 5 min.
The deposition of Al on the cathode is driven by the following
reduction mechanism of electroactive ion Al2 Cl− , stant theoretical amount of deposit. The theoretical amount of the
7
4Al2 Cl− − − (0)
7 + 3e → 7AlCl4 + Al . (1)
The recovery of the electroactive ion occurs on the anode
through Al dissolution from the anode and reaction with AlCl4 − .
Meanwhile, a parasitic reaction occurs between the electroactive
ion and H2 O in the environment, which generates HCl acidic gas
2
Sensors and Actuators A 316 (2020) 112384
and furthermore degrades the electrolyte. To suppress such a para-
sitic reaction, an inert and dry environment is required to carry out
the deposition process. In this study, the electrodeposition process
was performed under a continuously flowing dry N2 (O2 concentra-
tion less than 180 ppm) atmosphere inside a glovebox (GalaxyPC,
As-One Corp., Japan).
The electroplating process was carried out under various elec-
trical conditions: direct current (DC) and recurrent galvanic pulse
plating (RGP) with varied duty ratios at 10 mA/cm2 current density
and 30 ◦ C deposition bath temperature. The deposition bath tem-
perature is varied from 30 ◦ C to 50 ◦ C at RGP duty ratio of 0.9 with
a constant magnetic stirring. In the RGP processes, a sequence of
deposition and reverse current is applied alternatively at the same
current density with a ratio period of 30 s as illustrated in Fig. 2 b.
The purpose of such pulses with long period is to provide a peri-
odical etching effect to the deposit, which enhances the current
efficiency of the deposition process [34]. The theoretical amount of
deposit is maintained constant for all depositions equivalent to the
DC deposition for 60 min duration, which results in around 8 ␮m
thickness of deposits for all process conditions. To remove all poten-
tial residues, the samples were cleaned in a continuously flowing
deionized water immediately after releasing from the glovebox for
over 5 min. The cleaning process was then followed by dipping the
samples in organic solvents in an ultrasonic bath for over 5 min.
2.2. Evaluation
The visual morphologies and the material composition of the
deposited structures were observed using a scanning electron
microscope (SEM) equipped with an energy dispersive X-ray (EDX)
spectroscopy analyzer (SU-70, Hitachi Ltd., Japan). The atomic
arrangements of the deposits were characterized using another
SEM equipped with an electron backscatter diffraction (EBSD) spec-
troscopy analyzer (JSM-7100F, JEOL Ltd., Japan).
The electrical resistivities of the deposits were characterized
using a 4-point probe system (K-705RS, Kyowa Riken Co., Ltd.,
Japan). The mechanical hardness and elastic modulus of the film
were evaluated using a nanoindentation tester (PICODENTOR
HM500, Helmut Fischer GmbH, Germany) using a pentahedron
pyramid indenter, i.e. Vickers tip, made of diamond. All mea-
surements were performed under atmospheric pressure at room
temperature. The coefficients of thermal expansion (CTE) of the
deposits were characterized by the curvature of the specimen,
which is induced by the CTE mismatch between the deposited film
and the substrate. The radius of curvature was characterized using a
white light interferometry (WLI) surface topography measurement
system (MSA-500, Polytec GmbH, Germany).
3. Results and discussion
3.1. Deposition rate
Fig. 3 a and b shows the dependence of the deposition rate from
the duty ratio and bath temperature, respectively. Reducing the
duty ratio could improve the deposition current efficiency, implied
by a higher mean value of thickness of the deposited film at a con-
deposit is maintained equivalent to 60 min DC deposition accord-
ing to the Faraday’s law by also taking into account the reverse
current duration. The error bar of the thicknesses are dominated
by the surface roughness of the film, whose value was around 2
␮m. However, reducing the deposition current duty ratio comes
at a cost of lower deposition rate due to the longer period of the
reverse current for etching.
M.S. Al Farisi, T. Tsukamoto and S. Tanaka
Fig. 1. Fabrication process of the test specimens on a (a) Si substrate. (b) Cr/Au sputtering for electroplating seed layer and (c) Al electrochemical deposition.
Fig. 2. (a) Schematics of Al electrochemical deposition with the occurring reactions [34,35]. (b) Current profile of the RGP plating.
Fig. 3. The thickness of the deposited film and the deposition rate under (a) different deposition current duty ratios and (b) different deposition bath temperatures.
Changing the deposition bath temperature from 30 ◦ C to 40
◦C slightly reduces the deposition rate. Further increase of bath
temperature to 50 ◦ C slightly increases the deposition rate. These
results are consistent with previous study [34]. The deposited films
are characterized for their morphology, composition, microstruc-
ture, electrical, mechanical and thermal properties.
3.2. Morphology and microstructure
Fig. 4 a and b shows the surface and cross-section of the DC
deposited Al film, respectively. Similar morphology was obtained
for the other films, except the film deposited under RGP at 0.7 duty
ratio. A typical EDX spectrum obtained from the cross-section of the
film is displayed in Fig. 4 c. These SEM images and EDX spectrum
suggest that a high purity Al films were deposited for almost all
deposition conditions without any contamination from the ionic
liquid, e.g. Cl. The C content can be attributed to the measurement
environment and the O content is originated from the native oxide
of Al. Fig. 4 d and e shows the surface and cross-section of the RGP
deposited Al film with 0.7 duty ratio, respectively. The film has a
similar surface morphology compared to the films deposited under
other conditions. However, there exist a lot of voids in the middle
of the film as shown in its cross-section.
