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DOI: 10.1002/adma.200702006
Ultrathin Wear-Resistant Ionic Liquid Films for Novel
MEMS/NEMS Applications**
By Manuel Palacio and Bharat Bhushan*
Further proliferation of products based on microelectrome-
chanical systems (MEMS) and nanoelectromechanical systems
(NEMS) relies on a better understanding of the various me-
chanisms that control the performance and failure of these
devices. Adhesion, friction and wear at the nanometer size scale
become critical and can be detrimental to the efficiency, power
output and reliability of MEMS/NEMS devices.[1,2] For exam-
ple, adhesion is the major cause of the failure of accelerometers
used in automobile air bag triggering mechanisms[3] and in
micromirror components of commercial digital light processing
(DLP) equipment.[2,47] Wear has been found to compromise
the performance of NEMS-based atomic force microscopy
(AFM) data storage systems.[89] In order to improve tribologi-
cal performance, lubricants are applied to the MEMS/NEMS
device surfaces. The ideal lubricant should be molecularly
thick, easily applied, able to chemically bond to the micro/
nanodevice surface, insensitive to environment, and highly
durable.[1013]
An ionic liquid (IL) is a synthetic salt with a melting point
below 100  C. A room temperature ionic liquid is a synthetic
molten salt with melting points at or below room temperature.
One or both of the ions are organic species. At least one ion has
a delocalized charge such that the formation of a stable crystal
lattice is prevented and the ions are held together by strong
electrostatic forces. As a result of the poor coordination of the
ions, these compounds are liquid below 100  C or even at room
temperature.[14]
Ionic liquids are considered as potential lubricants. Their
strong electrostatic bonding compared to covalently-bonded
fluids, leads to very desirable lubrication properties. They also
possess desirable properties such as negligible volatility, non-
flammability, high thermal stability or high decomposition
temperature, efficient heat transfer properties, low melting
point, broad liquid range, as well as compatibility with lubricant
additives.[1517] Unlike conventional lubricants that are electri-
cally insulating, the cations and anions of the ionic liquid
[*] Prof. B. Bhushan, Dr. M. Palacio
Nanotribology Laboratory for Information Storage and
MEMS/NEMS (NLIM), The Ohio State University
201 W 19th Ave., Columbus, OH 43210 (USA)
E-mail: bhushan.2@osu.edu
[**] The authors gratefully acknowledge Dr. Barbara Kinzig for providing
the ionic liquid samples and Surfaces Research and Applications, Inc.
(Lenexa, KS) for financial support.
1194 2008 WILEY-VCH Verlag GmbH & Co. KGaA,Weinheim
provide a continuous path for charge conduction. Thus, they
can minimize the electrical contact resistance, and conducting
lubricants are needed for various electrical applications.[9]
These liquids can also be used to mitigate arcing, which is a
cause of electrical breakdown in sliding electrical contacts.[18]
In addition, ILs have high thermal conductivity which helps to
dissipate heat during sliding.[19] The use of ionic liquids instead
of hydrocarbon base oils (such as highly reformed mineral oils)
has the potential to dramatically reduce air emissions coming
from by-products of hydrocarbon oxidation. They are being
considered for MEMS/NEMS applications because of their
high temperature stability, electrical conductivity, and superior
lubrication properties.
The durability of ionic liquid films on various metal and
ceramic substrates has been investigated from the standpoint
of film formation (wettability) and film removal (friction and
wear), where it was found that certain cations and anions exhibit
better wetting, friction reduction and wear resistance proper-
ties. In general, ionic liquids exhibit better wettability on noble
metal and ceramic surfaces than on non-noble metal sur-
faces.[20] The flat imidazolium cation shows poorer wettability
compared to bulkier cations such as ammonium and sulfonium.
Among salts with the imidazolium cation, the presence of
longer organic side chains lead to a reduction of the coefficient
of friction.[2122] An anion effect is also observed, where oxy-
gen-rich anions show better substrate wettability and lower
wear compared to other imidazolium salts.[14]
Ionic liquids with the hexafluorophosphate anion have been
evaluated extensively using conventional friction and wear tests
and were found to exhibit improved friction and wear proper-
ties compared to conventional lubricants.[21,2325] The ionic
liquid containing the octyl sulfate anion has been developed
more recently and is of interest due to its resistance to hydroly-
sis.[14] Based on these findings, the ionic liquids of interest in this
study are 1-butyl-3-methylimidazolium hexafluorophosphate
(BMIM-PF6) and 1-butyl-3-methylimidazolium octyl sulfate
(BMIM-OctSO4). Their chemical structures are shown in
Figure 1.The immobilization of the ionic liquid on the silicon
substrate occurs by reaction of the anion with the hydroxyl
groups present on the silicon surface,[26] as shown in Figure 2 for
BMIM-PF6. A similar mechanism is responsible for the attach-
ment of BMIM-OctSO4.
A potential lubricant should exhibit low adhesion, friction
and wear. To date, the friction behavior of materials
coated with ionic liquids is known only at the microscale
from studies using conventional ball-on-disk or pin-on-disk
Adv. Mater. 2008, 20, 11941198

Figure 1. Chemical structures of the BMIM-PF6, BMIM-OctSO4 and Z-
TETRAOL molecules.
tribometers.[16,17,21,22,23,25,27] Adhesion and friction properties
at the microscale can be different from the nanoscale.[28]
Knowledge of the latter is important in optimizing lubrication
of MEMS/NEMS devices. Atomic force microscopy (AFM)
can address this need as it can be configured to measure
adhesion and friction forces at the nanoscale. An AFM tip
sliding on the sample surface simulates a single asperity contact
under light load conditions typically encountered during
MEMS/NEMS operation.
The surface potential, which is one of the electrical properties
that can be measured with an AFM, pertains to the potential
difference between two surfaces as they are brought together in
electrical contact and thermal equilibrium is achieved. Surface
potential mapping is a useful technique for wear detection.
DeVecchio and Bhushan[29] have shown that a surface potential
change is detectable even in cases where there is little or no
surface damage, making this a powerful technique for studying
the initiation of wear. The technique is well suited for wear
studies of MEMS/NEMS device components because it has also
been used for characterizing the wear of metals, ceramics and a
conventional perfluoropolyether (PFPE) lubricant.[30,31] More
recently, the change in surface potential has been used to
demonstrate how the presence of both immobile and mobile
lubricant fractions on a silicon substrate provide enhanced wear
protection compared to substrates containing only the immo-
bile lubricant.[32] It has also been shown that surface potential
measurements can elucidate the mechanism of triboelectric
charging of human hair.[3334]
In this study, AFM-based adhesion, friction and wear mea-
surements are presented for the first time for the ionic liquids of
interest coated on silicon. Untreated coatings are compared
with samples subjected to post thermal treatment (partially
bonded) and also with coatings that had thermal treatment
followed by solvent rinsing to remove mobile lubricant frac-
Figure 2. Schematic for the attachment of BMIM-PF6 to the silicon
substrate.
Adv. Mater. 2008, 20, 11941198 2008 WILEY-VCH Verlag GmbH & Co. KGaA,Weinheim
COMMUNICATION
tions (fully bonded). Lubricant removal and surface wear is
detected using surface potential measurements. These ionic
liquids are compared with a previously known excellent lubri-
cant, the perfluoropolyether (PFPE) Z-TETRAOL, from the
standpoint of adhesion, friction and wear resistance.
Figure 3 shows representative force plots obtained as the tip
approaches and retracts from the surface. The z-displacement
during pull-off is related to the adhesive force. Figure 4a
summarizes the adhesive force and coefficient of friction mea-
surements on the ionic liquids, with Z-TETRAOL and Si (100)
data provided for comparison. The adhesive force decreases in
the following order: untreated > partially bonded > fully bond-
ed. The mobile fraction on the untreated sample facilitates
formation of a meniscus, which increases the AFM tip-sample
adhesion. The adhesive force is highest in the untreated coating
since it has the greatest amount of the mobile fraction among
the three samples. Conversely, the sample with no mobile
lubricant fraction available (fully bonded) has the lowest adhe-
sive force.
A different trend is observed in the coefficient of friction (m)
plot. The partially bonded coatings have the lowest m values of
all the lubricants, implying that the combination of immobile
and mobile lubricants bonded to the substrate by thermal
treatment is the best way to facilitate sliding of the AFM tip
on the surface. The fully bonded coatings only have immobile
lubricant bonded to the substrate surface because the mobile
portion was removed by solvent rinsing, and the lack of mobile
lubricant molecules translates to slightly higher friction forces.