3
Sensors and Actuators A 316 (2020) 112384
An EDX spectrum obtained from the cross-section of the film
deposited by RGP with 0.7 duty ratio is shown in Fig. 4 f. The com-
position is summarized in Table 1 . The C content comes from the
measurement environment, while the O content is originated from
the native oxide of the Al film. Apart from these contents, in the solid
part of the deposit, the Al film with a high purity was obtained sim-
ilar to the DC deposited film. However, a significant amount of Ga,
Au and Si were found near the voids. The Au and Si are originated
from the seed layer and the substrate, respectively. Meanwhile, the
Ga content is originated from the focused ion beam (FIB) etching,
which was used to produce the cross-section. The redeposition of
Au and Si elements could be attributed to the non-uniformity of Al
nucleation throughout the surface area during the initial ratios of
the deposition process. This has caused the seed layer to be partially
etched during the reverse current application and form a Si-Au
intermetallic compound with the substrate [37]. In addition, the Au
content can also attributed to the formation of Al-Au intermetallic
compound [38]. Such intermetallic compounds were redeposited
during the forward current application, which contributed to the
formation of voids. Meanwhile, the Cr content originated from the
adhesion promotion layer was not detected, which could be due to
the low amount of Cr.
EBSD cross-sectional inverse polar figure (IPF) maps of the
resulting deposits are depicted in Fig. 5 . Cross sectional observa-
M.S. Al Farisi, T. Tsukamoto and S. Tanaka
Fig. 4. SEM (a) surface and (b) cross-sectional images of DC deposited film. (c) EDX spectrum taken from the cross-sectional area (a). SEM (d) surface and (e) cross-sectional
images of RGP deposited film with 0.7 duty ratio. (f) EDX spectra taken from the cross-sectional area (e). Cross marks indicate the EDX measurement points.
Table 1
Material composition of the electrochemically deposited Al films, taken from the cross-sectional areas in Fig. 4 .
Sample Atomic %
Al O C
DC (Fig. 4 b) 87.6% 2.9%
RGP, 0.7 duty ratio (Fig. 4 e, P1) 87.8% 2.2%
RGP, 0.7 duty ratio (Fig. 4 e, P2) 49.3% 8.6%
tion provides a more thorough analysis of the film in comparison to
surface observation [39]. It can be observed that the film exhibits a
columnar grain structure and the grain size increases from sev-
eral 100 nm near the substrate to several ␮m near the surface.
The fine grains near the seed layer can be attributed to the high
frequency nucleation processes during the initial stage of the depo-
sition, which is influenced by the microstructure of the seed layer.
After further deposition, the grain growth process becomes more
dominant to a certain limit, independent of the microstructure of
the underlying layer. Similar results were also obtained for electro-
chemically deposited Au and Cu [21,39].
The most fundamental information of microstructure of metallic
materials is the average grain size. Various mechanical properties,
such as hardness, stress-strain properties and fatigue correlate well
with the average grain size [40,41]. In particular, electrochemical
deposition process is well known for its controllability of the grain
growth process [4], which can be utilized for tailoring various mate-
rial properties. The Hall–Petch relationship between the average
grain size and the yield strength is formulated as [42]
1
 = 0 + kd− 2 , (2)
where  0 represents the lattice friction stress required to move an
individual dislocation, k represents a material-dependent constant
known as the Hall–Petch slope, and d represents the average grain
size. Based on this relation, the average grain size is often utilized to
describe the microstructure of polycrystalline materials. However,
for materials with non-uniform microstructure, i.e. heterogeneous
microstructures, their mechanical properties are also influenced
by their grain size distributions [43]. For instance, the broaden-
4
Sensors and Actuators A 316 (2020) 112384
Ga Au Si
9.5% – – –
10.0% – – –
12.1% 11.8% 2.1% 16.1%
ing of the grain size dispersion has been reported to reduce the
strength of a material [44]. Therefore, the average grain size infor-
mation does not adequately represent the physical characteristics
of heterogeneous microstructures.
In heterogeneous microstructures, larger grains often occupy a
significant volume of the material, even if they are less in num-
ber. These large grains are associated with lower strength due to
the length of the slip band, which causes them to yield earlier
[44]. Therefore, to accommodate the contribution of each grain
to the mechanical characteristics of polycrystalline materials, the
volume-weighted average grain size is considered [45]. The volume
averaged grain size is mathematically formulated as
1 
n
dv = Vi di , (3)
VT
i=1
where VT represents the total volume of the material, Vi and di rep-
resent the volume and the size of a grain i, respectively. According
to this definition, the magnitude of volume averaged grain size is
always larger than the average grain size. The volume averaged
grain size can also include the contribution of the grain size distri-
bution.
According to the abovementioned analysis, the EBSD IPF maps
are processed using GNU Octave to quantify the average grain size,
volume-averaged grain size and relative grain size dispersion. The
quantified magnitudes are presented in Fig. 6 . Fig. 6 a shows that
the average grain size, volume averaged grain size and relative
grain size dispersion drop with the decrease of duty ratio from
1 to 0.8. However, all those values again increase when the duty
M.S. Al Farisi, T. Tsukamoto and S. Tanaka
Fig. 5. EBSD cross-sectional IPF map of the deposited film under different conditions. (a) DC deposition and RGP deposition with (b) 0.9, (c) 0.8 and (d) 0.7 current densities
at 30 ◦ C. RGP deposition at 0.9 current density at (e) 40 ◦ C and (f) 50 ◦ C deposition temperatures.
ratio becomes 0.7. These results indicate that the grain growth can
be limited by tuning the current density and introducing reverse
current. This also in turn enhanced nucleation and resulted in finer
grain size at lower duty ratio. However, at 0.7 duty ratio, there exists
a huge void in between the fine-grain and large-grain regions.
Fig. 6 b shows the relation between microstructures and the
deposition temperature. With the rise of deposition temperature,
all the average grain size, volume-averaged grain size and the rel-
ative grain size dispersion decrease. This indicates that at higher
deposition temperature, the nucleation phenomena occur more
often, which limits the grain growth process. This mechanism
resulted in finer overall grain size at higher deposition temperature.
3.3. Electrical characteristics
The resistivities of the electroplated films are compared to those
of previously reported values [6] as shown in Fig. 7 a. In overall, the
electrical resistivity increases from 51 n m to 160 n m with
the decrease of the deposition duty ratio. The trend from 1 to 0.8
duty ratio could be partly attributed to the grain size refining, as
finer grain size has been associated to higher electrical resistivity
of pure thin film metals [46,47]. This effect is in part due to the
electron scattering at the grain boundaries [48]. On the other hand,
the increase of the electrical resistivity can also be partly attributed
to the existence of internal micro-voids in the films. Such voids may
have played a more dominant role in significantly increasing the
electrical resistivity of the film deposited under a duty ratio of 0.7.
The electrical resistivity of the deposited films also monoton-
ically increases from 45 n m to 85 n m with the rise of the
5
Sensors and Actuators A 316 (2020) 112384
deposition bath temperature from 30 ◦ C to 50 ◦ C, as shown in Fig.
7 b. This trend can also be attributed to the effect of the grain
size refining. Finer overall grain size deposited at higher deposi-
tion temperature accounts for higher electrical resistivity, which is
in agreement with previous studies.
3.4. Mechanical characteristics
The schematics of the nanoindentation experiment is illustrated
in Fig. 8 a. The indentation depth was maintained to be more than
100 nm and less than 10% of the film thickness to avoid the influence
of the native oxide layer and the substrate, respectively. The maxi-
mum force was maintained at about 5 mN. Fig. 8 b shows a typical
loading–unloading curve obtained from the nanoindentation test.
The nanoindentation hardness corresponds to the maximum load
P and the contact area projection of the indentation tip AP , which
is defined as [49]
P
Hf = . (4)
AP
The measured nanoindentation hardnesses of the deposited
films are compared to bulk Al and a 1 ␮m thin Al film deposited by
magnetron sputtering evaluated by the same instrument as shown
in Fig. 8 c. The measured values of the bulk and sputtered film are
in agreement with the reported studies [5,6]. A duty ratio of 1 indi-
cates the DC deposition. The values for the electroplated films are
in between those of the bulk and the sputtered film due to the grain
size difference in accordance to the Hall–Petch relation. Thicker film
is often associated with larger grain size. The mean value of nanoin-
M.S. Al Farisi, T. Tsukamoto and S. Tanaka
Fig. 6. Average grain size, volume averaged grain size and relative grain size disper-
sion of the resulting films deposited (a) using current-controlled DC and RGP with
varied duty ratios and (b) under varied deposition temperatures.
dentation hardness increases from 750 MPa to 853 MPa with the
decrease of the deposition current duty ratio from 1 to 0.8, and it
drops to 486 MPa upon further reduction of duty ratio to 0.7. This
can also be attributed mainly due to the grain refining as explained
in the previous section. The dropped figure at 0.7 duty ratio is due
to the existence of micro-voids and impurities as observed in the
previous section.
Fig. 8 c also shows the measured elastic modulus against the
deposition duty ratio. The elastic modulus of the film was deter-
mined from the unloading curve of the nanoindentation test during
the elastic recovery. The equation is derived from the Hertzian the-
ory of contact mechanics [50] and the geometrical consideration of
the diamond indentation tip as
1 − f2
Ef = √ ,
1−2
√
2 P
− Ei
i
S Hf
Fig. 7. Electrical resistivity of the deposited films (a) using current-controlled DC and RGP with varied duty ratios and (b) under varied deposition temperatures. The results
are compared to thin films deposited by other technique and bulk.
Sensors and Actuators A 316 (2020) 112384
where Ef and f are the elastic modulus and Poisson’s ratio of the
measured thin film, Ei and i are the elastic modulus and Poisson’s
ratio of the diamond indenter, P is the maximum applied load and
H is the measured nanoindentation hardness. Ei and i values are
assumed from the typical value of diamond indenter (Ei = 1141 GPa,
i = 0.07) [49] and f is assumed to be the same as the value for
polycrystalline Al (f = 0.34) [51].