However, m values for the untreated samples are higher than the
m of either the partially or fully bonded coatings. Due to the lack
of chemical bonding, the interaction of the lubricant to the
substrate is weakened and dewetting can occur. Water and
lubricant molecules are more likely to form a meniscus as the tip
approaches the surface. This provides greater resistance to tip
sliding, leading to higher coefficient of friction values. The
schematic in Figure 4a illustrates how the thermal and chemical
treatment (or lack thereof) affects the surface orientation of
lubricant molecules and how this molecular arrangement man-
ifests itself through the measured adhesive and friction forces.
Figure 4b shows the change in the coefficient of friction as a
function of the number of sliding cycles at 70 nN normal load.
Figure 3. Force as a function of tip-sample separation for uncoated and
coated silicon samples.
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Figure 4. (a) Summary of the adhesive force and coefficient of friction and
(b) durability data after 100 cycles for BMIM-PF6 and BMIM-OctSO4 at room
temperature (22  C) and ambient air (4555% RH). Data for the uncoated Si
and Z-TETRAOL are shown for comparison. Schematic in (a) shows the
effect of chemical bonding treatment and meniscus formation between the
AFM tip and sample surface on the adhesive and friction forces.
Only a small rise in the coefficient of friction was observed for
both Z-TETRAOL and the BMIM-PF6 surfaces, indicating low
surface wear. However, all three BMIM-OctSO4 samples ex-
hibited gradual change in m, implying that wear is taking place
after approximately 25 cycles for both the untreated and fully
bonded surfaces and 60 cycles for the partially bonded surface.
In some cases, such as in the fully bonded BMIM-OctSO4 and
the untreated Z-TETRAOL, a crossover is observed, where the
coefficient of friction increases from its initial value and exceeds
the m of silicon after a certain number of cycles. This is attri-
1196 www.advmat.de 2008 WILEY-VCH Verlag GmbH & Co. KGaA,Weinheim
buted to the transfer of lubricant molecules to the AFM tip and
the interaction of the transferred molecules with the lubricant
still attached on the Si substrate, which will increase the friction
force.
A summary of the surface height and the corresponding
surface potential map after wear testing is shown in
Figure 5a. Compared to the uncoated silicon surface, reduction
in the debris is observed in the partially bonded samples. This
indicates that the ionic liquids are providing wear protection.
The pile up of debris observed in the untreated samples could be
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Figure 5. (a) Surface height and surface potential maps after wear tests and
(b) bar chart showing surface potential change for various BMIM-PF6 and
BMIM-OctSO4 coatings. Data for the uncoated Si and Z-TETRAOL are
shown for comparison.
a combination of removed fragments of Si as well as the weakly
bound lubricant. In general, the samples containing the mobile
lubricant fraction (i.e., untreated and partially bonded surfaces)
exhibit a lower surface potential change compared to the fully
Adv. Mater. 2008, 20, 11941198 2008 WILEY-VCH Verlag GmbH & Co. KGaA,Weinheim
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bonded sample, which only has immobile lubricant molecules.
This is attributed to lubricant replenishment by the mobile
fractions, which can occur in the untreated and partially bonded
samples.[32] The average surface potential change on the tested
areas is summarized in Figure 5b. From the plot, it can be
observed that the small change in surface potential is generally
lower in the ionic liquid coatings compared to the Z-TETRA-
OL coatings and the uncoated silicon. This indicates that any
built-up surface charges arising from the wear test were imme-
diately dissipated onto the ionic lubricant surface. In the case of
Z-TETRAOL and the uncoated silicon with its native oxide,
the charges remained trapped in the test area, since these
materials are insulators. Based on these findings and previous
observations,[30][32][33] a considerable surface potential change
will be observed on the wear region when: (1) the lubricant has
been fully removed from the substrate; (2) the native SiO2 layer
has been abraded from the surface; (3) wear has caused sub-
surface structural changes; (4) charges build up as they are
unable to dissipate into the surrounding material.