The elastic moduli of the films deposited with different duty
ratios are compared to those of the bulk and sputtered Al. The
measured mean figures of the bulk and the sputtered film are
82 GPa and 92 GPa, respectively. The elastic moduli of the elec-
troplated films with 0.8–1 duty ratio showed a fluctuation in
between 78 GPa and 102 GPa, which are close to those of the
bulk and sputtered thin film. However, the figure drops to 41
GPa at 0.7 duty cycle. Such a drop can be attributed to the exis-
tence of micro-voids and impurities as observed in the previous
section.
Fig. 8 d shows the deposition temperature dependence of the
nanoindentation hardness and elastic modulus. The films were
deposited by the RGP with the duty ratio of 0.9. The nanoinden-
tation hardness of the film increase proportionally from 761 MPa
to 908 MPa with the deposition bath temperature from 30 ◦ C to 50
◦ C. The increase of hardness can be attributed to the grain refining
occurred in the films deposited under elevated bath temperatures.
However, there is less influence of the deposition temperature in
the elastic modulus of the resulting deposit as shown with the
fluctuation of the value at 78–88 GPa.
3.5. Thermal characteristics
The internal stress  of a film is inversely proportional to the
radius of curvature r of the substrate under atmospheric pressure,
which can be mathematically expressed as [52]
Es ts2
= , (6)
6(1 − s )rtf
where Es is the elastic modulus of the substrate, ts is the substrate
thickness, s is the Poisson’s ratio of the substrate and tf is the film
thickness. In this study, Es and s are assumed to be the typical prop-
erties of Si as 168 GPa and 0.34, respectively [53,54]. The substrate
thickness is ts = 400 ␮m.
The schematics of the evaluation system is shown in Fig. 9 a.
For a finite measurement length, the radius of curvature r can be
reformulated as
l2
r= , (7)
2ı
(5)
where l is the measurement length and ı is the difference of height
between the center part and the edge. A typical measurement result
6
M.S. Al Farisi, T. Tsukamoto and S. Tanaka Sensors and Actuators A 316 (2020) 112384

Fig. 8. (a) Schematics of the nanoindentation experiment performed in this study. (b) Typical loading-unloading curve from the nanoindentation test. The loading step is
utilized to evaluate the hardness of the film. The unloading step is utilized for evaluation of the elastic modulus of the film. Nanoindentation hardness and elastic modulus
of the deposited films (c) using current-controlled DC and RGP with varied duty ratio and (d) under varied deposition temperatures. The results are compared to thin films
deposited by other techniques and bulk.

Fig. 9. (a) Schematics of the CTE evaluation experiment performed in this study. (b) Typical deflection profile observed by the WLI at room temperature. CTE of the deposited
films (c) using current-controlled DC and RGP with varied duty ratios and (d) under varied deposition temperatures. The results are compared to Al thin film deposited by
another technique, bulk Al and Si.

7
M.S. Al Farisi, T. Tsukamoto and S. Tanaka
at room temperature is displayed in Fig. 9 b. The deflection profiles
of the substrate were measured at constant temperatures ranging
from 20 to 50 ◦ C. The internal stress difference changes with the
temperature due to CTE mismatch between the Si substrate and
the deposited Al film. The relationship between the CTE difference,
˛ and the internal stress difference caused by CTE mismatch, 
is expressed as
(1 − f )
˛ = , (8)
Ef T
where T, f and Ef are the temperature difference from the ref-
erence state, Poisson’s ratio and elastic modulus of the film. The
Poisson’s ratio of the film is assumed to be the same as that of bulk
Al, i.e. f = 0.34 [51]. The measurement results are displayed in Fig. 9
c and d. The CTE of the film deposited under DC is 20 ppm/K, which
is similar to the previously reported value of bulk Al and the aver-
age value of evaporated Al thin film [55]. A high variation of CTE
has been reported for evaporated Al film, with a high dependency
on film thickness [55].
A high dependency of the CTE to the deposition current duty
ratio and deposition temperature was found as shown in Fig. 9 c
and d. This can be attributed partly to the grain size difference of
the deposited films, in which the CTE of the deposit increases with
grain size. This is in agreement with the previous study [55], in
which thicker film can be associated with larger grain size. On the
other hand, the existence of internal micro-voids should also be
accounted. Such voids can mitigate the expanded volume of the
film, which in turn reduce the CTE. This is valid particularly in the
film deposited at duty ratio of 0.7 in which the CTE decreases even
though the grain size becomes larger. These results reflect the CTE
of the electrochemically deposited Al film, rather than the intrinsic
property of Al.
4. Conclusion
In this study, the basic material properties of electrochemically
deposited Al film from a chloroaluminate ionic liquid was com-
prehensively investigated. The influence of different deposition
conditions to the morphology and microstructure of the result-
ing deposit has been investigated. The fundamental characteristics,
such as the electrical resistivity, nanoindentation hardness, elastic
modulus and CTE, have been evaluated and discussed in relation to
the microstructure of the film.
In general, pure Al films with no observable voids have
been obtained. The deposits exhibit columnar grain microstruc-
tures with the grain size growing vertically, which resemble
the typical films deposited under electrochemical deposition.