From the nanoscale adhesion, friction and wear studies on the
ionic liquids BMIM-PF6 and BMIM-OctSO4, the following
conclusions can be drawn. All of the chemically treated
lubricant-coated samples show favorable lubrication, as seen
from the adhesive force and coefficient of friction being less
than that of uncoated silicon in all cases. Ionic liquids have
comparable coefficient of friction with the conventional lubri-
cant Z-TETRAOL. The partially bonded coatings have the
lowest coefficient of friction as they possess a desirable combi-
nation of lubricant bonded to the substrate as well as a mobile
fraction which facilitates tip sliding. All lubricants show favor-
able durability, with the partially bonded lubricant showing the
best characteristics. By configuring the AFM as a nano-Kelvin
probe, surface potential maps of the coated surfaces were
obtained after wear testing. The low post-wear surface potential
change observed on the silicon coated with ionic liquids is
indicative of enhanced charge dissipation compared to the
Z-TETRAOL-coated and uncoated surfaces, which are insu-
lating. Due to their low friction, wear resistance and favorable
charge dissipation properties, ionic liquids show strong poten-
tial as lubricants for MEMS/NEMS.
Experimental
The room temperature ionic liquids used in this study are 1-butyl-3-
methylimidazolium hexafluorophosphate, BMIM-PF6 (Merck, Darm-
stadt, Germany) and 1-butyl-3-methylimidazolium octyl sulfate,
BMIM-OctSO4 (Merck, Darmstadt, Germany). The performance of
these ionic liquids is compared with the perfluoropolyether (PFPE)
lubricant Z-TETRAOL (Solvay Solexis Inc.). The substrate used was
single-crystal Si(100) (10 10 0.5 mm3) with a native oxide layer on the
surface.[11,12] The wafer cleaning was undertaken by ultrasonicating in
acetone followed by isopropanol for 10 min each. Then, the cut wafer
was dip coated into a beaker containing a dilute solution of the lubricant
and withdrawn after 10 min. The solutions of the various lubricants are
0.2% (v/v) BMIM-PF6 in isopropanol, 0.2% (v/v) BMIM-OctSO4 in
isopropanol and 0.1% (v/v) Z-TETRAOL in HFE 7100 (a solvent
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consisting of isomers of methoxynonafluorobutane (C4F9OCH3)). Un-
treated samples did not undergo further thermal and chemical treat-
ment. Partially bonded samples were prepared by heating at 150  C for
30 min after dip coating, while the fully bonded samples were heated at
150  C for 30 min and washed in isopropanol (HFE 7100 in the case of Z-
TETRAOL) to remove the mobile fraction. The coating thickness was
found to be about 0.5 nm, 1.5 and 2.5 nm for the fully bonded, partially
bonded and untreated ionic liquid samples, respectively. Since ionic
liquids do not have polar end groups (as compared to Z-TETRAOL),
chemical bonding of the lubricant to Si is not obvious. However, it
appears that thermal treatment leads to bonding of the ionic liquid
because some coating is left after washing with isopropanol.[35] Mean-
while, the thickness of the Z-TETRAOL coatings was about 1, 3 and 7
nm for the fully bonded, partially bonded and untreated samples,
respectively.
Adhesion and friction experiments at the nanoscale were carried out
using a commercial Nanoscope IIIa MultiMode AFM (Veeco Instru-
ments, Santa Barbara, CA) in ambient conditions (22  C, 4555% RH)
using Si3N4 tips with a nominal 3050 nm radius mounted on triangular
Si3N4 cantilevers with a spring constant of 0.58 N m 1 as reported by the
manufacturer. The adhesion experiment was performed by pushing the
tip by about 50 nm into the sample. The adhesive force was determined
from the force plots by measuring the amount of tip-sample separation
during tip retraction multiplied by the spring constant. The friction force
was calibrated by the method described by Bhushan.[28] Briefly, the
trace minus retrace (TMR) value is recorded as a function of increasing
setpoint. The TMR is converted into the friction force by a calibration
technique. The first wear test is based on an established procedure
where the friction force was monitored as a function of the number of
sliding cycles.[11] The wear test used for the ensuing surface potential
measurements is as follows. The lubricated surfaces were worn using a
diamond tip with an apex angle of 60 and a tip radius of approximately
100 nm attached to a stainless steel cantilever. Wear scars with dimen-
sions of 5 5 mm2 were created and scanned for 20 cycles at a load of 10
mN. This experiment was performed for the untreated, partially bonded
and fully bonded lubricant samples. Surface potential measurements
were taken with the Nanoscope IIIa MultiMode AFM in lift mode at a
tip-sample separation of 10 nm. Electrically conductive silicon tips
coated with cobalt/chrome (MESP probes) were used.[29]
Received: August 10, 2007
Revised: October 19, 2007
Published online:
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