Finer grain size can be obtained by reducing the deposition
current duty ratio or increasing the deposition tempera-
ture. The electrical, mechanical and thermal properties of the
deposited films were found to be related to the microstruc-
tures.
The nanoindentation hardness and elastic modulus of the film
were characterized and varied between 486–908 MPa and 41–102
GPa, respectively. The electrical resistivity and the CTE varied
between 51–160 n m and 2–20 ppm/K, respectively. All these
properties were associated to the microstructure of the deposits.
Finer grain size is associated to higher electrical resistivity, higher
nanoindentation hardness and lower CTE. The results are compared
to those of Al thin films deposited using other techniques. These
results are important as a design guide to tailor various proper-
ties of the material for the future microsystem applications of the
film.
8
Sensors and Actuators A 316 (2020) 112384
Declaration of interests
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared to
influence the work reported in this paper.
Author statement
Muhammad Salman Al Farisi: Conceptualization, Methodol-
ogy, Investigation, Validation, Formal analysis, Resources, Writing
– Original Draft, Writing – Review & Editing, Visualization, Fund-
ing acquisition. Takashiro Tsukamoto,Shuji Tanaka: Resources,
Validation, Writing – Review & Editing, Supervision.
Declaration of Competing Interest
The authors report no declarations of interest.
Acknowledgements
This study was supported by Japan Society for the Promotion
of Science (JSPS) KAKENHI grant-in-aid for young scientist no.
19J11122 and the Division for Interdisciplinary Advanced Research
and Education, Tohoku University. The authors acknowledge Dr.
Takamichi Miyazaki from the Department of Instrumental Anal-
ysis, Graduate School of Engineering, Tohoku University for his
assistance in EBSD analysis. The authors also acknowledge Mr.
Masatoshi Tanno from the New Industry Creation Hatchery Center
(NICHe), Tohoku University for his assistance in nanoindenta-
tion testing. A part of the experiments were performed in the
Micro/Nano Machining Research and Education Center (MNC),
Tohoku University.
References
[1] J.R. Davis (Ed.), ASM Specialty Handbook: Aluminum and Aluminum Alloys,
ASM International, 1993.
[2] C. Charrier, P. Jacquot, E. Denisse, J.P. Millet, H. Mazille, Aluminium and Ti/Al
multilayer PVD coatings for enhanced corrosion resistance, Surf. Coat.
Technol. 90 (1–2) (1997) 29–34, http://dx.doi.org/10.1016/S0257-
8972(96)03080-0.
[3] J.H. Yun, B.Y. Kim, S.W. Rhee, Metal-organic chemical vapor deposition of
aluminum from dimethylethylamine alane, Thin Solid Films 312 (1–2) (1998)
259–264, http://dx.doi.org/10.1016/s0040-6090(97)00333-7.
[4] T. Watanabe, Structure Control Theory of Plated Film, 2002, pp. 339–349.
[5] Y.Y. Lim, M.M. Chaudhri, Y. Enomoto, Accurate determination of the
mechanical properties of thin aluminum films deposited on sapphire flats
using nanoindentations, J. Mater. Res. 14 (6) (1999) 2314–2327, http://dx.doi.
org/10.1557/JMR.1999.0308.
[6] M. Doerner, D. Gardner, W. Nix, Plastic properties of thin films on substrates
as measured by submicron indentation hardness and substrate curvature
techniques, J. Mater. Res. 1 (6) (1986) 845–851, http://dx.doi.org/10.1557/
JMR.1986.0845.
[7] M.W. Losey, J.J. Kelly, Electrodeposition, in: Compr. Microsystems, Elsevier
B.V., 2008, pp. 271–292 (Chap. 1.10).
[8] X. Zhang, J.K. Lin, S. Wickramanayaka, S. Zhang, R. Weerasekera, R. Dutta, K.F.
Chang, K.J. Chui, H.Y. Li, D.S. Wee Ho, L. Ding, G. Katti, S. Bhattacharya, D.L.
Kwong, Heterogeneous 2.5D integration on through silicon interposer, Appl.
Phys. Rev. 2 (2) (2015), http://dx.doi.org/10.1063/1.4921463.
[9] M.S. Al Farisi, H. Hirano, J. Frömel, S. Tanaka, Wafer-level hermetic
thermo-compression bonding using electroplated gold sealing frame
planarized by fly-cutting, J. Micromech. Microeng. 27 (1) (2017) 015029,
http://dx.doi.org/10.1088/1361-6439/27/1/015029.
[10] M.S. Al Farisi, H. Hirano, S. Tanaka, Low-temperature hermetic
thermo-compression bonding using electroplated copper sealing frame
planarized by fly-cutting for wafer-level MEMS packaging, Sens. Actuators A:
Phys. 279 (2018) 671–679, http://dx.doi.org/10.1016/j.sna.2018.06.021.
[11] M.J. Wolf, G. Engelmann, L. Dietrich, H. Reichl, Flip chip bumping
technology—status and update, Nucl. Instr. Methods Phys. Res. Sect. A Accel.
Spectrom. Detect. Assoc. Equip. 565 (1) (2006) 290–295, http://dx.doi.org/10.
1016/j.nima.2006.05.046.
M.S. Al Farisi, T. Tsukamoto and S. Tanaka
[12] T. Konishi, D. Yamane, T. Matsushima, G. Motohashi, K. Kagaya, H. Ito, N.
Ishihara, H. Toshiyoshi, K. Machida, K. Masu, Novel sensor structure and its
evaluation for integrated complementary metal oxide semiconductor
microelectromechanical systems accelerometer, Jpn. J. Appl. Phys. 52 (6 Part
2) (2013), http://dx.doi.org/10.7567/JJAP.52.06GL04, 0-6.
[13] S.E. Alper, K.M. Silay, T. Akin, A low-cost rate-grade nickel microgyroscope,
Sens. Actuators A: Phys. 132 (1 Spec. Iss) (2006) 171–181, http://dx.doi.org/
10.1016/j.sna.2006.03.031.
[14] J.D. Li, P. Zhang, Y.H. Wu, Y.S. Liu, M. Xuan, Fabrication of metallic micromirror
using electroplating technology, Microsyst. Technol. 17 (10-11) (2011)
1671–1674, http://dx.doi.org/10.1007/s00542-011-1353-4.
[15] E.T. Enikov, K. Lazarov, PCB-integrated metallic thermal micro-actuators,
Sens. Actuators A: Phys. 105 (2003) 76–82, http://dx.doi.org/10.1016/S0924-
4247(03)00065-7.
[16] S. Sun, X. Dai, Y. Sun, X. Xiang, G. Ding, X. Zhao, MEMS-based wide-bandwidth
electromagnetic energy harvester with electroplated nickel structure, J.
Micromech. Microeng. 27 (11) (2017), http://dx.doi.org/10.1088/1361-6439/
aa8077.
[17] J. Dittmer, L. Hecht, R. Judaschke, S. B”uttgenbach, RMS voltage sensor
based on a variable parallel-plate capacitor made of electroplated copper,
Microsyst. Technol. 16 (8-9) (2010) 1665–1671, http://dx.doi.org/10.1007/
s00542-009-1016-x.
[18] M. Becker, D. Lütke Notarp, J. Vogel, E. Kieselstein, J.P. Sommer, K.
Br”amer, V. Großer, W. Benecke, B. Michel, Application of
electroplating in MEMS-micromachining exemplified by a microrelay,
Microsyst. Technol. 7 (4) (2001) 196–202, http://dx.doi.org/10.1007/
s005420000086.
[19] J.Y. Park, G.H. Kim, K.W. Chung, J.U. Bu, Electroplated RF MEMS capacitive
switches, Proceedings IEEE Thirteenth Annual International Conference on
Micro Electro Mechanical Systems (2000) 639–644, http://dx.doi.org/10.
1109/memsys.2000.838593.
[20] C.W. Baek, Y.K. Kim, Y. Ahn, Y.H. Kim, Measurement of the mechanical
properties of electroplated gold thin films using micromachined beam
structures, Sens. Actuators A: Phys. 117 (1) (2005) 17–27, http://dx.doi.org/
10.1016/j.sna.2003.11.041.
[21] Y. Nakoshi, K. Suzuki, H. Miura, Effects of crystallinity on mechanical
properties of electroplated gold thin films used for three-dimensional
electronic packaging, Jpn. J. Appl. Phys. 58 (SB) (2019) SBBC04, http://dx.doi.
org/10.7567/1347-4065/ab00f4.
[22] A. Volinsky, J. Vella, I. Adhihetty, V. Sarihan, L. Mercado, B. Yeung, W.
Gerberich, Microstructure and mechanical properties of electroplated Cu thin
films, MRS Proc. 649 (2000), http://dx.doi.org/10.1557/PROC-649-Q5.3, Q5.3.
[23] D.T. Read, Y.W. Cheng, R. Geiss, Morphology, microstructure, and mechanical
properties of a copper electrodeposit, Microelectron. Eng. 75 (1) (2004)
63–70, http://dx.doi.org/10.1016/j.mee.2003.09.012.
[24] T. Fritz, W. Mokwa, U. Schnakenberg, Material characterisation of
electroplated nickel structures for microsystem technology, Electrochim. Acta
47 (1) (2001) 55–60, http://dx.doi.org/10.1016/S0013-4686(01)00576-X.
[25] A. Ul-Hamid, H. Dafalla, A. Quddus, H. Saricimen, L.M. Al-Hadhrami,
Microstructure and surface mechanical properties of pulse electrodeposited
nickel, Appl. Surf. Sci. 257 (22) (2011) 9251–9259, http://dx.doi.org/10.1016/j.
apsusc.2011.04.120.
[26] Q.X. Liu, S.Z. El Abedin, F. Endres, Electroplating of mild steel by aluminium in
a first generation ionic liquid: a green alternative to commercial Al-plating in
organic solvents, Surf. Coat. Technol. 201 (3–4) (2006) 1352–1356, http://dx.
doi.org/10.1016/j.surfcoat.2006.01.065.
[27] G. Yue, X. Lu, Y. Zhu, X. Zhang, S. Zhang, Surface morphology, crystal structure
and orientation of aluminium coatings electrodeposited on mild steel in ionic
liquid, Chem. Eng. J. 147 (1) (2009) 79–86, http://dx.doi.org/10.1016/j.cej.
2008.11.044.
[28] J.K. Chang, S.Y. Chen, W.T. Tsai, M.J. Deng, I.W. Sun, Electrodeposition of
aluminum on magnesium alloy in aluminum chloride
(AlCl3)-1-ethyl-3-methylimidazolium chloride (EMIC) ionic liquid and its
corrosion behavior, Electrochem. Commun. 9 (7) (2007) 1602–1606, http://
dx.doi.org/10.1016/j.elecom.2007.03.009.
[29] U. Bardi, S. Caporali, M. Craig, A. Giorgetti, I. Perissi, J.R. Nicholls,
Electrodeposition of aluminium film on P90 Li-Al alloy as protective coating
against corrosion, Surf. Coat. Technol. 203 (10–11) (2009) 1373–1378, http://
dx.doi.org/10.1016/j.surfcoat.2008.11.003.
[30] F. Endres, Ionic liquids: solvents for the electrodeposition of metals and
semiconductors, ChemPhysChem 3 (2) (2002) 144–154.
[31] J. Robinson, The electrochemical behavior of aluminum in the low
temperature molten salt system n butyl pyridinium chloride: aluminum
chloride and mixtures of this molten salt with benzene, J. Electrochem. Soc.
127 (1) (1980) 122, http://dx.doi.org/10.1149/1.2129601.
[32] S.Z. El Abedin, E.M. Moustafa, R. Hempelmann, H. Natter, F. Endres, Additive
free electrodeposition of nanocrystalline aluminium in a water and air stable
9
Sensors and Actuators A 316 (2020) 112384
ionic liquid, Electrochem. Commun. 7 (11) (2005) 1111–1116, http://dx.doi.
org/10.1016/j.elecom.2005.08.010.
[33] T. Jiang, M.J. Chollier Brym, G. Dubé, A. Lasia, G.M. Brisard, Electrodeposition
of aluminium from ionic liquids: Part II – studies on the electrodeposition of
aluminum from aluminum chloride (AICl3)–trimethylphenylammonium
chloride (TMPAC) ionic liquids, Surf. Coat. Technol. 201 (1–2) (2006) 10–18,
http://dx.doi.org/10.1016/j.surfcoat.2005.12.024.
[34] M.S. Al Farisi, S. Hertel, M. Wiemer, T. Otto, Aluminum patterned
electroplating from AlCl3-[EMIm]Cl ionic liquid towards microsystems
application, Micromachines 9 (11) (2018) 589, http://dx.doi.org/10.3390/
mi9110589.
[35] E. Berretti, A. Giaccherini, S.M. Martinuzzi, M. Innocenti, T.J.S. Schubert, F.M.
Stiemke, S. Caporali, Aluminium electrodeposition from ionic liquid: effect of
deposition temperature and sonication, Materials (Basel) 9 (9) (2016) 719,
http://dx.doi.org/10.3390/ma9090719.
[36] K.E. Haq, K.H. Behrndt, I. Kobin, Adhesion mechanism of gold-underlayer film
combinations to oxide substrates, J. Vac. Sci. Technol. 6 (1) (1969) 148–152,
http://dx.doi.org/10.1116/1.1492648.
[37] K. Nakashima, M. Iwami, A. Hiraki, Low temperature diffusion of Au into Si in
the Si(substrate)-Au(film) system, Thin Solid Films 25 (2) (1975) 423–430,
http://dx.doi.org/10.1016/0040-6090(75)90060-7.
[38] E. Philofsky, Intermetallic formation in gold-aluminum systems, Solid State
Electron. 13 (10) (1970) 1391–1394, http://dx.doi.org/10.1016/0038-
1101(70)90172-3.
[39] S.H. Kim, J.H. Kang, S.Z. Han, Electron backscatter diffraction characterization
of microstructure evolution of electroplated copper film, Mater. Trans. 51 (4)
(2010) 659–663, http://dx.doi.org/10.2320/matertrans.MG200910.
[40] E.O. Hall, Variation of hardness of metals with grain size, Nature 173 (4411)
(1954) 948–949, http://dx.doi.org/10.1038/173948b0.
[41] N.J. Petch, The cleavage strength of polycrystals, J. Iron Steel Inst. 174 (1953)
25–28.
[42] R.W. Armstrong, The influence of polycrystal grain size on several mechanical
properties of materials, Metall. Mater. Trans. 1 (5) (1970) 1169–1176, http://
dx.doi.org/10.1007/BF02900227.
[43] R.A. Masumura, P.M. Hazzledine, C.S. Pande, Yield stress of fine grained
materials, Acta Mater. 46 (13) (1998) 4527–4534, http://dx.doi.org/10.1016/
S1359-6454(98)00150-5.
[44] B. Raeisinia, C.W. Sinclair, W.J. Poole, C.N. Tomé, On the impact of grain size
distribution on the plastic behaviour of polycrystalline metals, Model. Simul.
Mater. Sci. Eng. 16 (2) (2008), http://dx.doi.org/10.1088/0965-0393/16/2/
025001.
[45] P. Lehto, H. Remes, T. Saukkonen, H. Hänninen, J. Romanoff, Influence of grain
size distribution on the Hall–Petch relationship of welded structural steel,
Mater. Sci. Eng. A 592 (2014) 28–39, http://dx.doi.org/10.1016/j.msea.2013.
10.094.
[46] J.M.E. Harper, C. Cabral, P.C. Andricacos, L. Gignac, I.C. Noyan, K.P. Rodbell, C.K.
Hu, Mechanisms for microstructure evolution in electroplated copper thin
films near room temperature, J. Appl. Phys. 86 (5) (1999) 2516–2525, http://
dx.doi.org/10.1063/1.371086.
[47] M.K. Loudjani, C. Sella, Relation between microstructure and electric
resistivity of copper, nickel, Nix Cu1 − x alloys and Ni/Cu bilayered thin films,
Int. J. Thin Film Sci. Technol. 4 (2) (2015) 75–82, http://dx.doi.org/10.12785/
ijtfst/040203.
[48] A.F. Mayadas, M. Shatzkes, Electrical-resistivity model for polycrystalline
films: the case of arbitrary reflection at external surfaces, Phys. Rev. B 1 (4)
(1970) 1382–1389, http://dx.doi.org/10.1103/PhysRevB.1.1382.
[49] G. Pharr, W. Oliver, Measurement of thin film mechanical properties using
nanoindentation, MRS Bull. 17 (7) (1992) 28–33, http://dx.doi.org/10.1557/
S0883769400041634.
[50] D.J. Shuman, A.L. Costa, M.S. Andrade, Calculating the elastic modulus from
nanoindentation and microindentation reload curves, Mater. Charact. 58 (4)
(2007) 380–389, http://dx.doi.org/10.1016/j.matchar.2006.06.005.
[51] W. K”Oster, H. Franz, Poisson’s ratio for metals and alloys, Metall. Rev.
6 (1) (1961) 1–56, http://dx.doi.org/10.1179/mtlr.1961.6.1.1.
[52] G.G. Stoney, The tension of metallic films deposited by electrolysis, Proc. R.
Soc. Lond. Ser. A: Contain. Pap. A: Math. Phys. Charact. 82 (553) (1909)
172–175, http://dx.doi.org/10.1098/rspa.1909.0021.
[53] W.D. Sylwestrowicz, Mechanical properties of single crystals of silicon, Philos.
Mag. 7 (83) (1962) 1825–1845, http://dx.doi.org/10.1080/
14786436208213849.
[54] J.J. Wortman, R.A. Evans, Young’s modulus, shear modulus, and Poisson’s ratio
in silicon and germanium, J. Appl. Phys. 36 (1) (1965) 153–156, http://dx.doi.
org/10.1063/1.1713863.
[55] W. Fang, C.Y. Lo, On the thermal expansion coefficients of thin films, Sens.
Actuators A: Phys. 84 (3) (2000) 310–314, http://dx.doi.org/10.1016/S0924-
4247(00)00311-3.
M.S. Al Farisi, T. Tsukamoto and S. Tanaka Sensors and Actuators A 316 (2020) 112384

Biographies
Shuji Tanaka received B.E., M.E. and Dr.E. degrees in
mechanical engineering from The University of Tokyo
in 1994, 1996 and 1999, respectively. He was Research
Muhammad Salman Al Farisi received his B.E. in mechan- Associate at Department of Mechatronics and Precision
ical engineering and M.E. in robotics from Tohoku Engineering, Tohoku University from 1999 to 2001, Assis-
University in 2016 and 2018, respectively. He is currently tant Professor from 2001 to 2003, and Associate Professor
a graduate student and a research fellow of Japan Soci- at Department of Nanomechanics from 2003 to 2013.
ety for the Promotion of Science (JSPS) at the Department He is currently Professor at Department of Robotics and
of Robotics, Graduate School of Engineering, Tohoku Uni- Micro System Integration Center (␮ SIC). He was also Fel-
versity. He is also concurrently a graduate student at the low of Center for Research and Development Strategy,
Inter-Graduate School Doctoral Degree Program on Sci- Japan Science and Technology Agency from 2004 to 2006,
ence for Global Safety, Leading Graduate School, Tohoku and is currently Selected Fellow. He was honored with
University. His research interests include the devel- many awards and prizes including The Young Scientists’
opment of micro-electro mechanical systems (MEMS), Prize, The Commendation for Science and Technology by the Minister of Educa-
MEMS materials, heterogeneous device integration and tion, Culture, Sports, Science and Technology (2009) and German Innovation Award,
packaging technologies. Gottfried Wagener Prize (2012). His research interest is industry-relevant MEMS
technology including MEMS sensors, MEMS packaging and integration, acoustic
wave devices, and piezoelectric devices and materials.
Takashiro Tsukamoto received his M. Eng. degree in
2002 in thermal engineering from Tokyo Institute of
Technology. He received M. Eng. degree in 2009 in micro-
electromechanical systems from Tohoku University. He
received his Dr. Eng. degree from Tohoku University
in 2012. Currently he is an associate professor in the
department of Robotics, Graduate School of Engineering
at Tohoku University. He is a member of the Institute of
Electrical and Electronics Engineers (IEEE), the Institute of
Electrical Engineers of Japan (IEEJ) and the Japan Society
of Mechanical Engineers (JSME). His research interest is
micro thermal devices and MEMS inertial sensors.

10